Loading...
HomeMy WebLinkAboutNC0000272_Color Reduction Plan Trial Docs_20120201 i Process Trial Documents cited in Update to the Color Reduction Implementation Plan — February 2012 Attached in order cited Evergreen 2011 — Annual Progress Report on Color, submitted to NC DWQ to meet requirements of Part I A.(8) item 8 of the May 2010 NPDES Permit, Evergreen Packaging Canton Mill, July 1, 2011. Adams 2002a — Blue Ridge Paper Products - Canton Mill — Trial Report — Hydrogen Peroxide (H2O2) on Hardwood Eo Stage, Bill Adams Process Engineer, Blue Ridge Paper Products Inc. Canton Mill, July 2, 2002. Adams 2002b — Blue Ridge Paper Products - Canton Mill — Process History Report — D-100 Kappa Factors Performance / Monitoring, Bill Adams Process Engineer, Blue Ridge Paper Products Inc. Canton Mill, July 10, 2002. Miller 2011 — H2O2 Hardwood and Pine Bleaching Trial Results, internal technical memo, Bill Miller, process engineer for Evergreen Packaging, January 24, 2012. McCracken 2011 — Statistical Overview of Peroxide Application on Softwood and Hardwood Fiberlines for Color at Canton Mill, P Qtr 2011, internal data evaluation prepared by Nick McCracken and the Canton Mill Color Team for Evergreen Packaging, December 2011. PITC 201 lb — Report 2011-054 — Evergreen Packaging Bleaching, Canton NC, Pruyn's Island Technical Center, August 3, 2011. McDonough 2011 - Laboratory Study of Likely Effects of Oxidatively Intensifying the Extraction States at Evergreen Packaging's Canton, NC Mill, Progress Report (DRAFT), Thomas J. McDonough, consultant to Evergreen Packaging, February 10, 2012. PITC 2001 — Report 2001-068, Part 1 —Laboratory CK and Lo-Solids Cooking with O-Do-Eop- D Bleaching Sequences on Softwood Furnish from Blue Ridge Paper, Part I —Softwood Results, Pruyn's Island Technical Center, December 6, 2001. PITC 2011 a— Report 2010-081 —Laboratory Cooking and Bleaching for Evergreen Packaging Canton,NC, Pruyn's Island Technical Center, January 31, 2011. McDonough 2011 — Laboratory Study of Likely Effects of Installing Two-Stage Oxygen Delignification at Evergreen Packaging's Canton, NC Mill, Thomas J. McDonough, consultant to Evergreen Packaging, June 29, 2011. FEB 2 2 2012 e July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 I. Introduction Part I A.(8.) item 8 of the May 2010 NPDES Permit states — The facility will provide annual progress reports to the Division on the color reduction efforts. This report fulfills the requirements of Part I A.(8.) item 8. Specifically, the report documents projects and best management practice (BMP) refinements completed by the Canton Mill Color Team during the period May 2006 through May 2011. The Color Team continued work on color performance improvement including several recommendations incorporated into the final permit between the May 2006 application and May 2010 NPDES permit renewal. II. Background Levels of color in the wastewater effluent from the Canton Mill are among the best of Kraft pulp and paper mills in the world [EKONO August 2005, NCASI August 2006]. This high level of color performance is achieved by in-process controls and best management practices. The mill will continue to operate the controls and practices proven successful for color prevention. These controls and practices go well beyond the' requirements of the EPA Cluster Rule for Pulp and Paper (40 CFR 430, Subpart B). Many, such as the Bleach Filtrate Recycling ProcessTM, are unique to the Canton Mill. The May 2010 NPDES permit includes a daily maximum effluent true color limit of 105,250 lbs per day. The permit also specifies a monthly average true color limit of 52,000 lbs per day and an annual average (calendar year) true color limit of 38,020 lbs Page 1 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No. NC0000272 per day. Compliance with these effluent limits requires significant management of mill operations related to color. Prevention of wastewater effluent color is a priority for mill operations every day. III. Color Performance Figure 1 illustrates the color performance of the Canton Mill since 1997. The mill has sustained and continued the color reductions achieved under the 1997 and 2001 NPDES permits. Annual average effluent true color in Figure 1 is presented in units of 1000 Ibs per day. The calculation of effluent color as a daily mass (lbs) is defined in Part I A.(8.) items 2&3 of the permit: color (lbs/day) = effluent flow (mgd) x effluent true color (platinum cobalt units) x 8.34. Effluent true color is measured using NCASI method 253 (1971). Figure 1 - Annual Average Effluent Color Blue Ridge Paper Canton Mill, 1997 thru 2010 70 a 62.2 BFR & Cluster Rule s 60 Color Improvement SO 47.8 C 3.4 44.6 — 41.1 4 42.7 41.2 39.7 39.1 37.1 . 37.8. 40 -- -- - - - 36.1 36.5 35.8 0 0 U 30 c 20 w obA o° C o° o� Zb o° o`' 06 °� °Cb o° '�° �° �° KZ �yo �yo° rp ryo ,yo �yo �o go �yo ,yo ,yo Page 2 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 The best color performance of the Canton Mill occurs during normal, or full, production. At normal production, the internal recycling and recovery of process filtrates, pulping liquors and other process wastewaters are balanced. Color materials are contained within the Kraft pulping process at efficiency greater than 99 percent. Color performance is affected by process variability. Color materials can be lost during startup and shutdown associated with a process upset, production curtailment or unplanned outage. Because of both economic impact and adverse affect on color performance, the mill has strong incentive to maintain process reliability and operate at normal production level. Effluent color early in 2009 was affected by weak product demand related to the 2008 Financial Crisis and global recession that resulted in a lower overall rate of mill production. Additionally, there was an unplanned pulp mill outage and color event in September 2009 associated with a recovery furnace tube failure that required emergency, life safety shutdown of the No. 10 Recovery Furnace. That single, unplanned outage event added more than 1000 lbs per day to the 2009. annual average effluent color. Effluent color at the end of 2009 and during the winter of 2010 was affected by extended cold wet weather and regional wood supply shortages that resulted in lower than normal rates of pulp production. Page 3 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 IV. Color Proiects and Refinements to Best Management Practices The Canton Mill has a standing Color Team that routinely meets to review color performance. The Color Team members include managers, supervisors and engineers involved with production, maintenance, wastewater treatment and regulatory affairs. The Color Team scope includes: • Monitor color performance and the effectiveness of mill systems to prevent effluent color • Identify and track corrective actions related to Cluster Rule BMP color events • Plan and review process trials related to effluent color • Plan and review the effectiveness of capital and expense projects related to effluent color The Color Team is continuously evaluating projects, trials and process initiatives. Not all of these are successful. Significant Color Team activities between 2001 and 2005 are documented in the May 2006 Color Compliance Report [BRPPI May 2006]. Significant activities from May 2006 through May 2011 are outlined in Tables 1 and 2. Capital projects in Table 1 are identified by Capital Improvement Project (CIP) number. Other projects were completed on operations and maintenance expense. Direct spending on Color Team related projects, trials and initiatives identified in Tables I and 2 during the period May 2006 through May 2011 exceed $ 3.0 MM capital and expense These costs are in addition to the on-going cost to operate and maintain color prevention systems at the Canton Mill. Page 4 July 1, 2011 — Annual Progress Report on Color Blue:Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 Table 1 Color Team Capital and Maintenance Projects 2006 - 2011 Year Project Description and Cost Information for Capital Projects 2006 Check valve installed in the#11 Recovery Boiler sump pump line. This prevents collected color materials from being inadvertently pumped into the CRP Feed Tank instead of the Wash Water Tank for.processing through the Evaporators. BMP improvement. o Completed November 2006, cnsd* 2007 Continued 4th stage hardwood BSW shower replacement begun in 2005. These shower bars were installed to improve washing and reduce carry-over into the bleach plant. Liebergott Recommendation. o Completed during 2007 Hwd semi-annual outage o CIP - 230014 o Cost- $90,000 CRP sump installation and controls. This sump was installed to contain color material event releases from the CRP system building. Also allows collection of color material related to CRP maintenance boil out. BMP improvement related to 2006 and 2007 color events. o Completed December 2007 o CIP - 218675 o Cost- $164,000 Piping to collect Sarco Strainer washes directly to Wash Water Tank instead of through sump area. Manual system of piping and valves. BMP improvement. o Completed in December 2007 o CIP -232234 o Cost- $64,000 High level interlocks on CRP slurry tank. High-level indicator shuts the#11 Recovery Boiler sump gate and the CRP sewer gate exiting the building. This allows material to be picked up in the sump if any overflows. BMP improvement related to 2007 color event. o Completed September 2007, cnsd* Page 5 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No. NC0000272 Table 1 Color Team Capital and Maintenance Projects 2006 - 2011 Year Project Description and Cost Information for Capital Projects 2007 Mini-Hoods on No. 10 Smelt Dissolving Tank(SMDT). Allows substitution of weak wash for clean water in SMDT demister creating more process demand for weak wash and reducing high pH material discharged to sewer. Related to TRW Recommendations regarding prevention of sewer-generated color—high pH. o Completed 2Q 2007, cnsd* Created audible alarms for mill sewers in the DCS for WWTP. Allows WWTP operators to locate potential elevated color streams in the mill sewers and contact specific areas of the mill.. BMP improvement. o Completed 2007, cnsd* 2008 Dregs filter feed improvements to improve reliability and reduce frequency of dregs sewering/overflow. Includes pipe separation, new lines and pump upgrades. Related to TRW Recommendations regarding prevention of sewer generated color—sulfide materials and high pH. o Completed in 2Q of 2008 o CIP - 232333 o Cost- $200,000 Creation of sample point inside CRP building to monitor color loading to mill sewer. This point is being used to monitor operations, in regards to color,within the CRP system. BMP improvement. o Completed 2008, cnsd* Determine CRP boil out strategy. Study included taking boil out water samples at periodic intervals to determine color load to mill sewer. BMP improvement possible with CRP recovery sump completed in 2007. o Completed 2008, cnsd* New set points for digester hog line conductivity probe. Better detection of digester liquor heater leaks and better process data for monitoring liquor heater failures. BMP improvement. o Completed March 2008, cnsd* Page 6 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No. NC0000272 Table 1 Color Team Capital and Maintenance Projects 2006 -2011 Year Project Description and Cost Information for Capital Projects 2009 Remote activation of shutoff valves on firewater quench to#11 Recovery Boiler cyclones during Emergency Shutdown Procedure (ESP). This mitigates potential volume of high color material.from cyclone overflow during an ESP. BMP improvement related to Sep 2009 color event. o Identified in 4Q 2009 o Completed on No. 11 Recovery Furnace 3Q 2010, cnsd* o Completed on No. 10 Recovery Furnace 2Q 2011, cnsd* Curbing around East Camp Branch color material storage tank, pumps and transfer piping. This is a proactive measure to segregate and prevent losses of high color material to the#4 sewer. BMP improvement. o Completed in 2009 o CIP -239011 o Cost—portion of$128,000 Installation of separate sump and conductivity meter for East Camp Branch tank, pumps and transfer piping. The sump and meter allow any losses from the East Tank to be monitored and contained before entering the#4 sewer. BMP improvement. - o Completed in 2009 o CIP - 239011 o Cost—portion of$128,000 Installation of 120 ft of concrete barrier around East Heavy Liquor Tank. BMP improvement in the Recovery area. BMP improvement. o Completed in 2009 o CIP—264956 o Cost- $20,000 Replacement of section (250 ft) of Wash Water line running from evaporators to Wash Water Tank. This is a proactive measure to prevent losses from this transfer line. BMP improvement. o Completed in 2009 o CIP—292829 o Cost—portion of$160,000 Page 7 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 Table 1 Color Team Capital and Maintenance Projects 2006 - 2011 Year Project Description and Cost Information for Capital Projects 2009 New flow meter at Evaporator area South Sump. Meter allows operators to determine if the sump is picking up any losses from the Evaporator area. BMP improvement. o Completed March 2009, cnsd* Level transmitter for Lime Kiln Sample Collection Tank put into DCS. Allows an operator to monitor tank level to prevent overflows of high pH material to the sewer and reduce the Sewer Generated Color phenomena. Related to TRW Recommendations regarding prevention of sewer generated color—high pH. o Completed 2009, cnsd* Manual back to Automatic on sumps. Sump indications now turn red and alert operators that they are in manual mode on DCS screens. BMP improvement related to color event. o Completed January 2009, cnsd* Replaced pump in the Evaporator area South Sump with a different style pump for increased reliability. New pump is a submersible type. BMP improvement related to color event. o Completed 2009, cnsd* Modified process lines and equipment on 5`h effect of Swenson evaporators to allow on-the-run cleaning. BMP improvement for process reliability to avoid carryover of color material into condensate systems. Reduces the volume of color material generated by evaporator boil out during outages. Color material carry over from evaporators into condensates is related to TRW Recommendations to prevent sewer-generated color. o Completed 3Q 2009, cnsd* Replaced slide rails and gates for isolating primary clarifiers at the Primary Influent Headbox at the WWTP. New gates are faster and easier for WWTP operators to divert high color material to the spare primary clarifier for capture,batch treatment and attenuation. BMP sustaining measure and improvement. o Completed December 2009 o CIP—287478 o Cost—$265,000 Page 8 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 Table 1 Color Team Capital and Maintenance Projects 2006 - 2011 Year Project Description and Cost Information for Capital Projects 2010 East Heavy/Tall Oil Sump transfer line repair..This was a proactive measure to prevent color material losses from this transfer line. BMP sustaining measure. o Completed August 2010, cnsd* Replaced decant line from Turpentine loading to 4A manhole: This is a proactive measure to prevent losses from this transfer line. BMP sustaining measure. o Completed 2010 o CIP—315223 o Cost- $275,000 Repair and recoating of west side of Camp Branch compound. Project to maintain integrity of spill containment. BMP sustaining measure. o Completed 2010 o CIP—315588 o Cost- $235,000 Several black liquor transfer line replacements including East Heavy storage tank and West GB Discharge. BMP sustaining measure. o Completed 2010, cnsd* Replaced conductivity and level switches in East Heavy compound with new, more reliable type. BMP improvement. o Completed 3Q 2010, cnsd* Relocation of sewer conductivity meter below Digester Area sumps. BMP optimization in this area. o Completed November 2010, cnsd* Red Liquor Tank shell replacement/repairs. BMP sustaining measure. o Completed May 2010 o CIP— 266446 o Cost—$265,000 Page 9 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 Table 1 Color Team Capital and Maintenance Projects 2006 - 2011 Year Project Description and Cost Information for Capital Projects 2010 Mini-Hoods on No. 11 Smelt Dissolving Tank(SMDT). Allows substitution of weak wash for clean water in SNOT demister creating more process demand for weak wash and reducing high pH material discharged to sewer. Related to TRW Recommendations regarding prevention of sewer-generated color—high pH. o Completed 3Q 2010, cnsd* North White Liquor Tank shell replacement/repairs. BMP sustaining measure and project related to TRW Recommendations regarding prevention of sewer-generated color—high pH white liquor. o Completed Dec 2010 o CIP—322435 o Cost—$724,000 2011 Process lines to allow front-end boil out of West GB Evaporator. Allows more frequent, less intense evaporator cleaning. BMP improvement for process reliability to avoid carryover of color material into condensate systems. Reduces the volume of color material generated by evaporator boil out during outages. Color material carry over from evaporators into condensates is related to TRW Recommendations to prevent sewer-generated color. o Completed May 2011, cnsd* Repaired drain valves on No. 2 and 3 Primary Clarifiers. Allows isolation of one of these larger volume clarifiers as the spare clarifier for high color material diversion during semi-annual outages. BMP sustaining measure. o Completed March 2011, cnsd* Pine Weak Liquor Tank shell replacement/repairs. BMP sustaining measure. o Completed May 2011 o CIP— 331985 o Cost—$349,000 *cnsd—cost not separately determined, completed on operations and maintenance expense Page 10 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 Table 2 Color Team BMP Refinements, Trials and Process Improvements 2006 - 2011 Years Refinement,Trial and/or Improvement 2006. Liebergott Process Improvements on-going o Improve performance of vacuum washers o Evaluate the elimination of wash water bypass on 151 decker shower o Evaluate the elimination of bypass of Eo filtrate to decker filtrate tank o Improve performance of decker showers on Pine 2007 Metso Project and Training o Shared savings program o CLOZ use study to have a lower Kappa factor, knowledge carried forward 2007 Strategy change in Hardwood Pre-bleach on showers. Original strategy was on-going to wash better with chance of overflows. Now manage to prevent those overflows. 2007 Thoroughly clean and jet lines and hardwood washer screens during each on-going scheduled outage. 2007 More extensive jetting/cleaning in fiberlines during semi-annual outages. on-going 2008 MRP improvements/time scheduled maintenance and operator rounds to on-going increase reliability. 2008 CRP boil out strategy. Amount of time boil out material is picked up. on-going Possible with CRP sump project completed in 2007. 2008 Use membrane caustic�with lower chloride concentration. Helps overall on-going efficiency of BFR system. 2009 Optimize use of polyamine for black liquor color in primary treatment during on-going color events. Batch treatment, as well as short period continuous use when influent is affected by black liquor. 2009 Swenson 5 effect spray bar strategy. Ability to clean evaporator on-the-run. on-going Improves process reliability and reduces volume of color material to recover during outages. 2010 Weak wash purge strategy to minimize potential sewer-generated color on-going during process upset, outage or reduced pulp mill production when demand for weak wash is out of balance with supply in causticizin . 2011 When both fiberlines are down,process contents of one of the spill tanks through the evaporators to free up spill tank volume before starting up. Page 11 July 1, 2011 — Annual.Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No. NC0000272 Table 2 Color Team BMP Refinements, Trials and Process Improvements 2006 - 2011 Year(s) Refinement, Trial and/or Improvement 2011 Alternative polymer study by Chemtreat at WWTP. Compared against current polyamine polymer in use for batch treatment of black color materials. No difference in color performance. 2011 West'GB Evaporator partial boil out strategy. Ability to clean process during on-going short outages as opportunities arise. Improves process reliability and reduces volume of color material to recover during outages. Several of the projects and process improvements listed in Tables 1 and 2 are related to 2006 Liebergott recommendations for existing process optimization [GL&V 2006]. These include projects for brown stock washing improvement and target pulp bleach Kappa factor. Other projects and improvements are related to sewer-generated color and polymer use optimization, which are Technology Review Workgroup (TRW) evaluation recommendations in Part I A.(8.) item 103-of the May 2010 NPDES Permit. The complete application to renew the NPDES permit was submitted by the Canton Mill in May 2006. The permit renewal process including review by the TRW, public comment and public hearings was completed in May 2010. During this time, the Canton Mill Color Team continued work on color performance improvement including several recommendations incorporated into the final permit. V. Summary Of the many color improvement initiatives evaluated and implemented at the Canton Mill, the following are essential to current(2011) effluent color performance: Page 12 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 • OD 100TM process — oxygen delignification, elemental chlorine-free (ECF) bleaching and enhanced fiberline brown stock washing • Bleach Filtrate Recyclinim (BFR) with the Minerals Removal Process (MRP) and the Chlorine Removal Process (CRP) • Cluster Rule Best Management Practices (BMP) program with color as the BMP monitoring parameter to detect process upsets and the loss of pulping liquors to the mill sewer system • Extensive sumps and systems to detect pulping liquor losses to capture and recover color materials within the pulp mill process • Spare primary clarifier maintained to capture, treat and attenuate high concentration color materials that may exceed capacity of the in-process sump and spill detection systems - • Mechanical seals on pumps in digester and knotter areas to minimize dilution of color materials that prevents efficient recovery • Interconnection of process spill sumps and equipment to increase the working volume for recovery of color materials during process upsets and outages • Segregation of black liquor from green and white liquor to avoid contamination that prevents recovery of black liquor materials ' • Segregation of bleach plant filtrates from high pH conditions in mill sewers to reduce sewer-generated color Page 13 July 1, 2011 — Annual Progress Report on Color Blue Ridge Paper Products Inc. dba Evergreen Packaging Canton,North Carolina NPDES Permit No.NC0000272 • Management of high pH materials when process filtrates are out of balance due to process upset or reduced pulp mill production • Outage cleaning of pulp washers and evaporators to maintain performance and reduce carry-over of color materials into bleach plants and into condensate systems • Low Flow Contingency Plan for Color [Evergreen 2011] and priority given to color management every day. The Canton Mill will continue to utilize the processes and practices proven successful for wastewater effluent color prevention. Prevention of effluent color is a priority for mill operations every day. References EKONO — Environmental Performance, Regulations and Technologies in the Pulp and Paper Industry, EKONO Inc,August 2005. NCASI—Technical Bulletin No. 919—Review of Color Control Technologies and Their Applicability to Modern Kraft Pulp and Paper Mill, National Council for Air and Stream Improvement, August 2006. BRPPI — Color Compliance Report prepared to fulfill requirements of the December 2001 NPDES Permit for the Canton Mill, Blue Ridge Paper Products Inc., May 2006. GL&V — Bleach Environmental Process Evaluation and Report prepared for Blue Ridge Paper Products Inc., Canton Mill,Norman Liebergott and Lewis Shackford, July 2006. Evergreen — Low Flow Contingency Plan for Color, submitted to NC DWQ on 26 May 2011 to meet requirements of Part I A.(8) item 12 of the May 2010 NPDES Permit, May 2011. Page 14 J Y , Blue Ridge Paper Products, Inc. - Trial Report Hydrogen Peroxide(H2O2) on Hardwood Eo Stage - MTA #402230 TO: Michael Ferguson . DATE: July 2, 2002 Fibedine Superintendent FROM: Bill Adams SUB: Apply H2O2 to HW Eo Stage Principal Process Engineer Background Summary: Per N.Liebergott of Liebergott&Associates, Inc. and L.Shackford &W.Miller of GL&V, in their"Bleach Environmental Process Evaluation and Report"dated June 8, 2001, a recommendation was made to run a trial in which hydrogen peroxide (H2O2) is applied to the Hardwood Eo stage. The recommendation for this trial was further included in Canton's 2001 NPDES Compliance Action List for October 1, 2003 Report. Several previous attempts have been made to use H2O2 on the Hardwood Eo stage to replace some C102 applied to the"D"stages. These attempts have had limited success. Generally,the conclusion has been that the presence of Non-Process Elements (NPE's) in the pulp react with the H2O2 to form radicals which do not brighten the pulp and can cause a reduction of pulp strength as measured by pulp viscosity. The H2O2 application point was relocated for this trial from the stock line between the thick stock pump (TSP) and chemical mixer to a port on the chemical mixer. This move was considered the best available application point for H2O.2 on Canton's HW Eo system. A trial was planned for 2002 in two parts: Part I would apply H2O2 to the HW Eo stage at the rate of about 6 WAD Ton while providing data with which to further optimize the bleach plant; Part II would apply H2O2 at about 6 WAD Ton under conditions that would best demonstrate the effectiveness of H2O2 on HW Eo. The two parts of the trial occurred before and after the HW Annual Outage, respectively.Total bleach application was identified as an important factor in the trial work as well as sewer color, bleaching costs, and pulp quality. To be considered successful, an equivalent amount of 0102 had to be removed to the amount of H2O2 applied, on a chemical cost basis. Atofina supplies the mill's H2O2 and was requested to update their pricing for H2O2 for this trial. Atofina chose to lower their H2O2 price to match the mill's standard C102 cost. This meant that for every pound of H2O2 applied, a pound of C102 must be removed in order to break even. A lower H2O2 price would have meant that less C102 must be removed for the amount of H2O2 applied. Data from The PQ Corporation indicates a significant improvement in H2O2 performance with the addition of MgSO4.As part of the trial, a"check trial"was planned in which one (1)tote-bin of MgSO4 would be applied to the HW Eo stage in addition to the H2O2. If successful,further trial work would be needed to demonstrate whether MgSO4 application with H2O2 could be made cost effectively. Bill Adams (828) 646-2868 402230 H2O2 on HW As Page 1 7/9/02 ' Blue Ridge Paper:Products, Inc. - Trial Report :! Hydrogen Peroxide (H202) on Hardwood Eo Stage - MTA#402230 Priorto starting this trial,the Hardwood fiberline bleaching operation was optimized by the adjustment of the D- 100 stage pH and by the reduction of Oxygen (02) application to the Eo stage. Results from the optimization projects are reported separately. For comparison,data is included in the Data Summary from several consecutive years, at about the same time of year that the trial work was performed. During the data set for 1998, H202 was being applied to the HW Eo stage. Data from the most recent two (2) months prior to the trial (3/1/02 thru 5112102) and post-trial data are available for comparison of recent data. The Data Summary summarizes these groups of data plus the two trial parts and Post Trial data. Trial Summary: Part I of the trial was begun on 5/13/02 by beginning H202 application to the HW Eo mixer at about 6 Ibs/AD Ton. Application rate was based on recommendations by Atofina, Canton's H202 supplier. Control is effected by the DCS system based on an application set point input by the operator. During this phase of the trial, H2O2 was applied at the rate of 5.8 WAD Ton. There were no issues involving the H202 system during this phase of the trial. Based on the performance of the HW bleach plant during Part I, it was recommended that the lower limit for ' C102 application on the D-100 stage be moved from 0.65%to 0.55%, allowing a lower D-100 brightness to be maintained. A temporary set of operating guidelines was developed for Part 11 of the trial-scheduled after the HW Annual Outage. Part 11 of the trial was begun on 6/3/02 by continuing H202 application to the Hardwood Eo mixer at about 6 WAD Ton. Control is effected by the DCS system based on an application set point input by the operator. During this phase of the trial, H2O2 was applied at the rate of 5.7 WAD Ton. There was an operational issue involving the H202 system during this phase of the trial when the H202 solution transfer pump to the Eo mixer failed. Data are excluded from the summary during the pump failure. Part 11 of the trial was completed on 6/19102 after MgSO4 was applied to the HW D-100 washer repulper to enhance H202 performance. To evaluate any effect the trial work might have had on sewer color,data from 2001 was collected, obvious out- liers discarded, averaged and the standard deviations calculated. These data are included in the Data Summary. Also attached are charts showing average colors,.average+/-1 Standard Deviation, and trial averages for the most pertinent sewer colors. Conclusion: No changes in C102 application were observed. The Hardwood fiberline was operated in a normal manner with the earlier noted exception of the D-100 stage optimization work(primarily limiting D-100 brightness to about 63 ' ISO). Chemical demands were comparable to previous data periods. H202 application was ineffective and is not cost effective. Bill Adams (828) 646-2868 402230 H2O2 on HW.xls Page 2 7/9/02 Blue Ridge Paper Products, Inc. - Trial Report Hydrogen Peroxide (H202) on Hardwood Eo Stage - MTA#402230 Non-process elements (NPE's) exist on Canton's fiberlines due to the degree of"closure"and water recirculation. NPE's react preferentially with H2O2 to form radicals,which, in turn, attack the carbohydrates in the pulp. As a result, H2O2 is exhausted before brightening can occur and pulp strength (as measured by viscosity)can be lost. There were no cost savings from this trial. In fact,the data suggest a cost increase of about$697,000 per year with the application of H2O2 on HW Eo. Added H2O2 costs are about$620,000 per year,the balance is primarily added C102 costs. Actual trial cost was$45,000 in direct H2O2 cost. In evaluating any changes to sewer color numbers, a great many factors may be affecting sewer colors at any given time, including pH's,specific streams and flows, temperatures,the presence (or absence) of active calcium ions, etc. To be confident that a change might have had a direct effect on sewer color, a change should occur that is no less than one (1)standard deviation from average;three.(3) standard deviations would increase confidence to over 95%_ None of the measured color data shows a greater than one(1)standards deviation change from 2001 averages. Therefore, it cannot be concluded that this trial had an effect on sewer color. Recommendations: Recommend NOT using hydrogen peroxide on the hardwood Eo stage at moderate application rates (up to 10 lb/Ton) except in cases of emergency or other extenuating reasons. Recommend revising the D-100 stage lower C102 application limit upward from 0.55 to 0.60. The recommended rate of 0.60 is less than the beginning minimum of 0.65. Hexenuronic Acids: Hexenuronsc Acids(Hex-A)are chemical groups that originate from hemicellulose, but chemically react more like lignin. They form during the Kraft cook from certain acid groups in Xylans. Hex-A raises"PW or"K" numbers, but Hex A does not darken the pulp. Hexenuronic acid was first described in publications in 1996. Direct measurement of Hex A at the mill level is difficult. Hex-A is primarily a hardwood phenomenon due to Xylan levels in hardwood being three (3)to four(4)times that of pine. By consuming potassium permanganate, digester"PN" numbers report Hex-A. A typical hardwood_pulp may have four(4) points of Hex-A with eight(8) points of lignin for a total"PN" of twelve (12). Removal of half the remaining lignin in the 02 delignification stage reduces the"PN"by four(4) points but appears to reduce the "PW by only 33%. By the start of the Eo stage, there is very little lignin left and most of the measured"PW is Hex-A(3 parts Hex A+ 1 part lignin=4 "PN' . Canton's hardwood delignification rate of around 33% is considered about normal for a single-stage 02 delignification system on hardwood pulp. Delignification is actually much betterthan the data suggests- interference from Hexenuronic Acids makes the performance only appear to be poor. Bill Adams (828)646-2868 402230 H2O2 on HW.xts Page 3 7/9/02 ' Blue Ridge Paper Products, Inc. - Trial Report ( , Hydrogen Peroxide (H2O2) on Hardwood Eo Stage - MTA #402230 In the bleach plant, Hexenuronic Acids consume C102 and permanganate, but do not decrease the pulp's brightness. Therefore, all of the Hex A does not need to be removed to bleach the pulp to high-brightness. Hexenuronic Acids contribute to variation of pulp quality measurements. Note: Thanks[ To Rogelio Vega-Canovas of Atofina for this information. / c � Bill Adams (828)646-2868 Principal Process Engineer CC: Bill Boris Johnnie Pearson Derric Brown./ Melanie Samuels Paul Geoghegan Steve Single Chris l-ifka File(x2) Pete Maxey Bill Adams (828) 646-2868 402230 H2O2 on HW.xls Page 4 7/9/02 s �, pami CLNlap T V 0 = e m m C w!� A C at� IM -{yyb � O N AN C n 1pp.VmVmYNf N A Nm Q VF9NMNNm N N� QUN01NNa1 - M a {y m m m nm 0 Nn m ANb < m mb m�AbN� mym � {mp e�r mnnMN N yq C O p N A b V n l•1 m W q M{D m m r N r p pml y YCCR NmMM m .ocJ�{ .Mj �(Iyp+�O pM �WOy+� GI CCIpp VV N1�0 C4 dM 6CI CI V < pl I°-T yNNNNH 13 N� �N NMm hN m IRN NmNNMMN N dim oMia 9 a MH rH WY1 p C g W d U o d U m RNI M Nt7M N N M A M U s U U U 6 6r Ify U C D�.{O( m mS ON N E z S a $ ° n " mat mry �j g M mmmmm.- aI mN e$N{yM1 o nH M IR N ' 'mpj p C�NNN(7 N NIV OQIp000 mN E c c dco d d do R � � la•V PmQv `+ MY a E o U0 n 2 R Z m Y S O'(p N al Ul b m m Iq q pq at ID H ^Qpp O d M o m 10 m.m N m1 m N N� N'a 01�S.O b p mm<NNCI V Y (VV n�IC II�O c 0 ryr- mn Cl lq m �m o000 0 o n 0 m r m�AnmA n o N .-ubbom M b•v N H 2 a m blm� rym � ry N m0 1p q al Naabm m W°� Ipmrm Nm 0 IDO Y at M gemm m aqm Ima b ga . b m (b l0 i W m :m0- G 00 " No FlMm 0 O V N pro V dd N..am A CC m IE M b b rym m q v me ry m rymm.; n p�.- yN a�o cyn A, a nv rymr,.-ny m .j lq N N MN fV N N a901 W o eQ- W�� oS eM- p I°I°'� ' wem- a bri QIG<C 1C OM o -> I i M Am b Iq (y N V q O b M pM�br n In OOR�. Rm A«m pmr m•m 01 �m a�QIO V "IQ Z d b b w w m m m III b lG Oa IG Ih IC ow n o v u 0 W m n c m Nry ryo o my b m r Iq lq m mm oe mm�o m rym mnoomm m rIR Z O0 cs a 0• 0• ^ O N NN yNN N pIN Y V MNmm m mm �. m'`Ic�r! mC Or n o Nml7 CONm W M M N cs p e � � �� q ' m r r v c o m o o 6 0. N a�b o N n m m p pp R G O OOOG C Gti bIYww IO Oi IG �IOO G �OOYYQ qp N zL m W �0 N ' ° mmmm m m m m I.' LL 0000000 O 00 p v' m rnn nn lO 6 y x b Q a N 6 6 �� n m 3 ' y m r a m o pp ggg Q�iiggppls� g N E @ n n ��0� �w Fdt rn A a�i n v�l �i @ i• r a is '» I`tivQr I'm n 9 IS v^ � rm � 3v� m� u�i ep'�r Fm a 1W N 9402230 HzOZ on HW Eo Stage Trial -Mill Sewer Color Data WWTP Primary Influent Color WWTP Secondary Effluent Color 75000 55000 70000 50000 65000 60000 45000 55000 40000 C)38788 50000 35000 45000 40000 30000 Trial Part I Trial Part II Trial Part I Trial Part II —Ave-1 Std —Average ®Ave+1 Std o Trial —Ave-1 Std —Average®Ave+1 Std O Trial 3A(Alkali) Sewer Color Hardwood Eo Effluent Color 16.00 10.00 15.00 9.00 14.00 8.00 13.00 7.00 12.00 6.00 11.00 5.00 . 97 2 10.00 4.00 9.00 3.00 8.00 2.00 7.00 1.00 6,pp 0.00 Trial Part I Trial Part II Trial Part I Trial Part II 'Ave-1 Std --Average ®Ave+ 1 Std O Trial —Ave-1 Std —Average —Ave! 1 Std O Trial Bill Adams (828) 646-2868 402230 H2O2 on HW.xls 7/9102 H Blue Ridge Paper - Canton Mill Process History Report i O: Michael Ferguson Data. July 10.2002 Fiberline Superintendent FROM: Bill Adams SUB: Process History-D-100 Kappa Factors Principal Process Engineer Performance/Monitoring Background Summary: Section A. (8.)5. Of the NPDES Permit(Permit No:NC0000272)requires the Canton Mill to address Process Optimization items identified in the study commissioned by the EPA Tech Team(aka, the"Liebergott/GL&V Report'). The information contained in this"Process History Report'addresses Item No's. 6&13 of this report-that is,to"reduce...D-1 stage kappa factor to 0.20-0.24...'. "Kappa Factor'is a mathematical method of stating the amount of active chlorine dioxide(CI02)applied per kappa unit, the measure of residual Iignin in the pulp. Canton does not determine the kappa number of pulp directly; Instead,the "K'number or"PN"number is determined. The kappa number can then be estimated based on the relationship of kappa numbers to"PIN!"numbers. This relationship was checked in 1995 by Champion Corporate Technology for Canton. The Kappa Factor formula is: %CI02 Applied in Whole Numbers ` 2.63 =Kappa Factor Pre-Bleach Kappa Number Kappa No. Conversion is: Kappa No. = 0.293+("K'No. ' 1.47) Canton reports chemical application in terms of"Bleached Air Dry Tons"of pulp(BADT). "Air Dry"tons are defined by industry convention to contain 10%moisture. "Air Dry"tons are the most common pulp unit used In the U.S. `=='Air Dry"tons are determined from"Bone Dry"tons—that is, pulp.that has no moisture. When pulp consistencies are determined,the results are generally on a"bone dry'basis. References to"Kappa Factor'in text sources I have been able to review generally avoid specifying whether the units are"air dry'or"bone dry'. An unscientific survey of peers and knowledgeable persons indicated that there Is not an industry standard-about 2/3 would use"air dry"numbers, but nearly every person had to think about which values to use. After the Ltebergott/GL&V audit,the question as to what basis to use was raised. Canton has traditionally used the "air dry'values,while the GL&V folks have traditionally used"bone dry'values. This difference in basis was not discovered until after the technology report had been submitted. Within the Canton Mill, the"air dry"vs."bone dry'discrepancy has caused confusion. The chemical application rates used by the DCS on the softwood(#2 Fiberline)fiberllne are generally"bone dry'while the application rates used on the hardwood (#1 Fiberline)fiberline are generally"air dry'. This discrepancy has existed from initial start-up of the DCS controls on each fiberline and is planned to be resolved(going to"air dry'basis). The discrepancy generally does not matter in terms of monitoring as actual chemical usage and actual"air dry'pulp tons are used to calculate chemical usage reports for mill management However,the values shown on the DCS are different from those calculated from daily data. Kappa Factors are calculated and displayed in the DCS system using DCS application rates and OCS production rates. Neither of these values is"official"in that they are not used to estimate reported costs, nor to determine and report pulp production. However,the Liebergott/GL&V audit team observed the erroneous Kappa Factors displayed by the DCS and made the above referenced recommendations that the mill reduce Kappa Factors. iudits by a variety of suppliers have generally Indicated Canton's kappa factors to be average or a little lower than average for the industry. Bill Adams(828)646-2868 NPDES Items .xis Page 1 7/11/02 Summary of Process Changes: decent fiberline bleaching changes that affect Kappa Factors are shown below. i• 5/17/01 D-1 Stage Optimization - Both Fiberiines 8/7/01 D-1 Stage Optimization - H202 Off Pine 11/1101 D-1 Stage Optimization - Pine Fiberiine 12/17/01 Pine Cooking Change (Extend Cooking Time) 2/5/02 HW Cooking Change (Extend Cooking Time) 3114/02 HW Optimization - D-100 pH 5/13/02 H2O2 Trial(HW)(Ended 6119102) 6/20102 Normal Operation Shown below are charts showing Kappa Factors over time. Kappa Factors have been calculated using both Air Dry and Bone Dry pulp tons. Chart#1 -Pine D-100 Stage Kappa Factors Pine D400 Stage Kappa Factors m o ^ 0.290 , N o N N n N O O 0.270 ^ N N Cl! O'O N N O 0.250 0 0 0 0.230 o N C 0.190 a5 ? cy ? 0.170 n ) ` 5i5 O? �qo °e OKappa Factor-AD MKappa Factor-BD Chart#2-Hardwood D-100 stage Kappa Factors Hardwood D400 Stage Kappa Factors m 0.310 ry N 0.290 N o _ ^ 0 0.270 Cl! O1 N 0.250 15' o N o N ry 0.230 0 O1 O N N N O O O N 19 n 0.210 f 0.190 0.150 g g m°� mg` i9AQ �e0aimg z m9� ad?e � �g� y€�5 z ' gF ��< °S o2 $ g gB QKappa Factor-AD OKappa Factor-BD Bill Adams(828)646-2868 NPDES Items .xis Page 2 7/11102 Average data for the three(3)days of the Liebergott/GL&V audit are separated in the above tables and marked in color. ,onclusions): Pine Fiberline(see Chart#1): The data shows pine kappa factor to be about 0.22 to 0.24, a little higher than the Liebergott/GL&V recommendation(AD Ton basis). The softwood fiberline is controlled so that about half of the total Clo application is made on each stage, a strategy that has proven sound over nearly ten(10)years of operation. A planned project to revise the softwood Og Delignification stage will reduce the kappa number of pulp going to the bleach plant and reduce CIOZ demand. The kappa factor will also be reduced when the OZ Delig project is completed. Color generated in the Pine D-100 stage is retained on the fiberline via the BFR" system. Hardwood Fiberline(see Chart#2): The data shows HW kappa factor to be between 0.18 and'0.21 (AD Ton basis)which Is lower than the Liebergott/GL&V recommendations. Other knowledgeable bleaching authorities have recommended hardwood kappa factors at similar levels. No changes are indicated. Recommendations: Continue refining/optimizing bleach plant performance as necessary. Dedicate the time required to revise the softwood DCS system to an"Air Dried"basis. Some time will be required to explain the change to the operators whose reference numbers will be slightly changed. Hexenuronic Acids: Hexenuronlc Acids(Hex-A)are chemical groups that originate from hemicellulose, but chemically react more like lignin. They form during the Kraft cook from certain acid groups in Xylans. Hex A raises"PM'or"K'"numbers and consumes CIO2, ut Hex-A does not darken the pulp. Hexenuronic acid was first described in publications in 1996. Direct measurement of Hex-A at the mill level is difficult. Hex A is primarily a hardwood phenomenon due to Xylan levels in hardwood being three(3)to four(4)times that of pine. By consuming potassium permanganate, digester"PN"numbers report Hex-A. Atypical hardwood pulp may have four(4) points of Hex-A with eight(8)points of lignin for a total"PN"of twelve(12). Removal of half the remaining lignin in the OZ Delignification stage reduces the"PW by four(4) points and appears to reduce the"PW by only 33%. By the start of the Eo stage,there is very little lignin left and most of the measured"PIN!"is Hex-A(3 pts Hex A+ 1 pt lignin=4"PN"). Canton's hardwood delignification rate of around 33%is considered about normal for a single-stage 02,delignification system on hardwood pulp. Delignification is actually much better than the data suggests-interference from Hexenuronic Acids makes the performance appear to be poor. In the bleach plant, Hexenuronlc Acids consume CI02 and permanganate, but do not decrease the pulp's brightness. Therefore, all of the Hex-A does not need to be removed to bleach the pulp to high brightness. Hexenuronic Acids contribute to variation of pulp quality measurements. Note: Thanksl To Rogelio Vega-Canvas of Atofina for this information. Bill Adams Principal Process Engineer CC: Bill Boris ` Johnnie Pearson r Derric Brown ✓ Melanie Samuels Paul Geoghegan Steve Single Chris Ufka File(x2) Pete Maxey Bill Adams(828)646-2868 NPDES Items.xis Page 3 7/11/02 f.evergreeff packaging Blue Ridge Paper Products Inc. - Canton Mill To: Michael Ferguson, Barry Covington Date: January 24, 2012 From: Bill Miller Subject: H2O2 Hardwood and Pine bleaching trial results Executive Summary: A mill bleaching trial applying hydrogen peroxide (H2O2) to the Hardwood E and Pine Eo stages was run for a 90 day period. The basis for the trial was to economically displace chlorine dioxide (C1O2) with H2O2 in the bleach lines. The 90 day trial period started June 23-25, 2011. Fiberline operating data from I"quarter 2011 and June 2011 were investigated for establishing a relevant economic baseline. The June 2011 period, following cold mill outage (CMO), was used. The D 1 stage trial kappa factor(KF)of 0.20 was targeted for both lines. The H2O2 charges were base loaded at 0.3% Ep stage Hardwood and 0.4% Eop stage Pine. These parameters established by Evonik(supplier) and Evergreen. The Ep/Eop stage CEK increase resulting from the reduced D 1 stage KF, would be partially offset by the H2O2 addition, minimizing C1O2 increase in the D2 stage. Costs savings from reduction in D 1 C1O2 usage would have to sufficient to offset cost of H2O2 and increased D2 stage C1O2 usage. NaOH cost for pH control are also included. For Hardwood, the July trial period looked promising, with a monthly average bleaching cost reduction from$34.66 base to $34.09 trial for an abnormally low average Post 02 (PO) K-no of 6.1. In the Aug.-Sept. trial periods, average PO K-nos increased to a more normal range of 6.3- 7.7 due to seasonal digester cooking changes. The H2O2 Ep stage reinforcement was not adequate to offset this added bleaching load at 0.2 KF. The Hardwood trial operating parameters resulted in D 1 average C1O2 flow reduction of 14 gpm, CEK increasing from a 1.8 baseline to 2.5 trial and D2 average C1O2 flow increase of 25 gpm. Overall average trial bleaching costs increased from $34.66 to $35.46. Hardwood average effluent color loading showed no appreciable net change. Average effluent color loading increased from 5500#/day baseline to 8300#/day trail for D 1 stage and dropped from 8700#/day to 6300#/day for Ep stage. Page 2 The Pine trial overall bleaching costs never economically justified the H2O2 costs, even during the July trial period with average PO K-nos of 8.0. Eop operating data indicates DI washer discharge (COD) from MRP and Eop recycle is consuming H2O2 applied to Eop stage. The Pine trial operating parameters resulted in a D 1 average C1O2 flow reduction of 6.5 gpm, CEK increasing from a 2.7 baseline to 3.4 trial and D2 average C1O2 flow increase of 14 gpm. Overall average trial bleaching costs increased from$33.08 to $37.60. Pine average effluent color loading increased from 940#/day baseline to 1090#/day trail for DI stage and dropped from 5840#/day to 18709/day for Eop stage. The Pine bleach plant average closure increased from 78%baseline to 85.2%trial, which accounts for a good portion of the Eop trial color loading decrease. Based on these trial results, the application of H2O2 as bleaching reinforcement in the Hardwood E stage and Pine Eo can not be economically justified. 1. Introduction: A hydrogen peroxide (H2O2) trial run in the Canton No. 1 Hardwood and No.2 Pine Bleach Plants was proposed due to favorable (H2O2) pricing from Evonik. The trial economic justification is l#/T of dry H2O2, applied as delignification reinforcement into the Hardwood E stage and the Pine Eo stage, has to displace %2#/T of applied C1O2. Cost adjustments for increased NaOH usage as pH control were also taken into consideration. The most effective approach for C1O2 reduction/displacement is reduce the D I kappa factors (KF) when H2O2 is applied to the Eo/E stages. The strategy is to make up for the reduced D 1 stage delignification by applying the H2O2 to the extraction stage, minimizing any CEK increase resulting from the D1 stage KF reduction. There will be an increase in D2 C1O2 charge, which is typically about''/2 (#/#basis) D 1 stage C1O2 reduction. A D I stage trial KF target of 0.20,with H2O2 base loaded at 0.3% Ep hardwood and 0.4%Eop Pine,was established by Evonik and Evergreen. C1O2 and NaOH usage and process parameters were monitored, and total bleaching chemical costs weighed against the cost with and without H2O2. Bleach stage effluent color was also monitored. The H2O2 addition started June 23-25, 2011 for both lines for a 90 day trial. The period following the CMO, June 1-25, was used as a baseline for bleach chemical cost comparison. The period leading up to the CMO, Jan-Mar 2011 was also evaluated but not used in the comparison. Page 3 The Pine trial was ended on Sept. 27,2010. The Hardwood trial was extended to Oct. 27, 2011 with increased D1 KF, but not used in financial evaluation. 2a. Hardwood Conclusions: • Adjustments in D1 KF resulted in-elevated CEK(Graph 1 in Appendix). The best results were at a D1 stage 0.226 KF, during the July period. • The D1 0.22-0.23 KF range was only effective for average.6.1 kajaani k-no (5.6 PN). • At 0.19-0.2 KF in D1, the H2O2 could not offset the loss of D1 delignification,resulting in elevated CEK(Graph 1) and increased applied C1O2 in D2 (Graph 2). The 30 gpm C1O2 reduction in D 1 resulted in 60 gpm C1O2 increase in D2. There was also a corresponding increase in D2 NaOH for pH control (Graph 3). • At 0.19-0.20 KF in D 1, the H2O2 cannot offset process changes resulting from seasonal cooking K-no swings. • Raising KF to 0.222 in Oct.period did not return favorable results due to unsteady operation from liquor inventories and digester repairs. • Hardwood average effluent color loading showed no appreciable net change at stage sewers. Average effluent color loading increased from 5500#/day baseline to 8300#/day trail for D 1 stage and dropped from 8700#/day to 6300#/day for Ep stage (Table 2 in Results). • Quality as measured by viscosity and brightness was unchanged by H2O2 addition(Table 2). • Long term use of H2O2 in the hardwood E stage shows limited financial opportunity and is not recommended. 2b. Pine Conclusions: • Small adjustments in D1 KF from 0.226 to 0.21, resulted in elevated CEK(Graph 5). The 5 gpm C1O2 reduction in D1 resulted in 15-30 gpm C1O2 increase in D2 resulting from elevated CEK (Graph 6). • H2O2 in Eop stage adds minimal delignification boost which limits D 1 KF reduction. • Increased level of NaOH to Eop for maintaining 10.0-10.2 pH indicates H2O2 reaction/consumption with recycled COD carryover from D 1 washer(Graph 7). Filtrate recycle is standard operation for recycling D1 and Eo filtrates on D1 washer showers. • Effluent color numbers are inconclusive. • Quality as measured by viscosity and brightness was unchanged by H2O2 addition (Table 5). • H2O2 addition to pine Eo stage is ineffective, demonstrating no financial opportunity. Future use is not recommended. Page 4 3. Results: Table 1: Hardwood H2O2 Trial Process Summary (averages) Pre Pre Shwr PB D1 D1 D2 BI BI cond mat D1 D1 H2SO4 mxr I Eo D2 NaOH D2 Period TPD Kno PN mmhos cond 9Pm KF % PH NaOH CEK 9PM gPM ISO 1st q.base 727 6.26 6.30 101.85 593.03 122.30 0.29 1.08 3.36 9.79 1.69 77.19 0.66 86.4 June base 730 6.19 5.65 115.01 426.05 107.43 0.25 0.68 3.17 10.48 1.82 62.66 0.13 86.6 Jul 752 6.12 5.64 60.43 421.26 95.67 0.23 0.74 3.28 10.52 2.05 61.05 0.11 86.7 Aug777 6.69 5.99 101.74 521.20 94.03 0.19 1.07 3.28 10.51 2.69 88.29 0.21 86.9 Set 762 6.31 5.96 156.26 501.98 91.20 0.20 1.01 3.17 10.92 2.70 94.64 0.50 86.4 Oct 764 6.39 6.08 152.98 536.81 101.01 0.22 1.10 3.10 11.71 2.58 101.72 0.96 86.3 July-Sept av 93.6 2.48 81.3 Table 2: Hardwood H2O2 Trial Environmental and Quality Summary (averages) D1 color Eo color period TPD #/da x 1000 #/da x 1000 Visc c s D2 ISO 1 st quarter base 726.99 5.42 6.20 16.27 86.44 June base 730.49 5.50 8.69 14.61 86.56 July 751.84 7.32 6.08 13.55 86.74 Aug777.36 7.78 6.75 14.12 86.59 Set 762.48 9.67 5.97 14.68 86.44 Oct 763.76 7.36 7.46 15.07 86.33 July-Sept av 8.3 6.3 Table 3: Hardwood H2O2 Trial Bleach Chemical Usage and Cost Summary (averages) total# total Ep# total D2# total# C102 NaOH H2O2 6102/T NaOH/T NaOH/T CI02/T/kno $/T $/T $/T Total $/T 1 st quarter base 34.57 17.77 1.20 5.52 18.48 3.86 0.00 36.49 June base 29.34 18.93 0.24 4.74 15.68 2.70 0.00 34.66 July 26.26 18.45 0.19 4.29 14.04 3.80 1.56 34.09 Aug29.55 17.83 0.35 4.42 15.80 3.70 1.56 35.25 Set 30.71 18.89 0.87 4.86 16.41 4.03 1.56 37.04 Oct 33.45 20.22 1.65 5.23 17.88 4.45 1.56 39.99 July-Sept avg I L I $35.46 Table 4: Pine H2O2 Trial Process Summary(averages) Eo Lab PO PO Pre BI D1 D1 % D1 D1 mxr NaOH D2 D2 period TPD PN Kno Kno QPM KF acid PH 9pM CEK gpm ISO list quarter base 643 9.71 10.37 9.73 124.5 0.21 .0.33 3.44 17.7 2.92 127.0 86.2 June base 628 8.99 9.82 9.53 126.5 0.23 0.09 3.28 15.1 2.66 121.6 86.6 July 672 7.99 10.26 10.18 130.3 0.21 0.33 3.33 20.0 3.13 135.7 86.7 Aug685 8.85 10.45 10.13 134.4 0.21 0.31 3.32 20.5 3.62 148.9 86.8 Sept. 690 9.67 9.72 9.34 134.2 0.22 0.28 3.35 21.3 3.36 154.5 86.5 1 609 9.9 33 3.2 14422 86.6Oct 3 6Jul -Se 132.9 37 Page 5 Table 5: Pine H2O2 Trial Environmental and Quality Summary(averages) D1 color Eo color 3A color #/day x #/day x #/day x period TPD 1000 1000 % closure 1000 D2 vise cps D2 ISO 1st quarter base 643 2.04 3.10 78.45 16.91 15.70 86.2 June base 628 0.94 5.84 78.00 16.89 15.96 86.6 July 672 0.92 1.78 89.66 7.57 15.74 86.7 Aug685 1.61 0.39 85.06 9.37 15.22 86.8 Se t. 690 0.73 3.44 81.38 11.77 15.15 86:5 Oct 609 5.2 4.1 64.8 12.7 14.9 86.60 July-Sept av 1.09 1.87 85.2 9.6 Table 6: Pine H2O2 Trial Bleach Chemical Usage and Cost Summary(averages) total# total# period CIO2/T NaOH/T C102$/T NaOH$/T H2O2$/T Total $/T 1st quarter base 49.6 36.2 26.50 7.38 0.00 33.88 June base 49.8 31.8 26.60 6.48 0.00 33.08 July 49.4 39.2 26.42 7.99 2.08 36.49 Aug52.1 39.5 27.84 8.04 2.08 37.96 Set 52.4 40.7 27.99 8.29 2.08 38.37 Oct 56.5 33.5 30.20 6.83 0.00 37.03 July-Sept av 37.60 3a. Hardwood Results: The Hardwood trial operating parameters resulted in the monthly average CEK increasing from a 1.8 baseline to 2.5 trial (Table 1), increasing overall monthly average bleaching costs from $34.66 to $35.46 respectively (Table 3). Hardwood trial results are summarized in Tables 1-3 above and Graphs 1-3 in appendix.. Trial periods are summarized on a monthly basis and shown sequentially on x axis of graphs. Table 1 shows: • Is`quarter base period shows high Pre Bleach(PB) mat conductivities, 0.29 KF, increased bleach chemical usage. This was a period of problematic brownstock washing operation, which was resolved during March outage. • D1 trial KFs ranged from 0.19-0.23, down from 0.25-0.29 in base periods preceding trial, 0.226 KF in July trial period being the most effective. • Trial period showed a 0.2 gpm increase in H2SO4 required to maintain D 1 mixer pH of 3.3. Page 6 • Kajaani K-nos and and lab PNs increased 6.1-6.7 and 5.6-6.1 respectively during trial period. • PB mat conductivity increased from 421 to 537 µmho during trial period. The increased mat conductivity correlated to increased H2SO2 usage for D1 pH control. • As the D1 KF was reduced, the CEK increased from 2.05 to 2.7,up from 1.7-1.8 in base periods (graph 1). • D2 C1O2 charge increased from 61-95 gpm as CEK increased(graph 2). • NaOH for Ep control to 10.2-10.5 pH increased about 1 gpm.NaOH for D2 pH control increased 0.4-0.8 gpm as D2 C1O2 charge increased (Graph 3). • H2O2 results were favorable at 0.23 KF, 6.1 k-no, 421 µmho mat conductivity. At increased K-nos and washer losses, H2O2 lost delignification efficiency. • Adjusting DI KF up to 0.222 in Oct. trial period did not show favorable results seen in July trial period. Higher PO K-nos from seasonal cooking changes,unsteady operation resulting from recovery liquor inventories and poor D 1 washer operation were contributors to diminished results. Table 2 shows: • D1 effluent color increased to 7,300-9,700/day during trial period. Ep effluent color was steady in a 6,000-7,500#/day range and 3A initially dropped to 7,600#/day, gradually increasing to to 12,000-12,500#/day. • D2 final viscosity initially dropped to 13.6 cps, but remained in the 14-15 cps range during most of the trial. • Final D2 brightness was above 86.0 ISO for trial period. Table 3 shows: • Initial July trial period showed favorable cost results of$0.57/T savings. This eroded to $0.60-$3.90/T loss. • pH control to Ep and D2 stages accounted for$1.10-$1.65/T of additional chemical cost. 3b. Hardwood Discussion The No. 1 hardwood bleach line showed the most potential for the H2O2 trial plan. The hardwood D1 stage was operating with KFs in the 0.25-0.29 range with E Stage CEK of< 2.0. Targeting a H2O2 trial D 1 KF of 0.2 would result in a Ep CEK of< 2.5. The increased D2 C1O2 usage resulting from the stated rise in CEK would be more than offset by the C1O2 reduction in D1, enough to justify the H2O2 operating costs. Once H2O2 flow was established at 0.3% addition rate, the D1 KF was gradually reduced to the 0.2 level. The bleach control KF curves were updated and control bias adjusted after about a week at each KF level. Page 7 This strategy worked for July, at a 0.22 KF, when PO Kajaani K-nos/lab PNs averaged 6.115.65 and fiberline operation was steady. During the Aug. and Sept. periods, the 0.2 KF level was established, the PB K-nos increased, and PB washer losses were higher, resulting in an Ep CEK> 2.5 (Graph 1). At these CEK levels, the D2 C1O2 levels increased to levels greater than the D1 reduction (Graph 2). At D2 C1O2 flow levels > 90 gpm, D2 NaOH flow pH control also increased, adding to the bleach chemical costs. In the Oct. period, the D1 KF was increased to the 0.22 level of July. The PO K-nos and washer losses were 6.4 and 537 µmhos respectively, notably higher than the July period. These process shifts resulting from seasonal cooking changes and unsteady recovery operation. Operating problems with the D1 washer were also encountered. With these process changes, the H2O2 addition could not keep the Ep CEK<2.5. From these observations it is concluded that the Ep stage H2O2 reinforcement is most effective in a narrow operating range of K-nos, with steady state operation. Any deviation in these or other front end operating parameters reduces the H2O2 delignification efficiency. 3c. Pine Results The Pine trial operating parameters resulted in the monthly average CEK increasing from a 2.7 baseline to 3.4 trial (Table 4), increasing overall monthly average bleaching costs from$33.08 to $37.60 respectively (Table 6). i Pine trial results are summarized in Tables-4-6 above and Graphs 5-7 in appendix. Trial periods are summarized on a monthly basis and shown sequentially on x axis of graphs. Table 4 shows: • lS`quarter base period shows very good bleach chemical usage, with KF averaging 0.21, which would be very difficult to improve upon with H2O2. • Trial period D1 KFs averaged 0.21-0.22, reduced from 0.23 base period. • D1 KF reduction resulted in CEK increase to 3.1-3.6 range (Graph 5). • Elevated CEK increased D2 C1O2 flow to 136-155 gpm range (Graph 6). • Lab PO PNs tracked significantly lower than Kajaani PO K-nos for July-Aug trial periods. CEKs for same periods do not indicate overbleaching. • Elevating Bo pH target to 10.0-10.2 range increased NaOH usage 5-6 gpm. • Oct. period results without H2O2 inconclusive due to annual outage and start up. Page 8 Table 5 shows: • No significant change in D1 effluent color. Eo effluent color dropped to 1780-390#/day range in July Aug trial periods while % closure was>80% during the entire trial period. 3A color initially dropped to 7,600#/day, gradually increasing to to 12,000-12,500#/day. • D2 final viscosity was> 15 cps and D2 final brightness> 86.5 ISO during entire trial period. Table 6 shows: • Bleach chemical costs were negative for the entire trial period., ranging$3.00-$5.25/T over June base period. • pH control to Eo stage accounted for$1.50-$1.80/T of additional chemical cost. 3d. Pine Discussion The No. 2 pine bleach line showed limited potential for the H2O2 trial plan. The pine D 1 stage, was operating with KFs in the 0.21-0.23 range with Eo Stage CEK in the 2.5-2.9 range. Targeting a H202 trial D 1 KF of 0.2 would result in an Eop CEK 3.0-3.25 range. The increased D2 C1O2 usage resulting from the stated rise in CEK would be more than offset by the C1O2 reduction in D1. Given this KF reduction is small,the resulting C1O2 savings would be hard pressed to justify the H2O2 operating costs. Once H2O2 flow was established at 0.4% addition rate, the D1 KF was reduced to the 0.2 level. The bleach control KF curves were updated and control bias adjusted after about a week at each KF level. This strategy showed the best results for July, at a 0.21 KF,-when PO Kajaani K-nos/lab PNs averaged 10.3/8.0. This discrepancy raised concern, test procedures and Kajaani bias were checked. The bleaching response reacted more in line with the K-nos. Results for all three trial periods saw Eop CEK levels mostly> 3.5, which results in high D2 C1O2 usage. The Eop stage pH control showed a substantial increase in NaOH to maintain the optimum > 10.0 pH for H2O2 bleaching. This suggest the H202 is being consumed by the D1 washer recycled COD. Spot checks of the D 1 washer discharge pulp showed COD levels of 70 kg/T. From these observations it is concluded that the Eop stage H202 reinforcement is not effective. H202 in the Eop is a consumed by high levels of recycled COD from D1 washer. The Pine bleach line already runs well at respectable 0.21-0.23 D1 KF levels. Target D1 KF below 0.21 results in a disproportionate increase in Eo CEK, which the applied H202 cannot control. Page 9 5.Appendix. Graph 1: Hwd D1 Kappa Factor vs CEK Graph 2: Hardwood D1 Kappa CEK/D1 and D2 C1O2 charge relationship 2.80 2.60 120 — ---- 2.40 110 .� 2.20 100 .. Y 2.00 a 90 0 80 1.80 N 1.60 O 70 —D1 GO'l 1.40 U 60 �_D2 Q02 1.20 50 1.00 40 0.255 0.225 0.194 0.200 0.221 1.82 2.05 2.69 2.70 2.58 Kappa Factor (KF) CEK Graph 3: Hwd D2 C1O2 gpm vs D2 NaOH 1.20 1.00 E a 0.80 o, 0 0.60 m Z 0.40 fV 0.20 0.00 62.66 61.05 88.29 94.64 101.72 D2 C1O2 gpm Page 10 Graph 5: Pine D1 Kappa Factor(KF)w CEK- Graph 6:DI and D2 C102 charge/CEK 3.8 relabonship 3.6 160.0 3�4 155.0 32 150.0 3.0 E 145.0 Ui 0. 2.8 0 - 140.0 2.6 C4 135.0 2.4 130.0 2.2 GPM 125�O �Dlclw GM 2.0 0.226 0.208 0.211 0.222 120.0 GPM 102 2.7 3.1 3.6 3.4 Kappa factor (KF) CEK Graph 7: Pine Eo%NaOH pH control 22.0 20.0 0 18.0 LLI 0 16.0 514.0 m Z 12.0 10.0 June base July Aug Sept. Trial Period Statistical Overview of Peroxide Application on Softwood and Hardwood Fiberlines for Color at the Canton Mill Canton, North Carolina 3rd Quarter 2011 Nick McCracken-Water Compliance Coordinator,Evergreen Packaging Canton Mill December 2011 The full-scale trial for the application of peroxide to the fiberlines at the Canton Mill began on June 22, 2011 for the pine fiberline and ran through September 27, 2011. The hardwood fiberline trial began on June 25, 2011 and ran through October 27, 2011. Color data from June through September on both fiberlines were used for the statistical analysis. The third quarter color data of 2010 were used for comparative purposes against the 2011 trial data because of the close similarities in pulp production and Permanganate Numbers (PN) prior to bleaching on both fiberlines. All data analyzed were checked against final averages from this time period and with a two-test series (Two sample T-test&ANOVA) for statistical significance. All statistically significant findings were of 95% or greater confidence. Measured color streams included: Primary Influent, Secondary Effluent, Acid Sewer, Pine Fiberline Bleach Plant, Hardwood Fiberline Bleach Plant, #3A Sewer and Evaporator Contaminated Condensates. Averages for the Primary Influent& Secondary Effluent streams were lower than the third quarter of 2010 data and were found to be statistically significant. Other averages that were below the third quarter comparison data and also found to be statistically significant were the #3A Sewer and Evaporator Contaminated Condensate. The Acid Sewer color average was lower during the trial period but the difference was not statistically significant. There was no reduction in the pine fiberline bleach plant combined color average. In fact, the overall average color number was higher than the color average observed in 2010. The pine Dl filtrate stream was the only one, from both fiberlines, to have a lower color average during the trial. This average was also statistically significant. The pine Eo filtrate stream was not statistically significant and demonstrated a higher color average than in 2010. The hardwood fiberline bleach plant combined color average increased and this increase was statistically significant. The overall average color number was higher than the color average observed in 2010. Both the Dl and Eo filtrate color averages were higher in comparison to the 2010 data and both were found to be statistically significant. Full-scale application of peroxide to the hardwood and pine fiberlines during 3rd Quarter 2011 was not beneficial to Secondary Effluent color at the Canton Mill. Both fiberline bleach plants experienced higher color averages when compared to the third quarter data of 2010. Other outside processes in the mill drove the color performance observed in the Primary Influent and Secondary Effluent averages. Attachment—power point presentation,peroxide trial analysis of color Canton Mill Full-Scale Trial of Enhanced Extraction with Peroxide on Eo stages (EoP) Analysis of Color 3rd Quarter 2011 Nick McCracken and Color Team Comparison • Used 3Q 2010 vs. 3Q 2011 Trial Period — Pulp production numbers comparable - 3Q 2010 — 1446 avg tons/cal day • Trial — 1455 avg tons/cal day Pre-02 PN #s comparable • 3Q 2010 Hwd — 9.6 • Trial (Hwd) — 9.7 • 3Q 2010 Pine'— 17.6 • Trial (Pine)- 17.6 z • PI & SE Color Performance Primary Influent 8 Secondary Effluent Color Comparison 30 2010".Trial 45,000 40,000 35,000 - 30,000 w 25.000 .- a i c 20,000 -- --- 15,000 "'.. 10,000 - 5,000 830PI Is Tnal R u 30 Sk_ ■Trial S, 3 PI & SE Stats • There is a statistical significance using a T-test and ANOVA analysis • Both tests showed a >95% confidence • PI difference of 6720 Ibs/day based on average • SE difference of 5476 Ibs/day based on average 4 Bleach Plant Numbers • Filtrate Numbers Compared: — Hwd D1 — Pine D1 — Hwd Eo — Pine Eo — Acid Sewer (PD1+PD2+HD1+HD2) — 3A Sewer (PEo+HEo+Excess Evap Condensates) — Hwd Total Bleach Plant Color — Pine Total Bleach Plant Color 5 D1 Filtrate Colors D7 Filtrate Color Numbers 3012010 vs.Trial Period 9,000 8,000 7,000 6,000 a 5,000 4,000 3,000 2,000 1,000 0 ■3QkMd ■Trial KW ■3Q Pine ■Trial Pine 8 D 1 Stats • Hwd D1 shows a statistical significance — >95% Confidence • Hwd D1 average was 1367 Ibs/day higher than 3Q 2010 • Pine D1 shows a statistical significance — >95% Confidence • Pine D1 average was 1273 Ibs/day less than 3Q 2010 7 Eo Filtrate Colors Eo Filtrate Color Numbers 3012010 vs.Trial Period 7,000 6.000 5.000 2 4,000 $� 3.000 2,000 1.000 0 03O RW ■Tdal Hwd 03Q Pim ■Trlel Phr B Eo Filtrate Colors HM EO 8 Plne EO Color Nombers lo,PomxlGx T6.1 E din9 9127l11 12 10 0 Alec . 4011 11,� <ec 4"�N, •a^,�.� .�s'�.^ °c��� ��R. —I �h•En—li "W Eul�IImY(EW Ee) 9 Eo Stats • Hwd Eo shows a statistical significance — > 95% Confidence • Hwd Eo average is 769 Ibs/day higher than 3Q 2010 • Pine Eo shows no statistical significance • Pine Eo average is 493 Ibs/day higher than 3Q 2010 10 Acid Sewer Color (PD1+PD2+HD1+HD2) Acid Sewer Color Numbers 30 2010 vs.Trial Period 7.500 7,000 6,500 T A 6,000 a_ 5,600 5,000 4,500 , •3Q10 ■TdN 11 Acid Sewer Stats • Acid Sewer showed no statistical significance • Acid Sewer average was 201 Ibs/day less than 3Q 2010 12 Hardwood Fiberline Total Bleach Plant Color Hwd Fibedine Total Bleach Plant Color 3Q 2010 vs.Trial 14,000 13,500 13.000 - — a 12,500 a 11,500 11,000 10,500 ■3Q10■Ttlel 13 Hwd Bleach Plant Stats Hwd Total Bleach Plant Color shows a statistical significance >95% Confidence • Hwd TBP Color average is 2071 Ibs/day higher than 3Q 2010 14 Pine Fiberline Total Bleach Plant Color Pine Fiberline Total Bleach Plant Color(AS+Eo Filtrate) 3Q 2010 vs.Trial 8,700 8,650 8,600 T ay 8.550 a_ 8.500 8.450 8,400 ■3Q10■Trial 15 Pine Bleach Plant Stats • Pine Total Bleach Plant Color shows no statistical significance • Pine TBP Color average is 147 Ibs/day higher than 3Q 2010 16 Contaminated Condensate Color Condensate Color Numbers 3Q 2010 vs.Trial 2,500 2,W0 1,500 1,000 500 0 i■3010 Caianr�eo�Trlel Contaminated 17 Contaminated Condensate Stats • Contaminated Condensate does show a statistically significant difference — >95% Confidence • Color concentration (ppm) • Overall loading (Ibs/day) • Color concentration was 58.7 ppm lower than 3Q 2010 • Color loading was 1228 Ibs/day lower than 3Q 2010 18 3A Sewer Color (PEo+HEo+Excess Evap Cond) 3A Sewer Color Numbers 30 2010 vs.Trial 11,500 11,000 10,500 10,000 :.. 9.500 $_ 9,000 8,500 8,000 7,500 7,000 330FC a Tnx 14 3A Sewer Stats • 3A Sewer color does show a statistical significance — 95% Confidence — 2 tests ran; T-test & ANOVA • 3A Sewer color average is 1437 Ibs/day lower than 3Q 2010 20 2071 136] Trial affected operations 69 14] 1 ] 493 (1437) (201) (12281 Non Trial mill operations Recovery,Kilns,aSW,Paper BBoaM (6720) (5476) � cao,m�maee cow o.ae.0 21 Conclusions • Both PI & SE were SS and their avg went down vs. 3Q 2010 • Other color streams looked at that were statistically significant: — 3 the avg went down (PD1 & 3A & Evap Cond) — 3 the avg went up (HD1 , HEo & HBP) • Other stream averages that were not SS: — 1 the avg went down (Acid Sewer) — 2 the avg went up (PEo & PBP) 22 Conclusions cont. • Is there a color benefit from Peroxide? — No-Bleach Plant color increased • 5 out of 6 color monitoring points in the trial affected area went up • Total bleaching costs increased$0.80 per ton on Hardwood and $4.52 per ton on Pine • Seasonal and other process variation contributed to color performance that was not associated with this trial • Exceptional evaporator performance and overall BMP closure drove PI and SE color performance — First time since CMO of 2003 that both sets of evaporators were cleaned at the same time — Both fiberlines cleaned and jetted washer during CMO — 'Exceptional color awareness and preparations around CMO 23 A%=TL Pulp & Paper Evergreen Packaging Bleaching Canton, NC Report: No.2011-054 Date issued: Date: August 3, 2011 Author: Pamela O'Leary Evergreen Packaging Attention: William Miller Contact:Andritz Inc. Division: Pruyn's Island Technical Center Project Manager: Michael Kingsley 13 Pruyn's Island Drive Glens Falls, NY 12801 Phone: (518)745-2999 Fax: (518)745-2971 E-mail: Michael.kingsley@andritz.com www.andritz.com Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted Wthout the written consent of ANDRITZ AG. AMRMTL Pulp a Paper Summary Evergreen Packaging supplied Andritz with mill oxygen delignified softwood and hardwood pulps for laboratory bleaching trials. We were to compare the effect on effluent color and fully bleached strength properties by changing the current Eo/E stages to Eop/Ep and pressurized Pht stages. Softwood was bleached using Do-Eo-D, Do-Eop-D and Do-Pht- D to a target 86% ISO brightness. Hardwood was bleached to the same brightness target using Do-E-D, Do-Ep-I) and Do-Pht-D. Observations • Mill softwood had a kappa number of 14.2 and viscosity of 14.3 mPa•s. • Mill hardwood had a kappa number of 6.8 and viscosity of 13.8 mPa•s. Bleaching Chemicals Con sum tion Summary Bleaching Sequence C1O2 H2O2 Final ISO Final Consumed Consumed Brightness Viscosity K /ADMT K /ADMT % mpa•s Softwood Do-Eo-D 25.2 - 86.1 11.2 (cor- rected Do-Eo -D 23.3 4.5 86.2 10.8 Do-Pht-D 21.4 5.4 86.4 10.7 Hardwood Do-E-D 17.5 -- 86.1 10.7 Do-E -D 12.6 2.7 86.3 10.8 Do-Ph,-D 8.8 4.5 1 86.5 11.3 Tear and Tensile Index@ 400 CSF of Fully Bleached Pulps Tensile Index Tear Index LIMS ID Descriptive ID (N•m/g)at 400 (mN•m'/g) at 400 CSF CSF 124576 Softwood Do-Eo-D 84.93 8.68 124582 Do-PHT-D 81.93 8.51 124579 Do-Eo -D 83.81 8.41 124572 Hardwood Do-E-I) 66.26 8.15 124745 Do-PHT-D 70.49 9.02 124818 1 Do-E -D 68.98 8.80 ConfldenW doc M.Atl rights reserved.No�plKaUon w diaclmure to thM pa t penrxlted rvikio t Ne wMlen cor N WANDRRZ AG. Page 2 of 11 AMMTL Pulp a Paper Experimental Standard Operating Procedures Procedure Description PITC-134 100% Chlorine Dioxide Substitution PITC- B8 Chlorine Dioxide Bleaching PITC-136 Alkaline Extraction PITC- B6 Oxidative Alkaline Extraction w/ eroxide Tappi T525 om-92 Diffuse Brightness TappIT230 Capillary Viscosity TappiT248 PFI Beatin of Wood Pulp ITappiT236 Kappa Number NCASI TB#253 Color in Effluent ITappIT227 Canadian Standard Freeness CaMberrti.I mcumml All r44s reserved.No Eupiration m d�Io N partials pm .. t M when rinser.of ANDRIT AG_ Page 3 of 11 &M U Pulp a Paper Test Results Table 1. Softwood Do-E-D Bleaching Sample Mill Post 02 Softwood Sample ID 124558 Kappa number 14.2 Viscosity, mPa s 14.3 ISO Brightness, % 35.2 Do Stage: 150eF. 40 min., 10% cons. Sample ID 124574 Kappa Factor 0.24 C1O2, % 1.29 H2SO4, % 0.35 Final pH 2.8 Consumed C1O2, % 1.29 ISO Brightness, % 51.9 Color, C.U. 1850 Eo Stage: 1750F, 60 min..35 psi 0 psi. 10 min.. 10% cons. Sample ID 124575 NaOH, % 0.9 Final pH 11.0 Kappa Number 3.2 Viscosity, mPa s 13.8 ISO Brightness, % 58.2 Color, C.U. 2390 D Stage: 165eF, 240 min., 10% cons. Sample ID 124576 CIO2, % 1.0 1.2 1.4 NaOH, % 0.45 0.54 0.6 Final pH 4.2 4.1 3.6 CIO2 Consumed, % 1.0 1.197 1.396 ISO Brightness, % 84.6 85.1 86.1 Color, C.U. -- -- 59 Viscosity, mPa•s 11.2 (corrected) Gpnfgent dppu t All rights reserved.No dug'Ice6on a d,sc ..Ip t Id pa ti.permitted wN ,ft vm1 m.,&ANDRIR AG. Page 4 M I I AM 1 L Pulp a Paper Table 2. Softwood Do-Eop-D Bleachng Sample Mill Post 02 Softwood Sample ID 124558 Kappa number 14.2 Viscosity, mPa-s 14.3 ISO Brightness, % 35.2 Do Stage: 150°F, 40 min., 10%, cons. Sample ID 124577 Kappa Factor 0.2 CIO2, % 1.08 H2SO4, % 0.49 Final pH 2.9 Consumed C1O2, % 1.08 ISO Brightness, %e 49.0 Color, C.U. 2125 Eop Stage: 175eF, 60 min.,35 psi. psi ' 0 psi. 10 min., 10%cons. Sample ID 124578 NaOH, % 1.1 H2O2, % 0.5 Final pH 11.0 Kappa Number 3.2 H2O2 Consumed, % 0.5 Viscosity, mPa-s 12.9 ISO Brightness, % 64.3 Color, C.U. 2045 D Stage: 165°F, 240 min., 10% cons. Sample ID 124579 C1O2, % 1.0 1.2 1.4 NaOH, % 0.45 0.54 0.6 Final pH 4.4 3.8 4.0 C1O2 Consumed, % 1.0 1.2 1.4 ISO Brightness, % 84.8 85.6 86.2 Color, C.U. --- --- 58 Viscosity, mPa-s --- --- 10.8 Gonfidentu document.All rights reserved.No du WA Pion or Gsd um to ftd pertiers gemtifmtl wi 1 Die wr m co s of ANDRIR AG, Page 5 of 11 AWMTL Pulp s Paper Table 3. Softwood Do-Pht-D Bleaching Sample Mill Post 02 Softwood Sample ID 124558 Kappa number 14.2 Viscosity, mPa-s 14.3 ISO Brightness, % 35.2 Do Stage: 150eF, 40 min., 10% cons. Sample ID 124580 Kappa Factor 0.2 CIO2, % 1.08 H2SO4, % 0.49 Final pH 2.9 Consumed C1O2, % 1.08 ISO Brightness, % 48.8 Color, C.U. 2125 PNT Stage: 2000F, 60 min., 100 psi. 15 min. 10%, cons. Sample ID 124581 NaOH, % 1.4 H2O2, % 0.6 Final pH 11.1 Kappa Number 2.8 Viscosity, mPa s 12.3 ISO Brightness, % 67.5 Color, C.U. 1640 D Stage: 165°F. 240 min., 10% cons. Sample ID 124582 CIO2, % 0.8 1.0 1.2 NaOH, % 0.30 0.40 0.50 Final pH 3.9 4.0 4.0 CIO2 Consumed, % 0.8 1.0 1.2 ISO Brightness, % 84.5 85.6 86.4 Color, C.U. -- -- 71 Viscosity, mPa s 10.7 ConfMenoal tloc Ml.All nghls reserved.No d ,,N Uon or die mum to tl pertlers pertMled w t ft rriam consent of ANDRITZ AG. Page 6 a t l AWMTL Pulp a Paper Table 4. Hardwood Do-E-D Bleaching Sample Mill Post 02 Hardwood Sample ID 124655 Kappa number 6.8 Viscosity, mPa-s 13.8 ISO Brightness, % 44.1 Do Stage: 1500F. 40 min., 10%cons. Sample ID 124570 Kappa Factor 0.26 C1O2, % 0.67 H2SO4, % 0.7 Final pH 2.5 Consumed C1O2, % 0.67 ISO Brightness, % 67.4 Color, C.U. 685 E Stage: 175°F. 60 min., 10% cons. Sample ID 124571 NaOH, % 0.9 Final pH 11 Kappa Number 2.7 Viscosity, mPa•s 13.1 ISO Brightness, % 68.4 Color, C.U. 570 D Stage: 165T. 160 min., 10% cons. Sample ID 124572 CIOZ, % 1.0 1.2 1.4 NaOH, % 0.40 0.48 0.56 Final pH C1O2 Consumed, % 0.997 1.190 1.394 ISO Brightness, % 85.5 86.1 86.7 Color, C.U. -- 27 -- Viscosity, mPa•s 10.7 C fM nl document All rights reserved.No dupli Aon or disdosum to Ihi por s pmnilted wi0mut t1w w tlm c N of ANDRITZ AG. page 7 of 11 AMRMTL Pulp & Paper Table 5. Hardwood Do-Pn-D Bleaching Sample Mill Post 02 Hardwood Sample ID 124655 Kappa number 6.8 Viscosity, mPa s 13.8 ISO Brightness, % 44.1 Do Stage: 1500F. 40 min., 10%cons. Sample ID 124743 Kappa Factor 0.21 CIO2, % 0.54 H2SO1, % 0.7 Final pH 2.7 Consumed CIO2, % 0.54 ISO Brightness, % 64.7 Color, C.U. 373 PHT Stage: 2000F, 60 min., 100 psi. 15 min. 10% cons. Sample ID 124744 NaOH, % 1.3 H2O2, % 0.5 MgSO4, % 0.1 H2O2 Consumed % 0.5 Final pH 11.3 Kappa Number 2.7 Viscosity, mPa•s 11.6 ISO Brightness, % 79.4 Color, C.U. 210 D Stage: 1650F. 160 min.. 10% cons. Sample ID 124745 CIO2, % 0.2 0.4 0.6 H2SO4, % 0.09 0.01 -- NaOH, % -- -- 0.05 Final pH 4.2 4.0 3.4 CIO2 Consumed, % 0.2 0.4 0.6 ISO Brightness, % 84.9 86.7 87.8 Color, C.U. -- 52 -- Viscosity, mPa s 11.3 Cwfitlenri tlocumml.All noM resmv W tl pfratbn or,A,tl m to Ihvtl px m pem,6b4 xet,out tl xeitlen a &t RITZ AG. page 8 a}11 AMR/TL Pulp a Paper Table 6. Hardwood Do-Ep-D Bleaching Sample Mill Post 02 Hardwood Sample ID 124655 Kappa number 6.8 Viscosity, mPa s 13.8 ISO Brightness, % 44.1 Do Stage: 150°F, 40 min.. 10% cons. Sample ID 124746 Kappa Factor 0.21 CIOz % 0.54 H2SO4, % 0.7 Final pH 2.7 Consumed CIO2, % 0.54 ISO Brightness, % 65.0 Color, C.U. 345 Ep Stage: 175eF, 60min., 10% cons. Sample ID 124747 NaOH, % 1.0 H2O2, % 0.3 Final pH 11.1 H2O2 Consumed, % 0.3 Kappa Number 2.7 Viscosity, mPa-s 12.0 ISO Brightness, % 74.8 Color, C.U. 365 D Stage: 165°F. 160 min.. 10% cons. Sample ID 124818 CI02, % 0.6 0.8 NaOH, % 0.04 0.24 Final pH 4.4 3.8 CI02 Consumed, % 0.6 0.8 ISO Brightness, % 85.7 86.3 Color, C.U. -- 32 Viscosity, mPa s 10.8 Confidential document.Ail dphM reserved.No 6 pPcalion or dlctlosme to Oird par pemMted without d,e wddeo oon of ANORIR AG. Page 9 of 11 AmxbTL Pulp a Paper Table 7. Physical Strength Properties PH Cond Burst Tensile Tear Tensile Elongation Descriptive CSF Wt Bulk Index Index Index T.E.A.U/m2) Stiffness LIMS ID ID (# (mL) (gm) (cm'/g) (kPa•m'/g) (N-m/g) (mN-m'/g) (kNlm) (mm) revs 124572 0 557 6.50 1.87 1.34 29.37 9.06 26.68 335.7 1.90 0.5 528 6.51 1.66 2.53 48.94 9.31 61.65 435.3 2.69 HW, Do-E-D 1.0 483 6.39 1.56 3.35 60.40 8.44 82.13 470.0 3.02 2.0 356 6.38 1.45 4.25 69.36 8.00 105.58 495.4 3.43 3.0 246 6.35 1.37 4.71 76.39 7.20 119.32 519.1 3.54 124576 0 691 6.63 1.76 2.40 36.64 22.11 58.16 356.5 3.17 0.5 660 6.56 1.56 4.25 60.34 12.96 89.49 473.6 3.23 SW, Do-Eo-D 2.5 520 6.58 1.42 5.30 81.19 9.69 108.98 576.5 3.00 5.0 350 6.28 1.39 5.83 86.49 8.26 118.57 568.7 3.22 7.5 235 6.38 1.35 6.16 88.63 8.31 129.55 587.9 3.37 124579 0 678 6.44 1.82 2.33 34.93 20.95 49.45 344.1 2.90 0.5 632 6.71 1.57 4.38 64.61 12.07 114.04 493.9 3.77 SW,Do-Eop-D 2.5 408 6.46 1.39 5.70 83.65 8.44 133.23 558.1 3.62 5.0 172 6.33 1.32 5.94 88.41 7.55 133.06 579.5 3.49 7.5 88 6.28 1.27 6.32 93.91 7.14 140.25 589.7 3.50 124582 0 696 6.48 1.86 2.22 33.44 23.08 44.76 332.5 2.73 0.5 652 6.44 1.58 4.07 62.12 13.11 95.83 463.4 3.43 SW, Do-PHT-D 2.5 461 6.46 1.41 5.39 79.90 8.80 120.16 543.8 3.40 5.0 201 6.33 1.31 5.91 88.56 7.58 130.04 576.0 3.39 7.5 91 6.37 1.28 6.23 96.06 7.31 148.79 614.6 3.56 124745 0 593 6.54 1.9 1.24 29.30 8.12 27.57 334.0 1.93 0.5 554 6.49 1.66 2.45 49.52 9.57 63.72 435.2 2.76 HW, Do-PHT-D 1.0 515 6.42 1.56 3.13 59.43 9.78 79.92 472.7 2.97 2.0 384 6.44 1.44 4.24 72.03 8.91 110.08 516.4 3.38 3.0 269 6.34 1.37 4.62 76.72 8.11 117.64 513.6 3.47 124818 0 556 6.46 1.90 1.39 30.64 8.54 25.90 341.7 1.79 0.5 536 6.47 1.65 2.60 51.95 9.40 66.86 445.5 2.76 HW, Do-Ep-D 1.0 484 6.46 1.53 3.31 61.04 9.18 82.53 478.8 2.97 2.0 377 6.52 1.44 4.08 71.15 8.69 110.91 522.4 3.40 3.0 260 6.38 1.36 4.45 72.30 8.05 111.83 509.0 3.42 Confpentiel dmuo nt.Al rghb reserved.No d.111,, Ion or disclosure to Mid Wart permitted wif ijt the w ,t consent of ANDRITZ AG. Page 10 of 11 AMRMTL Pulp a Paper Miscellaneous Information All samples included in this report will be held in cold storage for three months after issuance of the report. At that time, the samples will be discarded without notice. If there is a need to retain sam- ples longer than the three-month grace period, please contact PITC. COMB W doament Ad rights reserved.No duplication or diodosure to t W Ps PemiYal w g when 000 a o/ANDRRZ AG Page 11 of 11 a r Laboratory Study of Likely Effects of Oxidatively Intensifying the Extraction Stages at Evergreen Packaging's Canton, NC Mill Progress Report T om 7 l�Ic '-on , u h a ,,� Febr aK 109 201.2 (Draft 2) Confidential Executive Summary This report describes a study undertaken to study and document the effects of oxidatively reinforcing the Canton mill's extraction stages. The effect on effluent color was of particular interest; effects on chemical consumption and bleached pulp physical properties were also measured. Mill oxygen delignified softwood and hardwood pulps were subjected to laboratory bleaching trials. In the case of the softwood pulp trials, existing(EO) stage conditions were compared with conditions chosen to simulate(EPO) and(PO) stages.The(EPO) stage was simulated by adding 0.5%hydrogen peroxide. The (PO) stage(sometimes referred to as a pressurized peroxide or PHT stage) was simulated by increasing the temperature, oxygen pressure and peroxide charge. In the case of the hardwood pulp trials, the existing E stage conditions were compared with conditions chosen to simulate(EP) and(PO) stages. The(EP) stage was simulated by adding 0.3% peroxide. The PO stage was simulated by inargising the peroxide charge, pressurizing with oxygen and raising the temperature. In both cases the chlbijiie dioxide charge in the Do stage was decreased slightly and the chlorine dioxide charge in the D . take was adjusted to reach the desired target brightness. Effects on the color of all bleaching stag iefflu°nts were monitored. Effects on bleaching chemical consumption and bleached pulp physical proper ies w re als\oo measured. In the softwood case, adding peroxide to the(EO) stage result d n almost no�d1drease in total effluent color. Converting the(EO) stage to a (PO) stage decreas d ttZtotal color by 11 o Tot 1 chlorine dioxide consumption was reduced by 5.6— 10 lb/ton (0128 0Z%on pulp). `�. N' In the hardwood case, adding peroxide resulted in a 429/e rMuctio" or. Converting[h' E stage to a o!lyw (PO) stage gave a 50% reduction. Total chlorine dioxide c�b> ptrC was reduced by 12— 161b/ton(0.6— 0.8% on pulp) With a few exceptions, effects on the physic lip�'oche of both pulpgkpes were generally small or nonexistent.The exceptions were increases in elangaho tensile energky absorption of the softwood pulps and increases in maximum tearing resista'c stren��o�e, az(w�nod pulps, as well as increases in the tensile strength at which tna lum�teazin r il^',SCce s dried. The results suggest that there little to be gained b u° plementing the softwood pulp extraction stage modifications studied here. In the case of the hardwod ulp, however, adding peroxide to the extraction stage has the potential to' uAtantially decrease the col rj;of the pulp bleaching effluent and significantly decrease chlorine dioxide cobsutnpti&. Introcfull n The Canmploys the �-NoO)D�_cching sequence to produce bleached softwood and hardwood pulps. The trul tcommissioned a a oratory�study to predict the effects of intensifying the alkali extraction stages in the ..aching sequences of�both softwood and hardwood pulps. In the case of softwood,this amounted to con the(EO)' tage to either an (EPO) stage or a high-temperature pressurized peroxide nr stage, here denoted yFZP,O). In�the c�ase of hardwood the study assessed the effects of converting the E stage to a peroxide reinforcedi!exraction stage(EP) or a(PO) stage. These changes can be expected to reduce the color of the mill effluent. Post-oxygen mill pulps were the starting materials for the study. The kappa number and viscosity of the softwood pulp were, respectively, 14.2 and 14.3 mPa.s.The kappa number of the hardwood pulp was 6.8 and its viscosity was 13.8 mPa.s. After each stage, the pulps were characterized by suitable measurements (kappa number, brightness and/or viscosity, depending on the stage) and the color of the effluent from each of the last three stages was measured. In addition, fully bleached samples were subjected to laboratory refining and the physical properties of the refined pulps were measured. The experiments were performed at the Pruyn's Island Technical Center of Andritz Inc. The raw data and details of the experimental procedures used maybe found in their report.' 2 Results and Discussion Multistage Bleaching Tables I and 2 contain the results of the multistage bleaching experiments that were performed on the softwood and hardwood pulps, respectively. Effluent Color Figures land 2 illustrate the effects of reinforcing the extraction stage on the color of the bleaching stage effluents. Figure 1 shows that, in the softwood case, adding peroxide to an(EO) stage to convert it to an (EPO) stage resulted in almost no decrease in total color, measured as the sum of the three individual effluent color values. Increasing the temperature, oxygen pressure and per a charge, i.e. converting the (EO) stage to a(PO) stage,decreased the total color from 4299 units to nits (an I I%reduction). In both the(EPO)and(PO)cases, the attendant decreases in Do kappa CIO2 charge)caused slight increases in the color of the Do effluent. 6000 5000 4299 4228 4000 3836 ❑D1 0 ■E Y .0 3000 ■DO 0 0 U 2000 b low-, 1000 0 (EO) (EPO) (PO) Figure 1. Effects of extraction stage reinforcement on softwood bleaching effluent color In the hardwood case there were somewhat greater effects of reinforcing the extraction stage, as Figure 2 shows. Adding peroxide decreased the total color(again measured as the sum of the individual stage effluent color values)from 1282 to 742 units(a 42%reduction). Increasing the temperature, oxygen pressure and peroxide charge, i.e. converting the(EO)stage to a(PO) stage, further decreased the total color to 635 units (a 50%reduction relative to the value obtained when the extraction stage employed neither oxygen nor peroxide). 3 Table 1. Results of Bleaching Softwood Pulps Type of Extraction Stage (EO) (EPO) (PO) Unbleached kappa number 14.2 14 2 14.2 Viscosity, mPa•s 14.3 J4.13Y 14.3 ISO Brightness, % 35.2 = 352 35.2 Do Stage: 150°F,40 min., 10% cons. C102,% 1.29 1.08 1.08 H2SO4, % 0.35 0.49 0.49 Final pH 2.8 2.9 2.9 Residual g/L as C12 0 0 0 ISO Brightness, % 51.9 - 49.0 49.0 Filtrate color, C.U. 1850 2125 2125 Extraction Stage: 60 min., 10% cons. NaOH, % 1.4 Temperature, T 175� 175 200 02 Pressure(0/10/15/60 min.), psig ( 5101010) (3'5/0/0/0) (100/100/0/0) H2O2, % 0 0.5 0.6 Final pH 1.0 11.0 11.1 Kappa Number 3.2 3.2 2.8 Viscosity, mPa•s 1 .8 12.9 12.3 ISO Brightness, % 58.2 64.3 67.5 Filtrate color, C.U. 2390 2045 1640 i D, Stage: 165°F,240 min , 10% cons. C102, % .2 1.4 1.0 1.2 1.4 0.8 1.0 1.2 NaOH,%p 0.4 0.54 0.6 0.45 0.54 0.6 0.3 0.4 0.5 Final pH 4. 4.1 3.6 4.4 3.8 4.0 3.9 4.0 4.0 Residual C102, g/L 0 0.003 0.004 0 0. 0 0 0 0 Total Sequence C102,% 2.29 2.49 2.69 2.08 2.28 2.48 1.88 2.08 2.28 Viscosity, mPa•s -- -- 11.2 -- -- 10.8 -- -- 10.7 ISO Brightness, % 84.6 85.1 86.1 84.8 85.6 86.2 84.5 85.6 86.4 Filtrate color, C.U. -- -- 59 -- -- 58 -- -- 71 4 Table 2. Results of Bleaching Hardwood Pulps Type of Extraction Stage E (EP) (PO) Unbleached kappa number 6.8 A13.8 6.8 Viscosity, mPa•s 13.8 13.8 ISO Brightness, % 44.1 44.1 Do Stage: 150°F,40 min., 10% cons. C102,% 0.67 . 0.54 H2SO4, % 0.7 0.7 0.7 Final pH 2.5 2.7 2.7 Residual g/L as C12 0 (3445 0 ISO Brightness, % 67.4 64.7 Filtrate color,C.U. 685 373 Extraction Stage: 60 min., 10% cons. NaOH, % 1.3 Temperature, °F 175 200 02 Pressure(0/10/15/60 min.),psig (0/0/ 0 (0 /0) (100/100/0/0) H2O2, % = 0 0.3 0.5 Final pH 11.0 11:1 11.3 Kappa Number 2.7 2.7 2.7 Viscosity, mPa•s 12.0 11.6 ISO Brightness, % 68 4 74.8 79.4 Filtrate color,C.U. 570 365 210 D, Stage: 165°F,240 in' ., 10% cons. Ir C102. % 1.0 1.2 1.4 0.6 0.8 0.2 0.4 0.6 NaOH/H2SO4,% 0. 0/0 0.48/0 0.56/0 0.04/0 0.24/0 0/0.09 0/0.01 0.0510 Final pH -- -- 4.4 3.8 4.2 4.0 3.4 Residual C102, g/L 0003 0.010 0.006 0' 0 0 0 0 Total Sequence C102,% 1.67 1.87 2.07 1.14 1.34 0.74 0.94 1.14 Viscosity, mPa•s -- 10.7 -- 10.8 -- 11.3 -- ISO Brightness, % 85.5 86.1 86.7 85.7 86.3 84.5 85.6 86.4 Filtrate color, C.U. -- 27 -- -- 32 - 52 5 1600 1400 1282 1200 D1 rn 1000 c ® E 800 742 o 635 1-1 Do v 600 400 200 - , 0 E Ireinfor P) PO) Figure 2. Effects of extraction stage ent on hardwood bleaching effluent color The results s ,Figure. I and 2 ,uggest that there is little to be gained by implementing the softwood traction e modifications studied here. In the case of the hardwood pulp, however, adding de to the extr n aLtge has the potential to substantially decrease the color of the hardw bleaching of l pent. In regard to t ffluent color reductions, it should be noted that the reductions achieved in actual mill practice may be ly different. When individual stage effluents are combined the color that results is not the sum of the t ual stage effluents. One reason for this is that the color of extraction stage effluents is pH depen their color is decreased when they are acidified. Adding acidic D stage effluents to extraction stage effluents decreases their pH and therefore also decreases their color.This effect may be offset to some extent by a pH-dependent increase in the color of the D stage effluents. Chemical Consumption Figure 3 illustrates the favorable effect of reinforcing the extraction stage on total C102 consumption when bleaching softwood pulp. At a foal brightness level of 86.0,and under the conditions of these experiments, adding 10 lb of peroxide per ton of pulp to the(EO) stage may be expected to result in a reduction in total C102 consumption of 5.6 lb/ton(0.28%on pulp). Further intensifying the extraction stage by increasing the peroxide charge to 121b/ton, increasing the temperature and pressurizing with oxygen may be expected to result in a further reduction of 4.4 lb/ton(0.22% on pulp). In this case the 6 total reduction in C102 consumption would therefore be 10 lb/ton(0.5%on pulp)relative to the(EO) case, where peroxide was not used. 87.0 Z:(EPO) 86:5 r 85.5 85.0 ; 84.5 • , 84.0 1.6 1.8 2.0 2.2 2.4 2.6 2.8 - Total CI02(Do+D, ,0. Figure 3. Final brightness S. to O consum do ; softwood pulp. Figure 4 shows the correspo for the dw d pulp:Addmg 6 lb of peroxide per ton of pulp to the extraction stage resulte m a red cti n in tot 1 02 consumption of 12 lb/ton of pulp (0.6% on pulp.. Adding high-pressure oxygen an m ceasing t e eroxide charge to 101b/ton while also increasing the temperature resulted t a rther r uc 'on of 41b t n 0.2% on pulp). In this case the total reduction in C102 consumption woul t e f re a 16 /ton 0. n pulp)relative to the case where neither oxygen nor peroxide was us 87.0 86.5 86.0 ----------------- ---- --------------- ---------- N d i • i C t 85.5 ' , m � I 9 i i ♦E 85.0 I I •(EP) i 84.5 84.0 � 0.4 0.6 0.8 1.0 1.2 ,1 /11 6/ 1.8 2.0 2.2 2 4 Total CIO"(Do'+Dl),% Figure 4.Final brightness vs. total C102 consumption; hardwood pulp. Physical Properties of Bleache Pul s Softwood Pulps results in T ble 3 sho s that tht s udied•exxt a ti`n to a modifications had, with one Inspection of the es ✓ 4 r g possible exception, virtua . no effect n t e physical properties of bleached softwood pulp. Figure 5 demonstrates the lack o�n}' effects on he relationship between handsheet density and tensile strength and Figure 6 shows thair�,y�11 three a traction types�ga e pulps with the same tear-tensile characteristic. The possible exception is a effect n elon atlan d its associated effect on tensile energy absorption, as shown in Figures-7-and�8. Ta�b7e�3. h s Properties of Bleached Softwood Pulps Tensile Burst Tear Tensile Density Elongation Pulp ID PR CSF Index Index Index T.E.A. Q/m2) Softness lnd (#revsx 103) (ML) (gtZ) (H'u✓8) (kPa ml/&) (mN•m'/e) (kNMB) (EO) \0.0 691 0.568 36.64 2.40 22.11 58.16 3.17 356.5 Os 66D 0.64I 60.34 4.25 1296 89.49 3.23 473.6 2.5 \N520� 0.704 91.19 5.30 9.69 108.98 3.00 5765 5.0 350 0.719 86.49 5.83 826 118.57 3.22 568.7 7.5235 0.741 88.63 6.16 1 8.31 129.55 1 3.37 587.9 (EPO) 0.0 678 0.549 34.93 2.33 20.95 49.45 2.90 344.1 0.5 632 0.637 64.61 4.38 12.07 114.04 3.77 493.9 2.5 408 0.719 83.65 5.70 8.44 133.23 3.62 558.1 5.0 172 0.758 88.41 5.94 7.55 133.06 3.49 5795 7.5 88 0.787 93.91 6.32 7.14 140.25 3.50 589.7 (PO) 0.0 696 0.538 33.44 222 23.08 44.76 2.73 3325 0.5 652 0.633 62.12 4.07 13.11 95.83 3.43 463.4 2.5 461 0.709 79.90 5.39 8.80 120.16 3.40 543.8 5.0 201 0.763 88.56 5.91 7.58 130.01 3.39 576.0 75 91 0.781 96.06 1 6.23 1 7.31 1 148.79 1 3.56 1 614.E 8 120 "0 M(E ) i • 80 Z a f � 60 m N � 40 20 0 0.45 - 0.50 0.55 0.60 0.65 0.00.75 0.80 .85 Density,g/c s Figure 5.Softwood pulp to it index vs.sheet density 30 25 L 'z •(EO) •(EPO) N E, 2 ■(PO) z E axi 15 v y 0 • 5 i Zti,i 20 40 60 80 100 120 Tensile Index, N.m/g Figure 6.Softwood pulp tearing resistance vs. tensile index 9 4.00 3.80 3.60 E 3.40 E 3.20 c ° 3.00 A rn 0 2.80 •(EO) m 2.60 •(EPO) ■ Po 2.40 2.20 2.00 I u 0 20 40' 60 . 80 100 20 Tensile Index/. ' /g Figure 7.Softwood pulp lingation vs.TR ile Index ., 180 160 r 140 12 E 100 a/ a w"80` F I� 60 •(Eo) •(EPO) 4O ■(PO) 20 0 N 0v 20 40 - 60 80 100 120 Tensile Index,N.m/g Figure 8.Softwood pulp tensile energy absorption vs. tensile index Hardwood Pulps The results in Table 4 indicate that the studied extraction stage modifications had virtually no effect on the physical properties of bleached hardwood pulp, with one exception. Figure 9 demonstrates the lack of any effects on the relationship between handsheet density and tensile strength. The exception to the above statement is illustrated by Figure 10, which shows that intensification of the extraction stage increases the 10 maximum tearing resistance that can be achieved by refining and also increases the tensile strength at which the maximum tearing resistance is achieved. Table 4.Physical Properties of Bleached Hardwood Pulps Tensile Burst Tear Tensile DensPulp ID PH CSF ) ( Index Index index T.E.A. (/m2) Elonga-)ion ( Stiffness Inde (#)evs x 103) (ML) B/emnm (N-Mg) (kPa-rnVg) (mN.01g) mm) (kNMg) E 0.0 557 0535 29.37 1.34 9.06 26.68 1.90 335.7 0.5 528 0.602 48.94 2.53 931 61.65 2.69 435.3 1.0 483 0.641 60.40 3.35 8.44 / /6�82.13 3.02 470.0 2.0 356 0.690 69.36 4.25 8.00 ! /10559 3.43 495.4 3.0 246 0.730 1 76.39 4.71 1 7.2 :11: a / 11932 1 3.54 519.1 (EP) 0.0 556 0.526 30.64 139 Q 5�¢^ 25.90 1.79 341.7 0.5 536 0.606 51.95 2.60 ) :40 \ 66gZ\Z.88�6 2.76 445.5 9.18 2.0 377 0.694 71.15 ,,4/0 � 8.69 I10..9� 3.40 522.4 3.0 260 0.735 72.30 .F4:451 8.05 111.83 3.42 509.0 (PO) J3.0 593 0526 29.30 <` ' 124 8.1y 27.57 \,'°L93 341.7 554 0.602 49.52 \T45 57 63.72 287§� 445.5 515 0.641 59.43 3,1 79.92 2.97 478.8 384 '0.694 72.03 4.24\ 91 110.08 3.38 522.4 269 1 0.730 ,.76,j2 4.62 \\„ S.11 117.64 3.47 509.0 90' \ \: 80 •E ♦(EP) ■(PO) E 7U® • E D X 60 y 9 � C � d 5 N C ' ~ 40 30 '/• 20 0.45V.50 0.55 0.60 0.65 0.70 0.75 0.80 Density,g/cc Figure 9. Hardwood pulp tensile index vs. sheet density 11 10 ■ 10 ■ • 9 a E 9 • z E x" 6 d v c `m 6 E 7 7 iir ; �, 6 20 30 40 50 60� 70 80 `901N� Tensile TAU; m/g _ ,!Iiii Figure 10.Hardwood pulp tearing resistance vs, tensile index Summary and Conclusions Nil y Mill oxygen-delignified softwood and hardwood i ulps were-subjecte st6laboratory bleaching trials to evaluate the effects of potential^changes to the c ndt�ons t Ikal extraction stage. In the case of the i � s iin° softwood pulp trials, existi�g O}slag\e conditto s,ilwer compare ith conditions chosen to simulate (EPO) and(PO) stages�he(EPO) stage�las simul te�by adding 0.5% hydrogen peroxide. The(PO) stage(sometimes referred tons a pressurized peroxidejor,Pm stage)was simulated by increasing the temperature, oxygen press u e and peroxtd�charge.IInTh ase of the hardwood pulp trials, the existing E . stage conditions er ce o npared�vith conditions chosen.to simulate(EP) and(PO) stages. The(EP) stage was simulated y'ts g;03%peroxide. The PO stage was simulated by increasing the peroxide charge, pressurizing w t oxygen'andlraisinglthe temperature. In both cases the chlorine dioxide charge in the Do stage wa(d., reased slightir2fi'd the chl\n dioxide charge in the D) stage was adjusted to reach the desired tar�e,,t� b * fitness. Effe�CQs5 the color of all bleaching stage effluents were monitored. Effects on bleaching chd �al consumptto a d bleached pulp physical properties were also measured. In the softwood caa��e;+addmg pe�� zide to an(EO) stage to convert it to an(EPO) stage resulted in almost no decrease in totals Al,oe meas�ur as the sum of the three individual effluent color values. Increasing QQ ;:uu the temperature, oxyge�i�t Ppresssi nd peroxide charge, i.e. converting the(EO) stage to a(PO)stage, decreased the total color (Tin 4299 units to 3836 units (an 11% reduction). In both the(EPO) and(PO) cases, the attendant decreases in Do kappa factor(CIOZ charge) caused a slight increase in the color of the Do efffluent. In the hardwood case there were somewhat greater effects on effluent color. Adding peroxide decreased the total color(again measured as the sum of the individual stage effluent color values) from 1282 to 742 units (a 42%reduction). Converting the(EO) stage to a(PO) stage further decreased the total color to 635 units (a 50%reduction relative to the value obtained when the extraction stage employed neither oxygen nor peroxide). 12 Reinforcing the extraction stages decreased total chlorine dioxide consumption by as much as 10 lb/ton (0.5% on pulp) in the case of softwood pulp and by as much as 16 lb/ton(0.8% on pulp) in the case of the hardwood pulp. With a few exceptions, effects on the physical properties of both pulp types were generally small or nonexistent.The exceptions were increases in elongation and tensile energy absorption of the softwood pulps and increases in maximum tearing resistance strength and in the tensile strength at which the maximum tearing resistance is achieved. In general, the results suggest that there is little to be gained by implementing the softwood pulp extraction stage modifications studied here. In the case of the hardwood pulp,however, adding peroxide to the extraction stage has the potential to substantially decrease the color f the pulp bleaching effluent and significantly decrease chlorine dioxide consumption. ' ' Report:No.2011-054, Pruyn's Island Technical Center;'Andritz Inc. (August 3, LI I!r« ,f- . I -" If xa� s=L�ryl °In-• i n Hi�L 13 Andritz—Alstrom 02 Delig Studies CONFIDENTIAL BUSINESS INFORMATION 6 PRUYN'S ISLANID TECHNICAL CENTER REPORT 2001-068 PART 1. LABORATORY CK AND LO-SOLIDS COOKING WITH O-Do-Eop-D BLEACHING SEQUENCES ON SOFTWOOD FURNISH FROM BLUE RIDGE PAPER,BLUE RIDGE,NC Part 1. Softwood Results Part 2. Hardwood Results TO: Allen Turner Jay Miele Issued: December 6, 2001 Issued by: Scott Daley and Keith Crofut Tel.(518)745-2980 Fax(518)745-2971 Allen Turner Pruyn'sIsland Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Summary Blue Ridge Paper of Blue Ridge, NC requested the sales department of Andritz-Ahlstrom to investigate alternate methods of pulping and bleaching that would reduce their waste products and improve the quality of their hardwood and softwood paper products. As a result, the Pruyn's Island Technical Center produced Conventional Kraft (CK) and Lo-Solids® (LS) brownstock, oxygen delignified and fully bleached pulps for strength testing and comparison to current mill pulp samples supplied by the mill in June of 2001. Currently, the mill batch cooks-both softwood and hardwood pulp. The bleaching sequence is O- Do-Eo-D with hydrogen peroxide addition in the E stage when the softwood is produced. The fully bleached lab pulps were produced using the current mill sequences and an alternative hardwood sequence O-A-ZDo-Eo-D. Thd brightness targets were softwood ISO 88% and hardwood ISO 89%. Throughout the lab bleaching, the effluent colour was monitored and the metals content of the softwood bleach filtrates was determined. The mill supplied a MRP filtrate sample (sample ID 2001-002005) for use in all lab softwood Do stages. The mill also supplied unscreened brownstock, oxygen delignified, and fully bleached pulps. This part of Report 2001-068 deals with the softwood pulp production and bleaching only. For details concerning the hardwood see PITC lab report 2001-068 Part 2. Observations • Laboratory conventional kraft pulp kappa numbers ranged from 18.7 to 37.2 The viscosities ranged from 20.0 to 31.2. (Viscosity for Cook S3136 was not measured as the kappa number was greater than 35).The total brownstock yields ranged from 42.3 to 45.9 % on wood. • Laboratory Lo-Solids° pulps ranged in kappa number from 22.3 to 31.1. The viscosities of the lab LS pulps ranged from 30.2 to 41.7 mPa•s. The brownstock total yields ranged from 42.3 to 43.3 (total yield for cook AL773 was not measured as the kappa was not in the targeted range). • The bleaching results are summarized below: Brightness Viscosity C102Charge H20,Charge Pulp and Se4uence %ISO mPa•s Kg/BDMT Kg/BDMT Softwood Mill BS Lab O-Do-Eop-D 88.0 14.3 18.0 5.0 Mill Oz Lab Do Eop-D 88A 13.6 18.8 5.0 Mill Fully Bleached 87.6 15.7 --- --- Lab CK Lab O-Do-Eop-D 87.9 13.4 17.0 5.0 Lab LS Lab O-Do-Eop-D 89.5 17.1 16.3 5.0 • The strength results demonstrate Lab Lo-Solids pulps are superior in tear index versus tensile index when compared to mill pulps. (see Table 1-10 and Figure 1-5) c,ma=cnu an65etsivgslmushaWucal SettingsWemprary ltnmt FiloMMU001-068 P I SW Final Repa2tlac �njyn4 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Experimental The mill requested that the MRP filtrate be added to all softwood Do stages to simulate mill conditions. Standard OQerating Procedures PTTC-1`27 Lo-Solids®Cooking Simulation(27 Liter Circulating Digester) PITC-P6 Wood Chip Size and Thickness Distributions PTTC-1`7 Wood Chip Moisture Free Fraction PTTC-P8 General Wood Chip Handling PTTC-P9 Pulp Moisture Free Fraction PTTC-P10 Pulp Yield PTTC-PI l Pulp Defiberin ,Centrifuge Washin ,and Pin-shredding PTTC-P24 Conventional Kraft Cook(5 Liter Swing Digester) TappiT205 om-88 Forming Handsheets for Physical Tests of Pulp Tappi T248cm-85 Laboratory Beating of Pulp(PFI Mill Method) Tappi T227om-94 Freeness of Pulp Tappi 7220s 96 Physical Testing of Pulp Handsheets Tappi T403om-91 Bursting Strenpth of Paper Ta i T414om-88 Internal Tearing Resistance of Paper Tappi T494om-88 Tensile Breaking Properties of Paper and Paperboard PrfC-14 Dirt Count TAPPI T236 Kappa#of pulp SCAN N33 Residual hydroxide(hydroxide ion content)of black liquor SCAN N2:88 AA,EA,TA of white/green liquor-potentiornetric titration TAPPIMO Viscosity of pulp(capillary viscosity method) HUT Method 23.2.1995 Hexenuronic acid content of Kraft pulps PTTC-B3 Oxygen Deli nification PTTC-B4 Chlorination PTTC-115 Acid Hydrolysis(Ahl-stage) PTTC-B6 Alkaline Extraction PTTC-138 Chlorine dioxide bleaching PTTC-B11 Low&medium consistency ozone deli nification in fluidizing mixer PTTC-B 12 Hydrogen eroxide bleaching PTTC-B19 Pulp washing CPPA H.5 Colour of pulp mill effluents PTTC-A18 Carbohydrate content of wood or pulp by HPAEC-PAD Standard Methods 3111 Metals.b FAA Tappi T525 om-92 ISO brightness(pad formation and testing) C:a)onmaau and SenugA=,halydnnl ScUingsU mparuy Inu=ReAOLM0001.068 Part I SW Final Repomdoc 2 � �1 G4ON E Iit IIN 1 11 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Results Table 1-A.Mill Pulp and Filtrate Results Sample Login Kappa Viscosity Brightness Rejects Tappi Dirt Sample Description ID Plumber (diPa•s) %ISO %on Arealppm pulp (w.041)imi) Softwoods5=an44d Brownstock 2001-001999 --- ---- ---- 0.35 --- Lab Screened 2001-002000 21.5 22.0 29.3 -- 419.66 Brownstock Oxygen Delignified 2001-002003 ---- ---- 33.6 276.09 Fully Bleached 2001-002004 ---- 15.7 87.6 ---- 2.06 MRP Filtrate 2001-002005 Metals Content,mg1L Ca=35.88 Fe=0.88 Mg=9.64 Mn=3.52 Colour,C.U. 890 Part 1. Softwood Results. The following list of tables and figures summarizes the results of the work performed on the softwood furnish and the softwood mill and lab pulps. Table 1-1. Softwood Chip Size and Thickness Classifications. J Table 1-2.Laboratory Conventional Kraft(CK) Cooking of Softwood Ty Table 1-3.Laboratory Lo-Solids® (LS) Cooking of Softwood Table 1-4. Laboratory O-Do-Eop-D Bleaching of Mill Softwood Brownstock Pulp Table 1-5. Laboratory Do-Eop-D Bleaching of Mill.Softwood Oxygen Pulp - Table 1-6.Laboratory O-Do-Eop-D Bleaching of Lab Softwood CK Pulp Table 1=7.Laboratory O-Do-Eop-D Bleaching of Lab Softwood IS Pulp Table 1-8.Laboratory Two Stage Oxygen Delignifications of Mill Softwood-Brownstock Pulp Table 1-9. Strength Results for Selected Mill and Lab Softwood Pulps Table 1-10.Tear Index and Tensile Index at 400 CSF of Selected Softwood Pulps Figure 1-1. Total Yield versus Kappa Number for Lab Softwood Cooking Figure 1-2. Laboratory Cooking Response for Softwood Furnish Figure 1-3. Viscosity versus Kappa Number for Lab Softwood Cooking Figure 1-4.EA Consumed versus Kappa Number for Lab Softwood Cooking Figure 1-5. Tear Index versus Tensile Index for Selected Mill and Lab Softwood Pulps. Figure 1-6.Tensile Index versus PFI Revolutions for Selected Mill and Lab Softwood Pulps Figure 1-7. Strength Results for Mill Softwood Brownstock Pulp Figure 1-8. Strength Results for Mill Softwood Oxygen Pulp Figure 1-9. Strength Results for Mill Softwood Fully Bleached Pulp C.ANWmenu and SC ingsVnarsA4WAe41 Sellingau mpalM Inwrct r"0LK41a00l-M P+n I SW My R4pomdW 3 I T I A L Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part I Alpheretta,GA December 6,2001 Figure 1-10. Strength Results for Mill Softwood Brownstock Lab O-Do-Eop-D Bleached Pulp Figure 1-11. Strength Results for Lab Softwood Lo-Solids®Brownstock Pulp Figure'l-12. Strength Results for Lab Softwood Lo-Solids®Oxygen Pulp Figure'1-13. Strength Results for Lab Softwood Lo-Solids®O-Do-Eop-D Pulp Table 1-1. Softwood Chip Size and Thickness Classifications Chip Size Fraction Chip Thickness Fraction (mm) (%) (mm) (%) 0-3 0.1 0-2 1.3 3-7 2.5 2-4 25.2 7- 12.7 22.3 4-6 36.1 12.7-25.4 49.9 6-8 21.8 25.4-45 21.9 8- 10 7.7 45 and greater 3.3 10 and greater 7.8 C.Mmmenu end SeuingAmme0elda 1 Seldnga\Tempmary 1n iHcAOMV001-03 Pan 1 SW Final Repen.dm 4 • Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Table 1-2.Laboratory Conventional Kraft (CK) Cooking of Softwood Cook ID S3136 S5251 S6068 S3137 S5252 S6069 S3140 S3148 Cook Type CK CK CK CK CK CK CK CK Date of Cook 08.03-01 08-03-01 08-03-01 08-06-01 08-06-01 08-06-01 08.09-01 09-05-01 Furnish Southern Pine 2001-001990 Wood Charge(g od) 750 750 750 750 750 750 750 750 Steaming: Temperature(nC) - 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Time(min) 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Impregnation: EA Charge(%on wood NaOH) 19.2 19.2 19.2 21.6 21.6 21.6 21.6 21.6 Liquor Sulfidity(%AA) 27.0 27.0 27.0 27.0 27.0 27.0 27.0 31.2 AQ(%on wood) - - - - - - - - 1IW Ratio(L/1tg) 3.5 3.5 3.5 3.5 3-5 3.5 3.5 3.5 Temperature('C) 110.0 110.0 110.0 110.0 110.0 110.0 110.0 110.0 Time to Temperature(min) 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Time at Temperature(min) 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Co-current: Temperature(°C) 165.3 169.5 170.0 166.4 169.5 163.8 166A 166.4 Time to Temperature(min) 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 Time at Temperature(min) 88.0 91.0 102.0 111.0 107.0 104.0 112.0 109.0 Final Cooking Results: Residual pH 13.1 13.0 13.0 13.2 13.2 13.2 13.1 13.1 Residual EA(g/L NaOH) l(ki 8.3 7.0 12A 12.0 13.9 12.8 12.7 EA Consumed(%on wood NaOH) .#r 15.7 16.3 16.8 17.3 17.4 10.7 17.1 17.2 H-Factor 960 1430 1680 1320 1670 1040 1320 1290 Kappa Number 37.2 27.5 23.7 21.7 19.7 29.9 21.7 22.8 Viscosity(mPa•s) NM 30.6 27.0 24.5 20.0 31.2 25.4 24.5 Brownstock Total Yield(% on wood) 45.9 44.6 44.1 42.9 42.3 44.9 42.8 43.3 Total Rejects(%on wood) 0.91 0.76 1.05 0.11 0.39 0.49 0.30 0.09 Screened Yield(% on wood) 45.0 43.9 43.0 42.8 41.9 44.4 42.5 43.2 Knots>13 mm(%on wood) 0.61 0.63 °0:94,j 0.03 0.35 0.42 0.23 0.03 'CK=Conventional Kraft Process bAQ=Anthraquinone `SODA=Soda Process CD"umenn89d SetlivgsWarsfilNaal geNngATemponry Intoner PoeAOLICd\2001-068 Put i SW Final ReportdW 5 Allen Turner Prayn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA - December 6,2001 Table 1-3. Laboratory Lo-Solids® (LS) Cooking of Softwood Cook ID AL773 AL775 AL776 Date of Cook 2001-08-14 2001.08-15 2001-08-21 Wood Charge(g od) 3500 3500 3500 Steaming: Temperature(°C) 100.0 100:0 100.0 Time(min) 15 15 15 Impregnation: EA Charge(%on wood NaOH) 10.0 10.0 10.0 Liquor EA(g/L NaOH) 28.6 28.6 28.6 Liquor Sulfidity(%AA) 27.8 27.8 27.8 L/W Ratio(L/kg) 3.5 3.5 3.5 Temperature(°C) 110.0 110.0 110.0 Time to Temperature(min) 15 15 15 , Time at Temperature(min) 30 30 30 Pressure at Temperature(kPa) 923 939 911 Residual pH 12.9 13.0 . 13.0 Residual EA(g/L NaOH) 7.8 7.8 7.8 EA Consumed(%on wood NaOH) 7.3 7.3 7.3 Displacement 1: Temperature(°C) 162.4 164.5 -165.6 Time to Temperature(min) 15 15 15 Time at Temperature(min) 45 45 45 Pressure at Temperature(kPa) 1411 939 1349 EA Charge(%d on wood NaOH) 8.0 8.0 8.0 Liquor EA(glL.NaOH) 87.6 87.6 87.6 L/W Ratio(lAg) 3.5 3.5 3.5 Fresh Liquor Flow(mUmin) 53.0 53.0 53.0 Fresh Liquor Flow Time(min) 60 60 ` 60 Displaced Liquor Flow(mUmin) 53.0 53.0 53.0 Displaced Liquor Flow Time(min) 60 60 60 Residual Liquor pH 12.9 13.1 13.2 Residual Liquor EA(g/LNaOH) 1o.8 10.5 lu Displaced Liquor pH 12.9 13.0 13.0 Displaced Liquor Residual EA(g/L NaOH) 6.9 6.8 7.0 EA Consumed(%on wood NaOH) 6.3 6.4 6.4 C1Docum and SviinpM haMLaal Settinrs\Temponrylnt FaeetOLa4V001.06a Pan I SW Finalftomda 6 -� ll I A Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Table 1-3 (continued). Laboratory Lo-Solids® (LS)Cooking of Softwood Cook ID AL773 AL775 AL776 Co-current 1: Temperature(°C) 162.4 164.5 165.6 Time at Temperature(min) 60 60 60 Pressure at Temperature(kPa) 1120 1135 1278 L/W Ratio(IJkg) 3.5 3.5 3.5 Residual pH 12.9 12.9 13.0 Residual EA(g/L NaOH) 7.0 6.5 6.5 EA Consumed (%on wood NaOH) 1.3 1.4 1.4 Displacement2: Temperature(°C) 162.4 164.5 165.6 Time at Temperature(min) 180 180 180 EA Charge(%on wood NaOH) 0.9 6.9 6.9 Liquor EA(g/L NaOH), 44.7 44.7 44.7 Liquor Sulfidity(%AA) 27.8 27.8 27.8 L/W Ratio(IJkg) 3.5 3.5 3.5 Fresh Liquor Flow(mL/min) 30.0 30.0 30.0 Fresh Liquor Flow Time(min) 180 180 180 Displaced Liquor Flow(mL/min) 30.0 30.0 30.0 Displaced Liquor Flow Time(min) 180 180 180 Residual Liquor pH 13.0 13.1 13.1 Residual Liquor EA(g/L NaOH) 14.0 13.6 13.4 Displaced Liquor pH 13.0 13.1 13.1 Displaced Liquor Residual EA (g/L NaOH) 10.2 9.6 9.9 EA Consumed(%on wood NaOH) 2.9 2.9 3.0 Final Cooking Results: H-Factor 2400 2870 3150 Kappa Number 31.1 25.4 22.3 Viscosity(mpa•s) 41.7 35.2 30.2 Viscosity/Kappa Number Ratio 1.3 1.4 1.4 Total Yield(%n on wood) - NM 43.3 42.3 Total Rejects(%on wood) NM 0.17 0.11 Screened Yield(%on wood) NM 43.1 42.2 Knots>13 mm(%on wood) NM 0.10 0.08 Total EA Consumed(%on wood NaOH) 17.8 18.0 18.0 CADmmenu cnd Se&gAnmaba1r%Lma15e1ingATempam7 Imemel MakOLM0001-068 Pan I SW Fwl Repan.da Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-069 Part I Alpheretta,GA December 6,2001 Table 1-4. Laboratory O-Do-Eop-D Bleaching of Mill Softwood Brownstock Pulp Sample ID Mill Brownstock 2001-002000 Kappa number 21.5 Viscosity,mPa-s 22.0 Brightness,%ISO 29.3 Bleaching Sequence: O-Do-Eop-D O-Stage: 60 min. 90eC.80 psi 10% consistencv Sample ID 2001-00 2530 NaOH,% 1.6 Final pH 11.5 Kappa number 12.6 Viscosity, mPa-s 16.3 Brightness,%ISO 34.1 Filtrate Colour,C.U. 5330 Filtrate Metals,mg/1- Ca=35.8 Fe=0.17 Mg=1.60 Mn=0.70 D,o-Stage:50 min 60°C mill filtrate added back to 10 % consistency Kappa Factor 0.25 0•25 C102 charge,% 0.96 1.20 Mill Filtrate Colour,C.U. 890 890 Final pH 2.3 2.0 Consumed C102, % 0.96 1.20 Brightness, %ISO 49.4 54.6 Filtrate Colour,C.U. -- 980 Filtrate Metals,mg/L --- Ca=128.24 Fe=1.90 Mg=38.12 Mn=15.10 Eop-Stage•75 min 77°C 40 nsi.10%a consistency Sample ID 2001-00 2785 2852 NaOH charge, %n 1.3 1.3 H2O2,charge,% 0.3 0.5 Final pH 11.5 11.7 Consumed H2O2,% 0.3 0.5 Kappa number 2.7 2.1 Viscosity,mPa•s 15.3 14.8 Brightness,%ISO 65.2 71.6 Filtrate Colour,C.U. --- 1170 Filtrate Metals,mg/L --- Ca=4.49 Fe=0.30 Mg=1.72 Mn=0.40 D-State:240 min. 740C.10 % consistencv Sample ID 2001-00 2853 C102 charge,% 0.5 0.6 0.7 NaOH,% 0.1 0.13 0.18 H2SO4, % - --- -- Final pH 3.5 3.5 3.2 Consumed C102, % 0.48 0.57 0.65 Viscosity,mPa-s - 14.3 -- Brightness,%ISO 87.2 88.0 88.5 Filtrate Colour,C.U. --- 52 --- Filtrate Metals,mg/L Ca=6A8 Fe=0.15 Mg--1.20 Mn--0.43 Tappi Dirt Aredppm(>.o.wmm'). 23.99 Cl amen and SvUnpsMu,MU%L=a1 SaMgsWemporary lamm HmX0LK40001-06H Pan I SW FmM aepoMdw 8 U 91 PO F10 flil L Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta, GA December 6,2001 Table 1-5. Laboratory Do-Eop-D Bleaching of Mill Softwood Oxygen Pulp Sample ID Mill Oxygen Delignified 2001-002003 Kappa number 13.5 Viscosity,mPa•s 16.1 Brightness,%ISO 33.6 Bleaching Sequence: Do-Eop-D Dn-Stage:50 min..600C.mill filtrate added back to 10 % consistency Kappa Factor 0.20 0.25 CI02 charge,% 1.03 1.28 Mill Filtrate Colour,C.U. 890 890 Final pH 2.8 2.2 Consumed CI02, % 1.03 1.28 Brightness, %ISO 49.9 55.6 Filtrate Colour,C.U. No Sample 1070 Filtrate Metals,mg/L Ca=174.7 Fe=2.2] Mg=38.28 Mn=14.68 Ca=173.84 Fe=2.31 Mg=40.28 Mn=15A2 Eop-Stage:75 min.,770C.40 psi.10% consistency Sample ID 2001-00 2721 2832 NaOH charge, % 1.3 1.4 H2O2,charge, % 0.3 0.5 Final pH 11.5 11.7 Consumed H2O2, % 0.3 0.5 . Kappa number 2.6 2.0 Viscosity,mPa•s 14.5 13.9 Brightness, %ISO 66.4 71.9 Filtrate Colour,CU 1295 Filtrate Metals,mg/L Ca=8.42 Fe=0.31 Mg=1.56 Mn=0.64 Ca=6.94 Fe=0.29 Mg=1.58 Mn=0.50 D-Stage:240 min.,740C,10 %e consistency Sample ID 2001-00 2723 2833 C102 charge, % 0.4 0.5 0.6 0.7 0.5 0.6 0.7 0.8 NaOH,% 0.08 0.25 0.19 0.32 0.05 0.11 0.17 0.20 H2SO4,% 0..06 0.59 - --- - --- Final pH 3.5 4.4 3.8 4.5 3.3 3.4 3.8 3.9 Consumed 002, % 0.39 0.45 0.58 0.66 0.49 0.55 0.66 0.75 Viscosity,mPa•s -- - -- 13.6 - -- Brightness, %ISO 83.5 86.5 87.3 87.1 87.6 88A 89.0 89.1 Filtrate Colour,CU --- -- --- --- 31 --- -- Filtrate Metals, mg/L --- Ca=16.73 Fe=0.27 Mg=3.70 Mn=0.67. Tappi Dirt Areatppm(>.0.o4mm') Mocumena aM Svt!ngaYoor.NaNl. 1 Snangsnemporary inmmei RaNOLK0001-088 Pan I SW FvW Repomdm 9 COMMON, 01A1 Allen Turner Pruyn'sIsland Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Table 1-6. Laboratory O-Do-Eop-D Bleaching of Lab Softwood CK Pulp Sample ID Lab CK Brownstock S3137+S3140+S3148 (2001.00402+002698) Kappa number 21.6 Viscosity,mPa•s 24.6 Brightness, %ISO 32.5 Bleaching Sequence: O-Do-Eop-D O-Stage: 60 min.,90°C,80 osi 10% consistency Sample ID 2001-00 2561 NaOH, % 1.6 Final pH 11.3 Kappa number 12.6 Viscosity,mPa•s 19.2 Brightness, %ISO 37.3 Filtrate Colour,CU 4330 Filtrate Metals,mg/L Ca=17.22 Fe=0.23 Mg=1.62 Mn=0.34 Do-Stage:50 min..600C,mill filtrate added back to 10 % consistency Kappa Factor 0.25 CI02 charge,% 1.20 Mill Filtrate Colour,C.U. 890 Final pH 1.9 Consumed C102,% 1.20 Brightness,%ISO 55.5 Filtrate Colour,CU 1720 Filtrate Metals,mg/L Ca=72.10 Fe=3.19 Mg=24.92 Mn=6.92 Eop-Stage:75 tnin..77°C.40 ositdl0% consistence Sample ID 2001-00 2903 NaOH charge,90 1.3 H2O2,charge,% 0.5 Final pH 11.5 Consumed H2O2,% 0.3 Kappa number 2.22 Viscosity,mPa•s 13.5 Brightness,%ISO 72.3 Filtrate Colour,CU 1280 Filtrate Metals,mg/L Ca=3.06 Fe=0.30 Mg=0.88 Mn=0.13 D-Stage:240 min..74°C.10 % consistency Sample ID 2001-00 2904 C102 charge,% 0.4 0.5 0.6 NaOH,% 0.05 0.08 0.10 H2SO4,% _- Final pH 3.1 3.0 2.8 Consumed C102,% 0.39 0.49. 0.58 Viscosity, mPa•s -- 13.4 Brightness,%ISO 87.7 87.9 88.6 Filtrate Colour,CU -- 27 --- Filtrate Metals,mg/L Ca=23.22 Fe=0.38 Mg=3A4 Mn=0.51 Tappi Dirt Aredppm(>.o.04mma) C;1Dm cw and SevingNoarshaUUoca[Swings%TtnTomry laMurca MAOLK411001468Paz ISWFwl RWmdw 10 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpharetta,GA. December 6,2001 Table I-7. Laboratory O-Do-Eop-D Bleaching of Lab Softwood LS Pulp Sample ID Lab LS Brownstock AL7762001-002447 Kappa number 22.3 Viscosity,mPa•s 30.2 Brightness,%ISO 29.3 Bleaching Sequence: O-Do-Eop-D O-Stage:60 min.,90°C,80 psi 10% consistency Sample ID 2001-00 2560 NaOH,.% 1.6 Final pH 11.4 Kappa number 12.3 Viscosity,mPa•s 27.4 Brightness,%ISO 35.7 Filtrate Colour,C.U. 5640 Filtrate Metals,mg/L Ca=20.96 Fe=0.13 Mg=1.60 Mn=0.25 Dn-Stage:50 min.,60"C,mill filtrate added back to 10 % consistencv Kappa Factor 0.22 C102 charge, % 1.03 Mill Filtrate Colour,C.U. 890 Final pH 2.1 Consumed C102, % 1.03 Brightness,%ISO 51.7 Filtrate Colour,C.U. 1090 Filtrate Metals,mg/L Ca=111.62 Fe=1.14 Mg=23.54 Mn=6.58 Eon-Stage:75 min..77°C,40 psi,10% consistency Sample ID 2001-00 2855 NaOH charge, % 1.3 H2O2,charge,%4 0.5 Final pH 11.5 Consumed H2O7., % 0.5 Kappa number 2.1 Viscosity,mPa•s 17.5 Brightness,%ISO 70.9 Filtrate Colour,C.U. 1330 Filtrate Metals,mg/L Ca=71.14 Fe=3.27 Mg=24.96 Mn=6.75 D=Stage:240 min.,74"C.10 % consistency Sample ID 2001-00 2856 CIOZ charge,% 0.4 0.6 0.8 NaOH,% 0.07 0.55 0.60 H2SO4,% --- --- Final pH 3.3 5.6 7.6 Consumed CIOZ,% 0.4 0.45 0.48 Viscosity,mPa•s --- 17.1 -- Brightness,%ISO 87.1 88.5 86.4 Filtrate Colour,C.U. --- 34 --- Filtrate Metals,mg/L Ca=8.78 Fe=0.27 Mg=1.72 Mn=0.30 Tappi Dirt Alea/ppin(>.0.04mmd) 34.08 C`.1D�m and SeningAmvsb&IMocal5eningATemporuyln,emet Fdu%DLK4UMI.OUP. lSWFinal Repondw Il 1 -L Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Table 1-8. Lab Two Stage Oxygen Delignifications of Mill Softwood Brownstock Pulp Sample ID MM Brownstock 2001-002000 Kappa number 21.5 Viscosity, mpa•s 22.0 Brightness,%ISO 29.3 Oxygen Trial O 00 O-O Sample ID 2001-00 2530 2760 2763 Stage l NaOH,% 1.6 2.2 1.0 Time,min 60 30 30 Temperature,°C 90 100 100 Pressure,psi so 80 80 Consistency,% 10 10 10 Final pH --- --- 11.0 Stage 2 NaOH, % 1.0 Time,min - 60 60 Temperature,°C 90 90 Pressure,psi 80 80 Consistency, % -- 10 10 Final pH 11.5 11.7 11.5 Kappa number 12.6 9.8 11.3 Viscosity,mPa-s 16.3 14A 16.2 Brightness,%ISO 34.1 3&4 36.6 Filtrate Colour,C.U. 5330 6950 2715 Filtrate Metals, Ca=15.90 Fe=0.17 Mg=1.60 Ca=15.44 Fe=0.17 Mg--2.16 Ca=13.90 Fe=0.15 Mg=1.12 Mn=0.70 Mn--0.94 Mn=0.47 CDowmemsa ASct*pVmnEaaa.oalSmOSATemponrylne AeAOLMU001-09 Pu115Nflml Repomdw 12 r a aaa rn o 0 o No c c o c c O o cn o x .. x � � d R N �I n oo A to W A w 0o A 00 A N m A W A N as A U '+p fOi p o o ui O O O o In O o O C� O 0 o o In 0 0 o o i+, 0 O o o 0 0 0 o o in O Q o000 000o c`� 000 oo $ o oo8o 000 � qC W w A V P U A J J U a b O O v N J W OJO J b �O N lb. �O b U � G d S cn _ _ _ w rq O' iw A A lA J W A A in :4 W i+ N In LJ W A A Oh :4 laf A A lA L4 w A U O. 00 1a G in O S v O q O Y d T J G La > w J In LA 00 y as t, ae A 6 � 2 _ d� Q H FJ Lh LA O L+ A A �1 O N O L. �1 b A }J IJ L. CO O, T b Q, B. N W � 41 A U b J A N LA W w w N N N N N N N N N . .+ N w N y A N w w N N 0 0OQ .wn W is w Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Table 1-10 Tear and Tensile Index @ 400 CSF of Selected Softwood Pulps Tensile Tear Descriptive Index Index LIMS ID ID (N.nVg)at (mN-m2/g) at 400 CSF 400 CSF 2001-002000 Mill Brownstock 86.3 9.5 2001-002003 Mill Oxygen 84.6 8.2 2001-002004 Mill Fully Bleached 88.1 8.5 5 2001-002853 Mill BS Lab O-Do-Eop-D 86.0 8.8 2001-002447 Lab LS Brownstock 08.9 11.3 2001-002560 Lab LS Oxygen 95.0 11.1 2001-002856 Lab LS O-Do-Eop-D 90.2 0..6. — Mocumeau and Seninr%Xmirb IMu l$euings\TemponryInim F11,A0LK412001-068Pan I SWFinal Repomd 14 Allen Turner Prayn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-1. Total Yield versus Kappa Number for Lab Softwood Cooking 50 49 0 48 47 0046 � o rYi c 45 0 0 e 44 0 43 m 42 +CK,EA=192%on wood 41 ■CK,EA=21.6%on wood 40 ♦LoSolids 16 18 20 22 24 26 28 30 32 34 36 38 Kappa Number Figure 1-2. Laboratory Cooking Response for Softwood Furnish 38 36 " +CK, EA=19.2% on wood 34 ■CK, EA=21.6% on wood 32 ♦LoSolids L 30 E 28 Z a 26 a Y 24 22 20 18 16 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 H-factor C10ocmeems W Smin®ManSalM—I SeninSalhn"wy Int.d F1d10LK4'r001-W9 Part 1 SW RW ReWa.dw 15 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-3. Viscosity versus Kappa Number for Lab Softwood Cooking 50 45 40 N ao35 E °o c30 N O O -- 25 O u y 20ZL: — 15 IOCK,FA=1s.2%anWood ,EA=21.6%on wood 10 S ids 16 18 20 22 24 26 28 30 32 34 36 38 Kappa Number Figure 1-4. EA Consumed versus Kappa Number for Lab Softwood Cooking 22 = 21 ♦CK,FA=19.2°/n on wood 0 z 20 ■CK.EA=21.6%on wood 0 19 ♦Lo•sottds 0 18 0 e 17 m 16 E of 15 c rQOj 14 W 13 12 16 18 20 22 24 26 28 30 32 34 36 38 Kappa Number CVbcwntnv and Snungalnwa1u11\(.onl Srnive�\Trnpomry Imm¢�FiIn10LKQ2001-u68 Pan 1 SW Howl Rcpon.doc 16 Allen Turner Pcuyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-5. Tear Index versus Tensile Index for Selected Mill and Lab Softwood Pulps 30.0 Mill BS 25.0 —.—Mill Oxygen \ --MID Bleached + as L g MAI BS Lab O-D-Eop-D E 20.0 • —a—Lab LS BS Lab LS Oxygen Lab LS O-D-Eop-D 15.0 10.0 5.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 110.0 Tensile Index(N•mlg) Figure 1-6. Tensile Index vers'ls PFI Revolutions for Selected Mill and Lab Softwood Pulps 110.0 100D � W.0 E Mill BS % 70.0 a Mill Oxygen C m 60.0 •—Mill Fully Bleached F wD +Mill_BS Lab O-D-Eop-D — —Lab LS BS 40.0 --Lab LS Oxygen Lab LS O-D-Eop-D 20.0 0 1000 2000 3000 4DW MOD MOD 70M WW am PFI Revolutions CADa ma and Smingst hd0lnml Sm1aSs%TcTV=g lntcma Fdm\DLKA2001-00 Pan I SW Find Rtpomdm 17 a36n I Allen Turner I'myn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part I Alpheretta,GA December 6,2001 Figure 1-7.Mill Softwood Brownstock Pulp 2001-002000 30 150 I I i30 25 12110 % vI 100 v 20 90 is m I 80 c c 15 Y I .70 61) ' 7 � to 10 i I i 40 LL i 30 a. 5 20 i 10 0 0 100 200 300 400 500 600 700 800 900 . 1000 Canadian Standard Freeness +-Bulk —a Tear Index —A Burst Index - 9 PFI - o Tensile Index (10, ar-?/9) (MN'rr'?/g) (10' kP&rrf/g) (10- revs) '(N•rrJg) Figure 1-8. Mill Softwood Oxygen Pulp 2001-002003 150 I 140 130 2 120 5 110 X. v 20 I I 10 c I 90 x m ..T i 80 e c �- 15 i 70 H ri m' # so m' m 10 50 m 40 d 30 5 20 i 10 0 0 100 200 300 400 500 600 700 800 900 1000 Canadian Standard Freeness(mL) +(Bulk •-m--(Tear Index —i. Burst Index 1 —e—pFl13/9) —o—Tensile/In)de . (10' kPa rrtz/g) CVloconcnu end Smingf�ha NAW Seninga\Tcgmrvy la:m HaIDLKA2001469 Pan I SW Fiml RepooAm IS � Oil 5-1 AL Allen Turner Prayn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part i Alpheretta,GA December 6,2001 Figure 1-9. Mill Softwood Fully Bleached Pulp 2001-002004 30 150 140 25 130. 120 X ! I I 110 m '20 I 100 90ro- m N ' ! ' e c 15 I 70 I I 60 m 10 I I 50 m K_ 40 rL a 5 } I 20 10 0 0 100 200 3W 400 500 600 700 800 9W 1000 Canadian Standard Freeness(mL) -s Bulk Tear Index -i—Burst Index --' ---- - 10' cm'/g) mN•m'/g) (10' kPa•m'/g) r:jFigure 1-10. Mill Softwood BS Lab O-Do-Eop-D Bleached Pulp 2001-002853 3p 150 I ` 140 1 i 130 25 120 x i ' 110 m 10 20 I 100 90 m 15 m Y 70 In 60 IC i 10 50 W 40 a 30 5 20 10 0 1 0 100 20D 300 400 5W 600 700 800 9W 1000 Canadian Standard Freeness(my i Bulk —a—Tear Index Burs( Index 10' cm'!g) mN rrtZ/ ) (10' kPa m2/g) C\D.w and Scnip\mevWMl l Imemd FiWOLK61M-068 Pon 1 SW Find RepaMdoc t' FM ENT I A� Allen Turner Pruyn's Island Technical Center Andritz Ahistrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-11. Lab Softwood Lo-Solids°Brownstock Pulp 2001-002447 30 150 I 140 25 130 I 120 v110 v 20 100 c ' 90 m m 15 80 e c I I I 70 « F m I 50 m m 10 I 50 � I 40 a I I 30 5 20 i 10 0 0 100 200 300 400 500 500 700 800 900 1000 Canadian Standard Freeness(my +Bulk — —Tear Index —+—Burst Index 10' aTivg) TN•rr>=! ) (16" kPa•rr?/g) PM qnrtev Figure 1-12. Lab Softwood Lo-Solids Oxygen Pulp 2001-002560 150 140 I i I I 130 I i 120 x i I 110 m c 20 100 `m I I I m 15 I 80 Y 70 t- m' I 60 m 10 50 a®' 40 LL- IL 5 � I 20 10 0 1 1 F I I i 1 0 100 200 300 400 500 600 700 800 90D 1000 Canadian Standard Freeness ImQ —o—Bulk --0—Tear Index Burst Index —a PFI -o--•Tensile Index (10' aTf/g) (mN•rTf/g) (10' kPa-0/g) (10-2 revs) (N-nV9) C.U)mm u uM SminpVm bdN.e iSming,%Trn@orsy imams HaW MU004068 Pun I S W Flnal Rcpom&c 20 ° $ Irk Allen Turner Pruyn's Island Technical Center Andritz Ablstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-13. Lab Softwood Lo-Solids® O-Do-Eop-D Pulp 2001-002856 30 150 i I i I 140 130 25 j ! f 120 110 x v 20 100 m C i I C 90 )-rq 60 t" 15 m m I 70 «t- m 60 a mm 10 50 40 a i I 30 ! i i 20 10 01 0 100 200 300 400 500 600 700 800 900 1000 Cenadlan e Bulk —a—Tear Index —t-Burst Index 10' arp/g) (10, kP&rr?/9) CND=a nu and SndngsVmnAaIILLm1SmingsWcagarmy1mv F0co%OLKe1200"8PanISWFinalRcpm.dm 21 PRUYN'S ISLAND TECHNICAL CENTER REPORT 2010-081 LABORATORY COOKING AND BLEACHNG FOR EVERGREEN PACKAGING CANTON,NC TO: WILLIAM MILLER Issued: January 31, 2011 Issued by: Pamela O'Leary Tel.(518)745-2992 Fax(518)745-2971 William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report2010-081 Canton,NC January 31,2011 Summary As part of a bleaching study, Evergreen Packing supplied PITC with softwood chips, mill brownstock and fully bleached pulp. The mill wanted to compare the effect of two stage oxygen delignification on bleach plant filtrate color development and final strength properties. The kappa number on the mill brownstock tested too-low (23.2) to be used for our trials. Laboratory conventional kraft cooking produced pulps with 26.0 and 30.5 kappa numbers. Brownstocks were bleached using O-Do-Eo-D and 00-Do-Bo-D for comparison to a targeted 86% ISO brightness. Several 00 stages were performed targeting 60% delignification. All of the bleaching process conditions were supplied by the customer. Testing included kappa number, viscosity, chemical consumption and filtrate color after each bleach stage. Observations • Mill fully bleached pulps had a viscosity of 11.3 - 11.5 mPa-s and brightness of 85.5% - 85.6% ISO. • Mill brownstock had a kappa number of 23.2 and viscosity of 19.3 mpa•s. • Laboratory CK cooks produced kappa numbers 26.0 and 30.5. • Delignification for single stage oxygen run on the 26.0 kappa number pulp achieved 48.5% and a two stage achieved 61.4%. • Two- stage oxygen ran on the 30.5 kappa number pulp achieved 59.3% delignification. • The single 0 stage sequence consumed 20.6 kg/ADT of C102 in achieving 86.2% ISO brightness. • The two=stage 0 stage sequence consumed 16.0 kg/ADT of C102 in achieving 86.9% ISO brightness. • The 30.5 kappa number pulp consumed 17.8 kg/ADT of C102 in achieving 86.9% ISO brightness. • The color units ranged from 1490-55 for the single 0 stage sequence. • The color units ranged from 940-41 for the two-stage oxygen performed on 26.0 kappa brownstock. • The color units ranged from 1300-45 for the two-stage oxygen performed on 30.5 kappa brownstock. William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Standard Operating Procedures Descripfion PITC-P2 Conventional Kraft Cook - PITC-P6 Deten-nining size and thickness distributions of wood chips PITC-P7 Wood Chip Moisture Free Fraction PITC-P9 Determining the moisture free fraction of pulp PITC-P10 Determination of pulp yield PITC-P 12 Screening a Iar a amount of pulp TAPPI T230 Viscosity of pulp (capillaryviscosity method TAPPI T236 Kappa#of pulp TAPPIT248 Laboratory beating of pulp (PFI mill method TAPPI T525 om-92 ISO brightness ad formation and testing) PITC-B3 Oxygen Defignification PITC-138 Chlorine Dioxide Bleaching PITC-B6 Oxidative Alkaline Extraction PITC-B 19 Pulp washing NCASI TB#253 Color Determination TappiT227 CSF TappiT220 Bulk Tappi T403 Burst Ta _i T484 Tensile Tappi T414 Tear William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report2010-081 Canton,NC January 31,2011 Photograph N. Mill supplied furnish from the digester feed belt. 04 �L E.ueN�fPf NYC - William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Photograph#2. Representation of PITC chip classification. William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 0: Canton, Photograph . 11 1 1 from mill furnished digester feed belt before PITC laboratory oo c • t J y \ L[ � � •� tom! � x� 1 , William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report2010-081 Canton,NC January 31,2011 Table#1. Results of PITC chip classification. Job 2010-081 Lab+ID 120951 Descriptive ID Mill furnish digester belt feed chips Chip Size 0.0-3.0 mm(%) 0.1 Chip Thickness 0-2 mm(%) 2.4 Chip Size 3.0-7.0 mm(%) 2.9 Chip Thickness 2-4 mm(%) 29.2 Chip Size 7.0-123ram(°/o) 16.4 Chip Thickness 4-6 nun(%) 37.5 Chip Size 12.7-25.4 min(%) 59.1 Chip Thickness 6-8 nun(%) 16.7 Chip Size 25.4-45.0 mm(%) 19.2 Chip Thickness 8-10 mm(°/o) 7.4 Chip Size>45.0 mm(%) 2.4 Chip Thickness>10 mm(%o) 6.8 Table 2 . Summary of pulping conditions and pulping results. Furnish: 120951 Mixed southern softwood Cook ID BC1661 AC3465 AC3466 AC3474 Cook Type CK CK CK CK Screened Pulp Lab Plus ID 120973 121047 121117 121671 EA Charge Total (% on wood) 20.6 20.6 20.6 20.6 Impregnation (% on wood NaOH) 20.6 20.6 20.6 20.6 WL Sulfidity (% AA) 29.3 29.3 29.3 29.3 Cooking Temperature (°C) 172.5 169.5 169.5 167.0 EA Consumed (% on wood NaOH) Total 17.4 16.9 16.8 18.3 Impregnation Stage 9.3 9.5 9.3 9.7 Co-current 1 Stage 8.1 7.4 7.5 6.7 Residual EA(g/L NaOH) End of Impregnation 32.3 31.8 32.4 31.0 End of Co-current 1 9.3 10.7 10.9 12.0 H-factor 1780 1330 1320 1110 Kappa Number 20.3 26.0 25.9 30.5 Viscosity(mPa•s) 20.6 27.8 27.2 32.5 Viscosity/Kappa Number Ratio 1.0 1.1 1.1 1.1 Brownstock Brightness (% ISO) 29.8 29.0 30.7 29.0 Brownstock Total Yield(% on wood) 43.5 44.5 43.7 44.6 Rejects (% on wood) 0.2 0.5 0.3 0.4 Screened Yield (% on wood) 43.3 44.0 43.4 44.2 William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report2010-081 Canton,NC January 31,2011 Table 3 . O-Do-Eo-D Bleaching. Mill Fully Bleached Pulps Lab Cook ID AC3465 Date Received 9/23110 1/13/11 Sample ID 12- 1047 120939 122146 Kappa Number 26.0 -- -- Viscosity, mPa•s 27.8 11.5 11.3 ISO Brightness, % 29.0 85.5 85.6 O Stage: 92°C, 60 min., 100 psi., 10% cons. Sample ID 12- 1105 NaOH, % 2.0 Final pH 11.0 Kappa number 13.4 Delignification, % 48.5 Viscosity, mPa•s 20.8 ISO Brightness, % 37.2 Do Stage: 66°C.20 min., 10%cons. Sample ID 12- 1111 Kappa Factor 0.24 CI02, as Cl2,% 3.2 Final pH 2.5 Residual g/L as Cl2 0 ISO Brightness, % 54.3 Filtrate color;C.U. 745 Eo Stage: 80°C, 60 min.. 35psi-O psi 10 min.,10% cons. Sample ID 12- 1122 NaOH, % 1.2 Final pH 11.2 Kappa Number 3.2 Viscosity, mPa•s 19.3 ISO Brightness, % 60.9 Filtrate color, C.U. 1490 D Stage: 74°C. 240 min., 10% cons. Sample ID 12- - 1148 CI02, as Cl2,% 2.1 2.6 3.2 NaOH,% 0.30 0.45 0.54 Final pH 3.6 3.9 3.8 Residual CIOZ g/L 0 0.0005 0.0015 Residual g/L, as Cl2 0 0.0013 0.0039 Viscosity, mpa•s -- 17.4 -- ISO Brightness, % 85.7 86.2 87.0 Filtrate color, C.U. 66 55 33 William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Table 4 . 00-Do-Eo-D Bleachng. Lab Cook ID AC3465 AC3466 AC3466 AC3474 Sample ID 12 1047 1156 1156 1671 Kappa Number 26.0 25.9 25.9 30.5 Viscosity, mPa•s 27.8 27.2 27.2 32.5 ISO Brightness, % 29.0 30.7 30.7 29.5 00 Stage: 140 psi+ 100 psi., 10% cons Sample ID 12- 1106 1170 1171 1755 Time, min 20 + 60 20+60 20+60 20 + 60 Temperature, °C 85 + 92 89 + 93 93+99 89 + 99 NaOH, % 2.2 2.3 2.8 3.0 Final pH 11.0 10.8 11.0 11.0 Kappa number 12.3 12.2 10.0 12.4 Delignification, % 52.7 52.9 61.4 59.3 Viscosity, mPa•s 19.7 19.5 17.6 19.8 ISO Brightness, % 38.3 39.4 42.4 42.2 Do Stage: 66'C, 20 min.. 10% cons. Sample ID 12- 1113 1759 Kappa Factor 0.24 0.24 CIOZ, as CIZ,% 2.4 3.0 Final pH 2.6 2.4 Residual g/L as CIZ 0 0 ISO Brightness, % 63.3 60.1 Filtrate color, C.U. 450 495 Eo Stage: 80°C. 60 min., 35psi-O psi 10 min.,10%cons. Sample ID 12- 1185 1760 NaOH, % 1.1 1.0 Final pH 11.2 11.1 Kappa Number 2:8 3.1 Viscosity, mPa•s 16.7 19.4 ISO Brightness, % 67.0 64.6 Filtrate color, C.U. 940 1300 D Stage: 74°C. 240 min., 10%cons. Sample ID 12- 1200 1761 CIOZ, as Cl2,% 1.6 2.1 2.6 1.6 2.1 2.6 NaOH,% 0.20 0.36 0.45 0.25 0.36 0.45 Final pH 3.4 3.9 3.8 4.2 4.1 4.2 Residual CIOZ, g/L 0 0.0004 0.0011 0 0.0007 0.0015 Residual g/L, as C12 0 0.0011 0.0029 0 0.0019 0.0038 Viscosity, mPa•s -- 14.5 -- -- 17.7 -- ISO Brightness, % 85.5 86.9 86.9 85.4 86.4 87.3 Filtrate color, C.U. 69 41 56 - 45 -- William Miller Pruyn%Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Table 4.Physical Strength Properties Cond Wt Burst Tensile Tear Tensile Tensile A E. . Descriptive PFI CSF Bulk Index Index Index T. Stiffness Elongation Stiffness Thicknes LIMS ID ID (#revs) (mL) (9m) (cm'/g) (kPa•m'/g) (N•m/g) (mN-elg) /m2) (kN/m) (mm) Index s(mm) (kNm/g) 120938 0.0 649 6.55 1.72 2.75 41.55 17.65 64.66 392.2 3.17 5.99 0.563499 500 637 6.54 1.56 4.04 62.58 12.54 93.52 496.5 3.22 7.59s 0.509549 Mill Fully 2500 517 6.44 1.44 5.11 79.33 9.76 115.51 556.1 3.29 8.63 0.462635 Bleached 5000 357 6.51 1.37 5.75 85.27 8.29 143.59 567.4 3.79 8.72 0.446836 Rec'd 9/22/10 7500 239 6.63 1.34 5.85 85.11 8.32 . 125.03 611.6 3.20 9.23 0.444474 121148 0.0 704 6.54 1.73 2.42 38.14 30.12' 60.34 362.1 3.18 5.54 0.567080 500 683 6.56 1.52 4.73 67.14 17.99 111.82 485.3 3.66 7.40 0.497941 O-Do-Eo-D 2500 573 6.77 1.41 6.25 89.65 13.03 146.83 591.6 3.62 8.74 0.476199 26.0 BS 5000 439 6.46 1.36 6.67 95.15 11.89 157.23 578.2 3.85 8.95 0.438988 Kappa# 7500 321 6.49 1.34 7.10 94.93 11.49 147.74 588.5 3.60 9.07 0.433222 121200 0.0 700 6.54 1.70 2.37 35.87 27.95 56.24 340.5 3.14 5.21 0.555599 500 678 6.57 1.51 4.64 62.40 16.91 101.64 464.5 3.57 7.07 0.497230 00-Do-Eo-D 2500 579 6.50 1.38 6.09 81.37 12.49 131.54 539.9 3.64 8.31 0.446963 25.9 BS 5000 431 6.41 1.37 6.86 92.71 11.61 140.39 574.7 3.52 8.97 0.438432 Kappa# 7500 300 6.42 1.33 7.13 94.96 10.92 157.99 562.1 3.90 8.76 0.425907 121761 0.0 696 6.42 1.71 2.51 38.18 28.68 42.89 379.0 2.33 5.90 0.547420 500 665 6.64 1.50 4.85 67.74 16.77 103.26 496.6 3.31 7.48 0.497535 00-Do-Eo-D 2500 553 6.41 1.41 6.33 90.34 12.99 135.13 586.1 3.46 9.14 0.450672 30.5 BS 5000 409 6.46 1.35 6.80 93.64 11.49 157.07 596.5 3.88 9.23 0.434594 Kappa# 7500 279 6.58 1.32 7.08 97.49 10.78 170.33 597.2 3.98 9.08 0.433324 122146 0.0 692 '6.31 1.77 2.82 39.46 19.45 67.64 351.2 3.59 5.57 0.559511 Mill Fully 500 650 6.45 1.53 4.28 63.11 12.75 90.82 490.6 3.16 7.61 0.492048 Bleached 2500 504 6.53 1.39 5.36 81.50 9.68 124.00 554.0 3.42 8.48 0.454329 Received 5000 340 6.47 1.31 5.78 86.76 8.39 131.03 580.8 3.45 8.98 0.424586 1/13/11 7500 212 6.40 1.29 5.98 90.99 8.06 132.93 594.0 3.37 9.28 0.413639 William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Table 5 Tear and Tensile IndetA 400CSF of Selected Softwood Pulps Tensile Tear Index Index Descriptive (N•m/g)at (mrhm'/g)at LIMS ID ID 400 CSF 400 CSF 120938 Mill Fully Bleached 9 (reed 9/23/10) 83.7 8.7 121148 O-Do-Eo-D 26.0 kappa#Lab CK 95.1 11.8 121200 00-Do-Eo-D 25.9.0 kappa#Lab CK 93.2 11.5 121761 00-Do-Eo-D 30.5 kappa #Lab CK 93.9 11.4 122146 Mill Fully Bleached(reed 1/13/11) 84.8 8.9 William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Figure 1. Tensile versus Canadian Standard Freeness of laboratory cooks. Tensile vs CSF Index 140.00 120.00 - - - 100.00 - - — -. 'm E i 80.00 K N 9 C a 60.00 i; +fO-Oo-Eo-Od°ach r 40.00 tmAl N hbed�K2 20.00 0.00 0 100 200 300 400 500 e00 700 e00 CSF(MI) William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Figure 2. Tensile Index versus PFI. Tensile Index vs PFI Revs 140.00 120.00 100.00 rn 80.00 — N 0 9 C m •w 60.00 - - C m F 40.00 tmill fully bleach tO-Do-Eo-O -+ O&Do-Eo-D 20.00 9-00-Do-E,D -f-mill fully bleach#2 0.00 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 PFI(#of revs) William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Figure 3. Tear Index versus Tensile Index on PITC laboratory cooks. Tear Index vs Tensile Index 35.00 30A0 — 25.00 E 20.00 — E E x m a 15.00 — A A f 10.00 +mill sully bleach t0-Do-Eo-D �00-Do-Eo-D +00-DaEo-D 5.00 i Mlll WHY bleach#2 0.00 0.00 20.00 40.00 60.00 60.00 100.00 120.00 140.00 Tensile Index(N-nVg) William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report2010-081 Canton,NC January 31,2011 Miscellaneous Information All samples included in this report will be held in cold storage for three months after issuance of the report. At that time, the samples will be discarded without notice. If there is a need to retain samples longer than the three-month grace period, please contact PITC. Laboratory Study of Likely Effects of Installing Two-Stage Oxygen Delignification at Evergreen Packaging's Canton, NC Mill Final Report Thomas J. McDonough June 29, 2011 Confidential Executive Summary This report describes a study undertaken to-study and document the effects of replacing the Canton mill's single-stage oxygen delignification system with a two-stage system. The effect on effluent color was of particular interest.Pulps were prepared in the laboratory from Canton mill chips under conditions chosen to simulate(1) mill pulping to the normal kappa number level of 26 and(2) a scenario under which cooking would be terminated at a kappa number of 30.5 .The 26 kappa pulp was then subjected to single-stage and two-stage oxygen delignification, using mill conditions for the single-stage process and conditions for the two-stage process that were chosen to increase the degree of delignification to approximately 60%. The high-kappa pulp was also subjected to the same degree of two-stage oxygen delignification. All three oxygen pulps were subjected to D(EO)D bleaching to brightness levels in the 86—87 range. Relative to the single-stage(0)pulp, the two-stage(00) pulp of initial kappa 26 consumed 23%less C102 and had a viscosity of 14.5 units vs. 17.4 units for the 0 pulp. By employing the two-stage oxygen process the color of the first D stage filtrate was reduced from 745 units to 450, and the color of the(EO) stage filtrate from 1490 units to 940. However, at a fixed value of tensile strength (70 N.m/g), the tearing resistance of the 00 pulp (14.8 mMrrZ/g) was about 15% lower than that of the O pulp (17.0 mN.M2/g). The high-kappa pulp after two oxygen stages consumed 16% less C102 than the single-oxygen-stage pulp and had a fully bleached viscosity(179)which was virtually the same as that of the single-oxygen-stage pulp. In this case, the color of the first D stage filtrate was reduced from 745 units to 495, and the color of the(EO) stage filtrate from 1490 units to 1300.The tearing resistance of the fully bleached pulp (16.4 / mN.mZ/g) was only slightly lower than that of the reference(0) pulp. The tear strength deficiency of the 26 kappa pulp after two-oxygen-stages was not due to a fiber strength loss but rather to the fact that the 00 pulp had to be beaten to a higher sheet density in order to achieve a given tensile strength. Compared to the samples prepared in the laboratory, recent mill bleached samples had lower strength properties. This may reflect lower uniformity of treatment under mill conditions as well as detrimental effects of process equipment such as blow valves, pulps, etc., which laboratory pulps are not subjected to. Introduction The Canton mill employs the OD(EO)D bleaching sequence to produce bleached softwood pulp. The mill commissioned a laboratory study to predict the effects of replacing the current single-stage oxygen delignification system with a two-stage system, a change that can be expected to reduce the color level's of the mill's effluent. Mill chips were laboratory pulped to two different kappa numbers, one typical of that achieved in the mill (26), and one 4.5 units higher. One kappa 26 pulp sample was bleached under conditions chosen to simulate the OD(EO)D sequence currently used in the mill,as a control. A second, similar sample was bleached under conditions chosen to simulate replacement of the single oxygen stage with a two-stage system, leaving the unbleached(brownstock) kappa number unchanged. Finally, the 30.5 kappa number pulp was subjected to two-stage oxygen delignification followed by bleaching to high brightness. After each stage, the pulps were characterized by suitable measurements (kappa number, brightness and/or viscosity, depending on the stage) and the color of the effluent from each of the last three stages was measured. In addition, fully bleached samples were subjected to laboratory refining and the physical properties of the refined pulps were measured. - 1 - Results and Discussion Oxygen Delignification and Multistage Bleaching Table 1 shows the results obtained by oxygen delignification of the laboratory pulps.The unbleached 26 kappa pulp viscosities,27.2 and 27.8,were higher than those typically observed in the mill. As expected, the 30.5 kappa unbleached pulp had a viscosity (32.5) that was substantially higher than that of the 26 kappa pulp. Single-stage oxygen with 2.0%NaOH at 92°C achieved 48.5% delignification, which compares well with the recent average of 48.7% in the mill. To increase the degree of delignification of the 26 kappa pulp to 61.4% with two-stage oxygen it was necessary to apply 2.8%NaOH, with temperatures of 93 and 99°C in the first and second stages, respectively. Relative to the results in the single-stage case this increased the brightness from 37.2 to 42.4 and decreased the viscosity from 20.8 to 17.6 mPa.s. In the case of the 30.5 kappa unbleached pulp 59% delignification was achieved by increasing the caustic charge to 3.0%.This resulted in a brightness of 42.2 and viscosity of 19.8 mPa.s, Table 1.Laboratory Oxygen Delignification Results Single- Stage Two-Stage Oxygen Oxygen Unbleached Pulp Kappa Number 26.0 26.0 25.9 25.9 30.5 Viscosity, mPa•s 27.8 27.8 27.2 27.2 32.5 ISO Brightness, % 29.0 29.0 30.7 30.7 29.5 Oxygen Delignification 140+ 140+ 140+ 140+ Oxygen pressure, psig 100 100 100 100 100 Time, min 1 60 20+60 20+60 20+60 20+60 Temperature, °C 92 85 +92 89 +93 93 +99 89 +99 NaOH, % 2.0 2.2 2.3 2.8 3.0 Final pH 11.0 11.0 10.8 11.0 11.0 Kappa number 13.4 12.3 12.2 10.0 12.4 Delignification, % 48.5 52.7 52.9 61.4 59.3 Viscosity, mPa•s 20.8 19.7 19.5 17.6 19.8 ISO brightness, % 37.2 38.3 39.4 42.4 1 42.2 Table 2 contains the results of full bleaching of the oxygen delignified pulps. The single-oxygen-stage pulp was bleached to a brightness of 87.0 with a total C102 consumption of 2.43% (6.4% as C12). After two oxygen stages, the 26 kappa pulp was bleached to a brightness of 86.9 with a total C102 consumption of 1.71%and the 30.5 kappa pulp reached a brightness of 86.4 with a total C102 consumption of 1.94%. After full bleaching, the viscosity of the single-oxygen-stage pulp was 17.4. After two-stage oxygen and full bleaching, the 26 kappa brownstock yielded a viscosity of 14.5.The corresponding viscosity after full bleaching of the 30.5 kappa brownstock was 17.7,which was nearly the same as the fully bleached viscosity after applying a single oxygen stage to 26 kappa brownstock. At the normal brownstock kappa number of 26, going from one oxygen stage to two decreased the D.filtrate color from 745 to 450 units (a 40%reduction) and the(EO) filtrate color from 1490 to 940 units (a 37%reduction). When the brownstock kappa was increased from 26 to 30.5,the filtrate color reductions were smaller:,Going from one oxygen stage to two decreased the D°filtrate color from 745 to 495 units (a 34% reduction) and the(EO)filtrate color from 1490 to 1300 units(a 13%reduction). In all cases,the D, filtrate color, already low, was not changed significantly. - 2- Table 2. Results of Bleaching Oxygen Delignified Pulps No. of Oxygen Stages 1 2 2 Unbleached kappa number 26 26 30.5 Kappa number after oxygen 13.4 10.0 12.4 Viscosity, mPa•s 20.8 17.6 19.8 ISO Brightness, % 37.2 42.4 42.2 Do Stage: 66°C,20 nun.,'10% cons. C102, as C12,% 3.2 2.4 3.0 Final pH 2.5 2.6 2.4 Residual g/L as C12 0 0 0 ISO Brightness, % 54.3 63.3 60.1 Filtrate color, C.U. 745 450 495 (EO)Stage: 80°C,60 min.,35psi-O psi/10 min.,10% cons. NaOH, % 1.2 1.1 1.0 Final pH 11.2 11.2 11.1 Kappa Number 3.2 2.8 3.1 Viscosity, mPa•s 19.3 16.7 19.4 ISO Brightness, % 60.9 67.0 64.6 Filtrate color, C.U. 1490 940 1300 D, Stage: 74°C,240 min., 10% cons. C102, as C12,% 2.1 2.6 3.2 1.6 2.1 2.6 1.6 2.1 2.6 NaOH,%a 0.30 0.45 0.54 0.20 0.36 0.45 0.25 0.36 0.45 Final pH 3:6 3.9 3.8 3.4 3.9 3.8 4.2 4.1 4.2 Residual C102, g/L 0 0.0005 0.0015 0 0.0004 0.0011 0 0.0007 0.0015 Total Sequence C102.% 2.02 2.21 2.43 1.52 1.71 1.90 1.75 1.94 2.13 Residual g/L, as C12 0 0.0013 0.0039 0 0.0011 0.0029 0 0.0019 0.0038 Viscosity, mPa•s -- 17.4 -- -- 14.5 -- -- 17.7 -- ISO Brightness, % 85.7 86.2 87.0 85.5 86.9 86.9 85.4 86.4 87.3 Filtrate color, C.U. 66 55 33 69 41 56 1 45 3 Figure 1 shows the relationship between post-oxygen viscosity and kappa number.The decrease in kappa number achieved by increasing the severity of oxygen delignification is inevitably accompanied by a loss of viscosity(and, by implication, a corresponding loss in cellulose degree of polymerization). However, by increasing the unbleached kappa number, the viscosity after two oxygen stages (represented by the lower square data symbol) was restored to a value close to that obtained after a single oxygen stage. 35 30 Y! L EZ=6 ached n Stock a 25 N O O In > 20es 15 5 10 15 20 25 30 35 .Kappa Number Figure 1. Viscosity vs. kappa number after oxygen delignification Figure 2 illustrates the favorable effect of two-stage oxygen on total C102 consumption. At a final brightness level of 87.0,and under the conditions of these experiments, a 23%reduction in total C102 consumption may be expected when the brownstock kappa number is 26.Raising the brownstock kappa number to 30.5 causes a modest increase, but the decrease in C102 consumption is still significant. Relative to the base case(kappa 26 brownstock, one oxygen stage), the decrease is 16%. 88 y=6.W..76.66 y=3.66X+60.13 Y=&M.nm 87 .. ... --- . - ..:_.. —___...______...._. .— N d - t 86 OI m 85 •♦10-Stage 2 0.Stages ♦HI-K+20.Sta es 84 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 Total C102(Da+D1)as C102,% Figure 2.Final brightness vs.total C102 consumption 4 Physical Properties of Bleached Pulps Table 3 contains the results of physical properties testing of pulp bleached in the mill, pulp bleached in the lab with a single oxygen stage, and 26 kappa and 30.5 kappa pulps bleached in the lab with two oxygen stages. Table 3.Physical Properties of Bleached Ptd s Tensile Burst Tear Tensile Pulp PFI CSF Density Index Index Index T.E.A. Elongation Stiffness Index ID (revs) (mL) (g/cna3) (N.m/g) (kPa-0/g) (�•�/g) Q/m2) (Earn)10') (kNnVg) 0.0 649 0.58 41.55 2.75 17.65 64.66 3.17 5.99 0.5 637 0.64 62.58 4.04 12.54 93.52 3.22 759 Mill Bleached 2.5 517 0.69 79.33 5.11 9.76 115.51 3.29= 8.63 5.0 357 0.73 85.27 5.75 8.29 143.59 3.79 8.72 7.5 239 0.75 85.11 5.85 8.32 125.03 3.20 9.23 0.0 704 .0.58 38.14 2.42 30.12 60.34 3.18 5.54 0.5 683 0.66 67.14 4.73 17.99 111.82 3.66 7.40 O-Do-Eo-D 2.5 573 0.71 89.65 6.25 13.03 146.83 3.62 8.74 5.0 439 0.74 95.15 6.67 11.89 157.23 3.85 8.95 75 321 0.75 94.93 7.10 11.49 147.74 3.60 9.07 0.0 700 0.59 35.87 2.37 27.95 56.24 3.14 5.21 0.5 678 0.66 62.40 4.64 16.91 101.64 3.57 7.07 00-Do-Eo-D 2.5 579 0.72 _ 81.37 6.09 12.49 131.54 3.64 8.31 Kappa 26 5.0 431 0.73 92.71 6.86 11.61 140.39 3.52 8.97 7.5 300 0.75 94.96 7.13 10.92 157.99 3.90 8.76 0.0 696 0.58 38.18 251 28.68 42.89 2.33 5.90 00-Do-Eo-D 0.5 665 0.67 67.74 4.85 16.77 103.26 3.31 7.48 Kappa 30.5 2.5 553 0.71 90.34 6.33 12.99 135.13 3.46 9.14 5.0 409 0.74 93.64 6.80 11.49 157.07 3.88 9.23 7.5 279 0.76 97A9 7.08 10.78 170.33 3.98 9.08 Figure 3 shows the relationship between tearing resistance and tensile strength for each of the four pulp types. It is apparent that,at a tensile index of 70 N.m/g the 26 kappa pulp after two oxygen stages had a roughly 15%lower tear relative to the base case(single-oxygen stage applied to 26 kappa pulp). This tear strength deficiency was reduced to about 5%by raising the unbleached kappa number from 26 to 30.5. The"mill bleached"pulp had lower tear strength than the lab single-oxygen-stage pulp. This may be explained by harsher physical treatment of mill pulp due to blow valves, pumps and other process equipment. At first glance, the tear strength deficiency of the 00 pulp suggests that it has lower fiber strength than the 0 pulp; the tear strength of well-bonded beaten pulps is dominated by fiber strength since tear failure in such pulps occurs primarily by fiber breakage, rather than by bond failure and fiber pullout. On closer examination, however, a different conclusion can be reached, as explained below. 5 35 30 \ ,A •Mill Bleached \,� ♦ODIEO�D rn E 25 \ ■OODIEOID 20 \ D \ C F 15 10 5 20 30 40 50 60 70 80 90 100 110 Tensile Index,N.m/g Figure 3. Tearing resistance vs. tensile index. Fiber Strength vs. Bond Strength Figure 4 is a plot of tensile strength versus sheet density. Such plots typically display a linear rise followed by a leveling off to an almost horizontal plateau.As beating progresses, fiber conformability is increased, resulting in increased bonded area and greater overall level of bonding, which is manifested in higher sheet density and higher tensile strength. As beating progresses beyond a certain point, however, bond strength becomes so great that fiber breakage becomes significant and the tensile strength of the sheet is determined by fiber strength. Thus,the tensile strength at which the leveling off occurs can be taken as a measure of fiber strength. 110 100 •Mill 8lexthed 90 •oIXE01D ■OOIXE E 80 ♦Hi-K-0OD(EO)D ■ i i w 70 � i a � c y 60 � ac 50 f � i i 40 i i i 30 i 20 0.50 0.55 0.60 0.65 0.70 0.75 0.80 Sheet Density,g/cm3 Figure 4. Tensile strength vs.sheet density 6 The current data are no exception to this rule. All of the lab oxygen delignified pulps, whether single stage or two-stage level off at about the same value of tensile strength.To the extent that this limiting tensile can be taken as a measure of fiber strength, it may be concluded that these pulps have equally strong fibers. It is also significant that, in the earlier stages of beating, the 26 kappa 00 pulp has a lower tensile strength at a given density.This suggests that this pulp has lower specific bond strength than the 0 pulp. The tensile strength of the mill pulp levels off at a lower value, suggesting that the less uniform and harsher treatment suffered by the pulp in the mill has resulted in fiber strength losses. Figure 5 shows how tear strength is affected by beating. As beating progresses and sheet density is increased, the tear strength is decreased as a result of the adverse effect of increased bonding on the degree to which tear failure occurs by fiber pullout, as opposed to fiber breakage. (Since fiber breakage offers less resistance to tear failure than fiber pullout the tear strength decreases with beating.) A conclusion that may be drawn from Figure 5 is that,at a given sheet density, all of the lab oxygen delignified pulps have the same tear strength, regardless of the number of oxygen stages used. 35 •MIII Bleached 30 ♦OD(EO)D � ■OOD(EO)D "E 25 ♦Hi-K-OOD(EO)D z E x 20 m a c m 15 10 5 0.55 0.60 0.65 0.70 0.75 0.80 0.85 Sheet Density,g/cm' Figure 5. Effect of beating on tear strength. The 26 kappa two-oxygen-stage pulp had lower tear strength at fixed tensile strength than the corresponding single-oxygen-stage pulp, not because its fibers were weaker but rather because it had to be beaten to a higher sheet density to achieve the same level of tensile strength(as shown in Figure 4), with the result that its tear was lower(as shown in Figure 5). In contrast,the high-kappa two-oxygen-stage pulp had a tensile-density relationship that was nearly the same as that of the 26 kappa two-oxygen-stage pulp, with the result that both pulps had similar tear at fixed tensile. Burst Strength and Tensile Stiffness Figure 6 shows the relationship between tensile strength and burst strength for the four pulp types. At a given tensile strength level, the burst strength tends to be lowest for the mill bleached pulp and highest for the 26 kappa two-stage oxygen pulp. This may reflect differences in the shape of the stress-strain curves for the different pulp types. As is apparent from Table 3, the mill bleached pulp is stiffer and has lower 7 elongation and tensile energy absorption than the oxygen bleached pulps. This causes it to fail earlier when subjected to increasing bursting pressure. There is also evidence that the 26 kappa two-stage oxygen pulp has higher burst at a given tensile than the single-stage oxygen pulp, a difference that correlates with its lower stiffness, as shown in Figure 7. The burst-tensile characteristic of the high-kappa two-oxygen- stage pulp was similar to that of the 26 kappa single-oxygen-stage pulp. This correlates with the fact that the two had similar stiffness values, as shown in Figure 7. 8 7 •Mill Bleached ♦OD(EO)D / T 6 ■OOD(EO)D •HI-K-OOD(EO)D a 5 Y K v N / c 4 / rq / / M 3 / 2 1 20 30 40 50 60 70 80 90 100 110 Tensile Index, N.m/g Figure 6. Burst index vs. tensile index 10 • E Oi a%i 8 c .i•/ • / '` •Mill Bleached G m 6 / ■OOD(EO)D F ♦Hi-K-OOD(EO)D 4 0.55 0.60 0.65 0.70 0.75 0.80 0.85 Sheet Density,g/cm' Figure 7. Tensile stiffness index vs. sheet density 8 Response to Refining As shown in Figure S, the unbeaten mill pulp sample exhibited lower freeness than the oxygen delignified samples,which were similar to each other in regard to freeness. As beating progressed, this difference in freeness persisted. The lower freeness of the mill pulp suggests that it had higher specific surface at any given level of refining. A likely explanation is that the mill pulp had a higher content of fines, either because of a different species composition(higher hardwood content) or because of the harsher treatment inflicted by mill mechanical processes (mixing, pumping, etc.). The high-kappa pulp after two oxygen stages beat at a slightly faster rate than the other two lab pulps. In future experiments it would be desirable to measure and control the species composition and to measure the fines content and fiber length distribution,for example by use of the Fiber Quality Analyzer. 600 700 600 >EL 500 400 `n300200 ♦ HI-K-OOD(EO)D 100 0 0 1 2 3 4 5 6 7 6 9 PFI Revs x 104 Figure S. Freeness vs. number of revolutions in the PFI mill Figure 9 compares the rate of densification of the three pulps during beating. At intermediate levels of refining the oxygen pulps densified at similar rates and more rapidly than the mill pulp. Assessment of the "Mill Bleached" Pulp Sample The properties of the sample of mill-bleached pulp were generally inferior to those of the single-oxygen- stage lab pulp. At the same tensile strength level the tearing resistance of the mill bleached pulp was more than 30% lower than that of the single-oxygen-stage lab pulp. It had a lower maximum tensile strength and lower tear at the same density. Both observations suggested that it had weaker fibers than the lab pulps. At a given level of refining the mill pulp had both lower freeness and lower sheet density than the lab pulps.These discrepancies between the properties of the mill pulp and the lab pulp intended to simulate it were of some concern. They are probably due, at least in part,to the relatively harsher and less uniform treatment experienced by the pulp under mill conditions, as compared to the gentler and more uniform treatment under lab conditions. They may also reflect differences between mill operating conditions prevailing at the time of collection of the sample submitted to the lab from more normal mill operating conditions. Measurement of the viscosity of the mill bleached sample submitted to the lab yielded a value of 11.3 - 11.5 mPa.s, which is consistent with its lower tear strength. 9 To allow further investigation of the degree to which the present mill pulp sample was representative, the mill provided data on pulp from presumably normal production runs. The data included physical properties measurements on nine samples for which viscosity data were also available. Tear-tensile plots for these nine samples are shown in Figure 10, which also includes the"Mill Bleached"pulp data from Figure 3 and the results of evaluation of a second"Mill Bleached" sample that was collected after completion of the initial lab study. 0.80 0.75 ■ �U 0.70 ■ 0 0.65 1 O •Mill Bleached ♦OD(EO)D t 0.60 ■OOD(EO)D N ♦Hi-K-OOD(EO)D 0.55 0.50 0 1 2 3 4 5 6 7 8 9 10 PFI Revs x 10-3 Figure 9. Sheet densification during refining 35 •Mill Bleached •Visa 135 30 •Visc.14.6 •Visc.11.6 •Visc.12.1 •Visc.10.3 .Visc.17.7 •Visc.12.3 p, 25 s Visc.14.61 •Visc.13.6 E ♦Mill Bleached 2 E 20 x d 15 `m v 10 5 0 20 30 40 50 60 70 80 90 100 110 120 130 140 Tensile Index,N.m/g Figure 10.Tear vs. tensile for pulps produced in the mill 10 It is apparent from Figure 10 that the"Mill Bleached"sample evaluated as part of the current lab study had lower tear strength than all of the previously evaluated samples, confirming that it was not typical of the mill production samples previously evaluated.This conclusion was reinforced by the fact that a second mill sample, "Mill Bleached 2" had strength characteristics that were very similar to those of the first one. This suggests current mill process operations subject the pulp to harsher conditions than during past operations, when the previous samples were taken. Regression equations for each of the plots in Figure 10 were used to calculate the tear index at a tensile index of 70 N.m/g. The resulting tear indices are plotted against pulp viscosity in Figure 11. 20 m E i 18 E O k a a C 16 O Y•031Pa8]91 d N C F 0 14 0 0 ) 0 x m O 9 ' C 12 R d f 10 8 10 12 14 16 18 20 Viscosity,mPa.s Figure 11.Tear index interpolated to 70 tensile index vs. viscosity(historical mill data). Figure 11 suggests that the viscosity reduction that results from switching from a one-stage to a two-stage oxygen delignification process is likely to have pulp strength implications. Summary and Conclusions Pulps were prepared in the laboratory from Canton mill chips under conditions chosen to simulate(1) mill pulping to the normal kappa number level of 26 and(2) a scenario under which cooking would be terminated at a higher kappa number(30.5).The 26 kappa pulp was then subjected to single-stage and two-stage oxygen delignification, using mill conditions for the single-stage process and conditions for the two-stage process that were chosen to increase the degree of delignification to approximately 60%. This higher degree of delignification was achieved by applying 2.8% caustic(vs. 2.0% in the single-stage system) and subjecting the pulp to a 20-minute, 140 psig, 93°C first stage followed by a 60-minute, 100 psig, 99°C second stage. The high-kappa pulp was also subjected to two-stage oxygen delignification. In this case, 59%delignification was achieved by applying 3.0%caustic and first-and second-stage oxygen temperatures of 89 and 99°C. All three oxygen pulps were subjected to D(EO)D bleaching to brightness values in the 86—87 range and the physical properties of the bleached pulps were determined after laboratory refining. Relative to the single-stage(0)pulp, the two-stage(00)pulp of initial kappa 26 consumed 23%less C1O2 and had a viscosity of 14.5 units vs. 17.4 units for the 0 pulp. By employing the two-stage oxygen process the color of the first D stage filtrate was reduced from 745 units to 450,and the color of the(EO) stage filtrate from 1490 units to 940. However, at a fixed value of tensile strength(70 N.m/g), the tearing ' 11 i resistance of the 26 kappa 00 pulp (14.8 mN.m2/g) was about 15% lower than that of the 0 pulp (17.0 mN.m2/g). The high-kappa two-oxygen-stage pulp consumed 16%less C1O2 and had a viscosity(17.7) which was virtually the same as that of the single-oxygen-stage pulp. In this case, the color of the first D stage filtrate was reduced from 745 units to 495, and the color of the (EO) stage filtrate from 1490 units to 1300.The tearing resistance of the fully bleached pulp (16.4 mN.m2/g) was only slightly lower than that of the reference(0)pulp. The tear strength deficiency of the 26 kappa two-oxygen-stage(00) pulp was not due to a fiber strength loss but rather to the fact that the 00 pulp had to be beaten to a higher sheet density in'order to achieve a given tensile strength. The 00 pulp had lower specific bond strength(lower bond strength per unit of bond area)than the 0 pulp. At a given tensile strength, the 00 pulp had higher burst strength than the 0 pulp. This correlates with the lower tensile stiffness of the 00 pulp. During refining, the 00 pulp densified more rapidly than the 0 pulp, although its freeness fell at the same rate. This suggests that the fibers of the 00 pulp have cell walls that are more readily destructured and/or hydrated. Comparison with historical mill data showed that tear strengths of both of the"Mill Bleached" samples evaluated as part of the current lab study were at the lower end of the range over nearly the whole range of tensile indices, which implies that current mill process conditions are harsher and result in lower pulp strength than when previous samples were taken for strength evaluation. Analysis of mill data suggests that the viscosity reduction that would result from adding a second stage of oxygen delignification is likely to have pulp strength implications. Utilization of two-stage oxygen delignification mill pulp may be expected to lead to lower final viscosity than the current 11.3-11,5 mPa.s, and correspondingly lower physical strength properties. Recommendations for Further Study It may be desirable to perform a second comparative evaluation of one- and two-stage oxygen delignification under conditions that closely mimic those of the mill process. More specifically,by proceeding according to the following steps: a) Obtain representative samples of the pulp entering the O-stage, with its accompanying liquor. Make a composite of samples gathered over several shifts. b) Measure the unwashed kappa number of this sample, and then wash a subsample thoroughly to get a washed kappa number, to characterize the degree of washing that has been achieved in the mill. c) Have the lab separate liquor from the sample, wash the pulp,then add liquor back in the amount needed to raise the kappa number to that of the unwashed sample. d) Do one- and two-stage oxygen delignification of samples having unwashed kappa number equivalent to mill values,using samples prepared as in step (c) above. e) Complete the bleaching sequence on both pulps, using the mill's kappa factor(presumably based on the washed kappa number of the oxygen stage pulp) in the Do stage. Simulate bleach washer inefficiency by carrying over 20%of the filtrate from each stage to the next. f) Do measurements as in the previous experiments: brightness, residuals, viscosities, combined effluent color,PFI runs and physical properties. Reverted brightness may also be of interest. g) Do additional measurements to facilitate interpretation of the results: Fiber Quality Analyzer(FQA) determination of fiber size distributions, coarseness and fines content on both unbeaten and refined pulps. This would address questions that could arise about the relevance of the previous results, in view of the difference between the properties of the lab-bleached and mill-bleached pulps. 12