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HomeMy WebLinkAboutNC0000272_Process Trial Docs Cited_20120201 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 (112O2) 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, 3rd Qtr 2011, internal data evaluation prepared by Nick McCracken and the Canton Mill Color Team for Evergreen Packaging, December 2011. PITC 201lb — 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 2011a—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. 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 lbs 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 62.2 BFR & Cluster Rule 60 ------------------------------------------------------------------------------------------------------------------- Color Improvement - c 47.8 5� 4 .741.244.E r 4'I.'I 43.4 42.7 41.2 39.7 39.1--- 37.1 - 0 40 --- ------- ------- ------- ------- ------- ------- ------- --------------- 36.1 36.5 37 9 35.9 U30 --- ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- ------- --- 20 w ���A ���� �gg� �000 boo^ �oo�. �003 �oQ� �oo� ti�Q� �001 �oo� �oo� �o,�o 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 Projects 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 I 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 5th 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 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 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 Year(s) 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 1st 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 CL02 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 51 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 10.13 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 RecyclingTM (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 Blue Ridge Paper Products, Inc. - Trial Report Hydrogen Peroxide (H202) on Hardwood Eo Stage - MTA #402230 TO: Michael Ferguson DATE: July 2, 2002 Fiberline 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 CI02 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 H2O2 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 CI02 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 CI02 cost. This meant that for every pound of H2O2 applied, a pound of CI02 must be removed in order to break even. A lower H2O2 price would have meant that less CI02 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. r Bill Adams (828) 646-2868 402230 H2O2 on HW .xls Page 1 719/02 Blue Ridge Paper Products, Inc. - Trial Report Hydrogen Peroxide (H2O2) on Hardwood Eo Stage - MTA #402230 Prior to 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, H2O2 was being applied to the HW Eo stage. Data from the most recent two (2) months prior to the trial (3/1/02 thru 5/12/02) 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 H2O2 application to the HW Eo mixer at about 6 Ibs/AD Ton. Application rate was based on recommendations by Atofina, Canton's H2O2 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 H2O2 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 II of the trial -scheduled after the HW Annual Outage. Part II of the trial was begun on 6/3/02 by continuing H2O2 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 lb/AD Ton. There was an operational issue involving the H2O2 system during this phase of the trial when the H2O2 solution transfer pump to the Eo mixer failed. Data are excluded from the summary during the pump failure. Part II of the trial was completed on 6/19/02 after MgSO4 was applied to the HW D-100 washer repulper to enhance H2O2 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. H2O2 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 CI02 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) standard deviation change from 2001 averages. Therefore, it cannot be concluded that this trial had an effect on sewer color. Recommendations: r _. 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: Hexenuronic 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 better than the data suggests- interference from Hexenuronic Acids makes the performance only appear to be poor. Bill Adams (828) 646-2868 402230 H2O2 on HW .xis Page 3 7/9/02 ' Blue Ridge Paper Products, Inc. - Trial Report Hydrogen Peroxide (1-1202) on Hardwood Eo Stage - MTA #402230 In the bleach plant, Hexenuronic 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: Thanks! To Rogelio Vega-Canovas of Atofina for this information. Bill Adams (828)646-2868 Principal Process Engineer CC: Bill Boris Johnnie Pearson Derric Brown / Melanie Samuels Paul Geoghegan Steve Single Chris Lifka File (x2) Pete Maxey Bill Adams (828) 646-2868 402230 H2O2 on HW .xls Page 4 7/9/02 N O W n ¢ UwNNInw NMm w wtl' 6UVVVpp!llN�Hinm �ii umiU N h M O W m W Q W O h h V W W W M W N y p q �b N M M M M W O d W W UI m W N M [� V• O b h W W W CJ Q M W W W N h b W f, � �0 Q Its 1f1 W m Q Q C) p p1" M N N M �W W W y Y1 tD W h Ih fV b t`l t+! 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(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(CIOZ)applied per kappa unit, the measure of residual lignin in the pulp. Canton does not determine the kappa number of pulp directly; instead,the 'V number or"PN" number is determined. The kappa number can then be estimated based on the relationship of kappa numbers to"PN"numbers. This relationship was checked in 1995 by Champion Corporate Technology for Canton. The Kappa Factor formula is: %CIOZ 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 Liebergott/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)fiberline 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 DCS 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. P ;udits 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: 5/17/01 D-1 Stage Optimization - Both Fiberlines 8/7/01 D-1 Stage Optimization - H202 Off Pine 11/1101 D-1 Stage Optimization - Pine Fiberline 12117/01 Pine Cooking Change (Extend Cooking Time) 215102 HW Cooking Change (Extend Cooking Time) 3/14/02 HW Optimization - D-100 pH 5/13102 H202 Trial(HW)(Ended 6/19/02) 6/20/02 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 D-100 Stage Kappa Factors o � 0.290 m N o N N r N O O 0.270 0.250 0 " o (V N N 0 NN o N O N O N 0,230 N o rn o 0.210 �+r 0.190 rt 0.170 } j 0.150 ' N� m z d o o P e2 o f o�o ❑pia a0aa z �`�i Elul x�'Zi 1O z m O.-- Q o O n O i U p O ©Kappa Factor-AD F l Kappa Factor-BD Chart#2- Hardwood D-100 stage Kappa Factors Hardwood D-100 Stage Kappa Factors m 0.310 N 0.290 o n CI! N 0.27D p O N NO m N N 0.250 0.230 o w N o o N N N O O N 0.2100.190 0 0.170 <r 0.150 pp Ol Q .E2in w E.'- `� dUaa UU2 qm yv� ON�S�ro o c o z m Q m a t o 0 2 o E o 3 b 0 u Y = 2 v1D ' n O OZ U On Om O Kappa Factor-AD 0 Kappa Factor-BD Bill Adams (828)646-2868 NPDES Items .xis Page 2 7/11/02 ,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 CI02 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 O�Delignification stage will reduce the kappa number of pulp going to the bleach plant and reduce CI02 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 BFRTM 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: Hexenuronic 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"PN"or"K" numbers and consumes C102, [ 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. 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 OZ Delignification stage reduces the"PN" by four(4) points and appears to reduce the"PN" by only 33%. By the start of the Eo stage,there is very little lignin left and most of the measured"PN"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 OZ 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, Hexenuronic 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: Thanks!To Rogelio Vega-Canovas of Atofina for this information. Bill Adams Principal Process Engineer CC: Bill Boris Johnnie Pearson Derric Brown Melanie Samuels Paul Geoghegan Steve Single `- Chris Lifka File(x2) Pete Maxey Bill Adams(828)646-2868 NPDES Items .xls Page 3 7/11/02 r.evergreem 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 1"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 D1 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 D1 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 D1 washer discharge (COD) from MRP and Eop recycle is consuming H2O2 applied to Eop stage. The Pine trial operating parameters resulted in a D1 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 D 1 stage and dropped from 5840#/day to 1870#/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 1#/T of dry H2O2, applied as delignification reinforcement into the Hardwood E stage and the Pine Eo stage, has to displace 1/2#/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 D1 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 D 1 stage KF reduction. There will be an increase in D2 C1O2 charge, which is typically about %2 (#/#basis) D 1 stage C1O2 reduction. A D1 stage trial KF target of 0.20,with H202base 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 D 1 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 D1, 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 D1 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 D1 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 D 1 and Eo filtrates on D 1 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 Eo D2 NaOH D2 period TPD Kno PN mmhos cond m KF % pH NaOH CEK 9Pm 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 July 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 1 764 1 6.39 1 6.08 1 152.98 1 536.81 1 101.01 1 0.22 1 1.10 1 3.10 1 11.71 1 2.58 1 101.72 1 0.96 86.3 July-Sept avg I I I I 1 1 93.6 1 1 1 1 1 2.48 1 81.3 Table 2: Hardwood H2O2 Trial Environmental and Quality Summary(averages) D1 color Eo color period TPD #/day x 1000 #/day x 1000 Visc cps D2 ISO 1st 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 Sept 762.48 9.67 5.97 14.68 86.44 Oct 763.76 7.36 7.46 15.07 86.33 July-Sept avg 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 C102/T NaOH/T NaOH/T C102/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 Sept 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 $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 913M KF acid 913M CEK gpm ISO 1st 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 1 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 Oct 609 9.9 10.0 9.74 133.1 0.24 0.17 3.32 15.5 3.2 142.2 86.6 July-Sept avg 132.9 3.37 146.3 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 visc 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 Sept. 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 avg 1.09 1.87 85.2 9.6 Table 6: Pine H2O2 Trial Bleach Chemical Usage and Cost Summary (averages) total# total# period C102/T NaOH/T C102 $/T NaOH $/T H2O2 $/T Total $/T 1 st 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 Aug 52.1 39.5 27.84 8.04 2.08 37.96 Sept 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 avg 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: • 1St 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. • D 1 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 D1 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 D 1 pH control. • As the D 1 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 D1 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 DI 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 6.1/5.65 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 D 1 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 DI 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). 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: • 1St 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 Eo 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 DI 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 H2O2 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 D 1 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 H2O2 is being consumed by the DI 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 H2O2 reinforcement is not effective. H2O2 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 DI KF levels. Target D 1 KF below 0.21 results in a disproportionate increase in Eo CEK, which the applied H2O2 cannot control. Page 9 5. Appendix. Graph 1: Hwd D1 Kappa Factor vs CEK Graph 2: Hardwood D1 Kappa CEK/D1 and D2 C102 charge relationship 2.80 2.60 120 2.40 110 2.20 100 Y 2.00 Q 90 U 1.80 N 80 1.60 O 70 V �D1 G02 1.40 60 - D2 G02 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 C102 gpm vs D2 NaOH 1.20 1.00 Q. 0.80 =O 0.60 m N 0.40 0 0.20 0.00 62.66 61.05 88.29 94.64 101.72 D2 C102 gpm Page 10 Graph 5: Pine D1 Kappa Factor(KF)vs CEK Graph 6:D1 and D2 C102 charge/CEK 3.8 relationship 3.614W 160.0 3.4 155.0 3.2 150.0 W 3.0 E 145.0 V 2.8 0) 140.0 2.6 N 0 135.0 2.4 V 130.0 toz c;oz 2.2 GPM 2.0 125.0 �W C10z 0.226 0.208 0.211 0.222 120.0 41 GPM 2.7 3.1 3.6 3.4 Kappa factor(KF) CEK Graph 7: Pine Eo%NaOH pH control 22.0 20.0 18.0 W p 16.0 5 14.0 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 D 1 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 D1 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 V Quarter 2011 Nick McCracken and Color Team 1 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 2 PI & SE Color Performance Primary Influent&Secondary Effluent Color Comparison 3Q 2010 vs.Trial 45,000 40,000 35,000 30,000 25,000 20,000 15,000 10,000 5,000 0 ❑3Q PI ❑Trial PI ■3Q SE ■Trial SE 3 P 1 & 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 D1 Filtrate Color Numbers 3Q 2010 vs.Trial Period 9,000 8,000 7,000 6,000 m 5,000 a a 4,000 3,000 2,000 1,000 0 . j AL ■3Q Hwd ■Trial Hwd ■3Q Pine ■Trial Pine 6 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 3Q 2010 vs.Trial Period 7,000 6,000 5,000 4,000 a N a 3,000 2,000 1,000 0 ■3Q Hwd ■Trial Hwd ■3Q Pine ■Trial Pine 8 Eo Filtrate Colors Hwd EO&Pine EO Color Numbers for Peroxide Trial Ending 9127/11 12 10 8 T 9 Ian 6 F 4 2 0 141 —Hwd Eo—Pine Eo—Linear(Hwd Eo)—Linear(Pine Eo) 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 3Q 2010 vs.Trial Period 7,500 7,000 6,500 m y 6,000 a 5,500 5,000 4,500 ■3Q10 ■Trial 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 Fiberline Total Bleach Plant Color 3Q 2010 vs.Trial 14,000 13,500 13,000 m 12,500 a y a 12,000 11,500 11,000 10,500 ■3Q10�Trial 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 m y 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 30 2010 16 Contaminated Condensate Color Condensate Color Numbers 3Q 2010 vs.Trial 2,500 — 2,000 T 1,500 v N n 1,000 500 Ah ■3Q10 Contaminated■Trial 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) 3ASewer Color Numbers 3Q 2010 vs.Trial 11,500 11,000 10,500 10,000 m 9,500 v a 9,000 8,500 8,000 7,500 7,000 ■3Q10�Trial 19 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 Trial affected operations 2071 Mi 1367 769 147 Pine D1 Pine Eo Pine BP 1273 493 Evap Condensate 3A (1437) F)kS (201) (1228) Non Trial mill operations Recovery,Kilns,BSW,Paper&Board PI SE (6720) (5476) Color Increase Color Decrease 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 MMT 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 without the written consent of ANDRITZ AG. MMT Pulp & 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-D 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 Consumption Summary Bleaching Sequence C102 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-Pht-D 8.8 4.5 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•m2/g) at 400 CSF CSF 124576 Softwood Do-Eo-D 84.93 8.68 124582 Do-PHT-D 81.93 8.51 124579 Do-Eop-D 83.81 8.41 124572 Hardwood Do-E-D 66.26 8.15 124745 Do-PHT-D 70.49 9.02 124818 Do-Ep-D 68.98 8.80 Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 2 of 11 MMT Pulp & Paper Experimental Standard Operating Procedures 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 Beating of Wood Pulp Tappi T236 Kappa Number NCASI TB#253 Color in Effluent TappiT227 Canadian Standard Freeness Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 3 of 11 MMT Pulp & 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: 150°F, 40 min., 10% cons. Sample ID 124574 Kappa Factor 0.24 CIO2, % 1.29 H2SO4, % 0.35 Final pH 2.8 Consumed C1O2i % 1.29 ISO Brightness, % 51.9 Color, C.U. 1850 Eo Stage: 175°F, 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: 165°F, 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 C102 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) Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 4 of 11 %MT Pulp & 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 CIO2, % 1.08 ISO Brightness, % 49.0 Color, C.U. 2125 Eop Stage: 175°F, 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: 165T, 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 Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 5 of 11 %MT Pulp & 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: 150T, 40 min., 10% cons. Sample ID 124580 Kappa Factor 0.2 CIO2, % 1.08 H2SO4, % 0.49 Final pH 2.9 Consumed CIO2i % 1.08 ISO Brightness, % 48.8 Color, C.U. 2125 PHT Stage: 200T, 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: 165T, 240 min., 10% cons. Sample ID 124582 C1O2, % 0.8 1.0 1.2 NaOH, % 0.30 0.40 0.50 Final pH 3.9 4.0 4.0 C1O2 Consumed, % 0.8 1.0 1.2 ISO Brightness, % 84.5 85.6 86.4 Color, C.U. -- -- 71 Viscosity, mPa-s -- -- 10.7 Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 6 of 11 %MT Pulp & 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: 150T, 40 min., 10% cons. Sample ID 124570 Kappa Factor 0.26 CIO2, % 0.67 H2SO4, % 0.7 Final pH 2.5 Consumed CIO2i % 0.67 ISO Brightness, % 67.4 Color, C.U. 685 E Stage: 175T, 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 C1O2, % 1.0 1.2 1.4 NaOH, % 0.40 0.48 0.56 Final pH CIO2 Consumed, % 0.997 1.190 1.394 ISO Brightness, % 85.5 86.1 86.7 Color, C.U. -- 27 -- Viscosity, mPa-s -- 10.7 -- Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 7 of 11 %MT Pulp & Paper Table 5. Hardwood Do-Pht-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: 150T, 40 min., 10% cons. Sample ID 124743 Kappa Factor 0.21 CIO2, % 0.54 H2SO4, % 0.7 Final pH 2.7 Consumed CIO2i % 0.54 ISO Brightness, % 64.7 Color, C.U. 373 PHT Stage: 200T, 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: 165T, 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 C1O2 Consumed, % 0.2 0.4 0.6 ISO Brightness, % 84.9 86.7 87.8 Color, C.U. -- 52 -- Viscosity, mPa-s -- 11.3 -- Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 8 of 11 %MT Pulp & 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: 150T, 40 min., 10% cons. Sample ID 124746 Kappa Factor 0.21 CIO2, % 0.54 H2SO4, % 0.7 Final pH 2.7 Consumed CIO2i % 0.54 ISO Brightness, % 65.0 Color, C.U. 345 Ep Stage: 175T, 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 CIO2, % 0.6 0.8 NaOH, % 0.04 0.24 Final pH 4.4 3.8 CIO2 Consumed, % 0.6 0.8 ISO Brightness, % 85.7 86.3 Color, C.U. -- 32 Viscosity, mPa-s -- 10.8 Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 9 of 11 AMMTL Pulp & Paper Table 7. Physical Strength Properties PFI Cond Burst Tensile Tear Tensile Elongation Descriptive CSF Wt Bulk Index Index Index T.E.A.0/m2) Stiffness LIMS ID ID (# (ml-) (gm) (cm'/g) (kPa•mZ/g) (N•m/g) (mN•m2/g) (kN/m) (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 Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG. Page 10 of 11 MMTL Pulp & 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. Confidential document.All rights reserved.No duplication or disclosure to third partiers permitted without the written consent of ANDRITZ AG Page 11 of 11 Laboratory Study of Likely Effects of Oxidatively Intensifying the Extraction Stages at Evergreen Packaging's Canton, NC Mill Progress Report Thomas J. McDonough February 10, 2012 (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 Pm 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 increasing the peroxide charge, pressurizing with oxygen and raising the temperature. In both cases the chlorine dioxide charge in the Do stage was decreased slightly and the chlorine dioxide charge in the D1 stage was adjusted to reach the desired target brightness. Effects on the color of all bleaching stage�effluents were monitored. Effects on bleaching chemical consumption and bleached pulp physical proprties were also measured. In the softwood case, adding peroxide to the(EO) stage resenpulp). n almost no decre se in total effluent color. Converting the(EO) stage to a (PO) stage decreasedal color by 11 0. 1 chlorine dioxide consumption was reduced by 5.6— 10 lb/ton(0,28—0 . % In the hardwood case, adding peroxide resulted in a 42%.reduction in color. Converting E stage to a (PO) stage gave a 50% reduction. Total chlorine dioxide consumptiortwas reduced by 12— 16 lb/ton(0.6— 0.8% on 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 of the hardwood pulps, as well as increases in the tensile strength at which the um tearing resistance is achieved. �% 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 of the pulp bleaching effluent and significantly decrease chlorine dioxide consumption. Introduction The Canton mill employs the D(EO)D bleaching sequence to produce bleached softwood and hardwood pulps. The mill commissioned a laboratory study to predict the effects of intensifying the alkali extraction stages in the bleaching sequences of both softwood and hardwood pulps. In the case of softwood, this amounted to converting the(EO) stage to either an(EPO) stage or a high-temperature pressurized peroxide stage, here denoted by (PO). In the case of hardwood the study assessed the effects of converting the E stage to a peroxide reinforced extraction stage(EP) or a(PO) stage. These changes can be expected to reduce the color of the mill's 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 may be found in their report! 2 Results and Discussion Multistage Bleaching Tables 1 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 peroxide charge, i.e. converting the (EO) stage to a (PO) stage, decreased the total color from 4299 units to 3836 units (an I I%reduction). In both the(EPO) and(PO)cases, the attendant decreases in Do kappa factor(C102 charge)caused slight increases in the color of the Do effluent. Nit 6000 5000 4299 4228 4000 3836 El D1 y El 3000 El 0 0 U 2000 1000 ji (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 14.3 14.3 ISO Brightness, % 35.2 35.2 35.2 Do Stage: 150°F,40 min., 10% cons. NW 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. 1 1.4 Temperature, °F 175 5 200 OZ Pressure(0/10/15/60 min.), psig 5/0/0/ 510/0/0) (100/100/0/0) H2O2, % 0 0.5 0.6 Final pH 1.0 11.0 11.1 Kappa Number 443.2 3.2 2.8 Viscosity, mPa•s 13.8 12.9 12.3 ISO Brightness, % 58.2 64.3 67.5 Filtrate color, C.U. 41k 2390 2045 1640 D, Stage: 165°F,240 min., 10% cons. C102, % 1.0 1.2 1.4 1.0 1.2 1.4 0.8 1.0 1.2 NaOH,% 0.45 0.54 0.6 0.45 0.54 0.6 0.3 0.4 0.5 Final pH 4.2 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 6.8 6.8 Viscosity, mPa•s 13.8 13.80 13.8 ISO Brightness, % 44.1 44. 44.1 Do Stage: 150°F,40 min., 10% cons. C102,% 0.67 0.54 0.54 H2SO4, % 0.7 0.7 0.7 Final pH 2.5 2.7 2.7 Residual g/L as C12 0 0 0 ISO Brightness, % 67.4 65.0 64.7 Filtrate color, C.U. 685 345 373 Extraction Stage: 60 min., 10% cons. NaOH, % 0.9 1.0 1.3 Temperature, T 175 175 200 02 Pressure(0/10/15/60 min.), psig (0/0/0/0) (0/0/0/0) (100/100/0/0) H2O2, % 0 0.3 0.5 Final pH 11.0 11.1 11.3 Kappa Number 1W AW 2.7 2.7 2.7 Viscosity, mPa•s 13.1 12.0 11.6 ISO Brightness, % 68.4 74.8 79.4 Filtrate color, C.U. 570 365 210 Dl Stage: 165°F,2 , 10% cons. C102, % 1.0 1.2 1.4 0.6 0.8 0.2 0.4 0.6 NaOH/H2SO4,% 0/0 0.48/0 0.56/0 0.04/0 0.24/0 0/0.09 0/0.01 0.0510 Final pH FOO-03 - -- -- 4.4 3.8 4.2 4.0 3.4 Residual C102, g/L 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 1000 ❑D1 El 800 742 5 635 El DO U 600 400 200 0 E (EP) (PO) Figure 2. Effecto4foettraction stage reinforcement on hardwood bleaching effluent color The results shown in Figures 1 and 2 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 of the hardwood pulp bleaching effluent. In regard to these effluent color reductions, it should be noted that the reductions achieved in actual mill practice may be slightly different. When individual stage effluents are combined the color that results is not the sum of the individual stage effluents. One reason for this is that the color of extraction stage effluents is pH dependent; 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 final 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 12 lb/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 •(EO) 86.5 (EPO) ■(Po> • 86.0 -------------------------- --------- ----------- C s 85.5 m 85.0 84.5 84.0 1.6 1.8 2.0 2.2 2.4 2.6 2.8 Total C102(Do+ D,), Figure 3. Final brightness vs. total C102 consumption; softwood pulp. Figure 4 shows the corresponding effects for the hardwood pulp.Adding 6 lb of peroxide per ton of pulp to the extraction stage resulted in a reduction in total C102 consumption of 12 lb/ton of pulp (0.6% on pulp.. Adding high-pressure oxygen and increasing the peroxide charge to 10 lb/ton while also increasing the temperature resulted in a further reduction of 4 lb/ton(0.2% on pulp). In this case the total reduction in C102 consumption would therefore be 16 lb/ton(0.,8% on pulp)relative to the case where neither oxygen nor peroxide was used. 7 87.0 86.5 86.0 ----------------- ---- ---------------- ---------- CD c s 85.5 ' rn i i i ♦E 85.0 (EP> 84.5 84.0 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 Total C102(Do+ D,), % Figure 4. Final brightness vs. total C102 consumption; hardwood pulp. Physical Properties of Bleached Pul s Softwood Pulps Inspection of the results in Table 3 shows that th studied extra tion stage modifications had, with one possible exception, virtually no effect on the physical properties of bleached softwood pulp. Figure 5 demonstrates the lack of any effects on the relationship between handsheet density and tensile strength and Figure 6 shows that the all three extraction types gave pulps with the same tear-tensile characteristic. The possible exception is an effect on elongation and its associated effect on tensile energy absorption, as shown in Figures 7 and 8. Table 3. Physical Properties of Bleached Softwood Pulps Density Tensile Burst Tear Tensile Pulp ID PH 'SF s Index Index Index T.E.A. (j/m2) Elongation Stiffness Index (#revs x 10') (m1.) (g/cm) (N'tn/g) (kPa'm2/g) (mN-m2/g) (mm) (kNm/g) (EO) 0.0 691 0.5 88 36.64 2.40 22.11 58.16 3.17 356.5 05 660 0.641 60.34 4.25 12.96 89.49 3.23 473.6 �.5 520 0.704 81.19 5.30 9.69 108.98 3.00 576.5 5.0 350 0.719 86.49 5.83 8.26 118.57 3.22 568.7 7.5 235 0.741 88.63 6.16 8.31 129.55 1 3.37 587.9 (F110) 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 3.49 579.5 7.5 88 0.787 93.91 6.32 1 7.14 140.25 3.50 1 589.7 (110) 0.0 696 0.538 33.44 2.22 23.08 44.76 2.73 332.5 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 7.58 130.04 3.39 576.0 7.5 91 1 0.781 96.06 6.23 1 7.31 1 148.79 3.56 614.6 8 120 100 •(EO) ♦(EPO) • • 80 •(PO) z K r d 60 d y (D 40 F ♦ • 20 0 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 Density,g/cm3 Figure 5. Softwood pulp tensile index vs. sheet density 30 25 •(EO) 01 w 20 ♦(EPO) ■(PO) Z E x 15 m c L 10 • H � 5 0 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 m 3.00 a� c 2.80 •(EO) w 2.60 ♦(EPO) 2.40 (PO) 2.20 2.00 0 20 40 60 80 100 120 Tensile Index, N.m/g Figure 7. Softwood pulp Elongation vs. Tensile Index 180 160 140 120 100 a u; 80 60 •(EO) ♦(EPO) 40 ■(PO) 20 0 0 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 Density Tensile Burst Tear Elonga-lion Tensile Pulp ID PF1 CSF 3 Index Index Index T.E.A. 0/m2) Stiffness Index (#revsx 10') (mI) (hem) (N-m/g) (kPa.m2/g) (mN.m2/g) ( ) (kNm/g) F, 0.0 557 0.535 29.17 1.34 9.06 26.68 1.90 335.7 0.5 528 0.602 4894 2.53 9.31 61.65 2.69 435.3 1.0 483 0.641 60.40 3.35 8.44 82.13 3.02 470.0 2.0 356 0.690 69.36 4.25 8.00 105.58 3.43 495.4 3.0 246 0.730 76.39 4.71 7.20 119.32 3.54 519.1 (FP) 0.0 556 0.526 30.64 1.39 8.54 25.90 1.79 341.7 0.5 536 0.606 51.95 2.60 9.40 66.86 2.76 445.5 1.0 484 0.654 61.04 3.31 9.18 82.53 2.97 478.8 2.0 377 0.694 71.15 4.08 8.69 11091 3.40 522.4 3.0 260 0.735 72.30 4.45 1 8.05 111.83 3.42 509.0 PO) 0.0 593 0.526 29.30 1.14 8.12 27.57 1.9 341.7 0.5 554 0.602 49.52 2.45 9.57 63.72 445.5 1.0 515 0.641 59.43 3.13 9.78 79.92 2.97 478.8 2.0 384 0.694 72.03 4.14 8.91 110.08 3.38 522.4 3.0 269 0.730 72 4.6' 8.11 1 117.64 3.47 509.0 90 80 •E ♦(EP) � 70 • Z x 60 0 m a C .y 50 C N ~ 40 30 1• 20 0.45 0.50 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 rn N E 9 • z E x 8 A m a c 8 •E W CEP) 7 ■(Po) 7 6 20 30 40 50 60 70 80 90 Tensile Index,N.m/g Figure 10. Hardwood pulp tearing resistanceNs. tensile index Summary and Conclusions Mill oxygen-delignified softwood and hardwood pulps were subjected o'laboratory bleaching trials to evaluate the effects of potential changes to the conditions of the alkali extraction stage. 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 PFrr 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 increasing the peroxide charge, pressurizing with oxygen and raising the temperature. In both cases the chlorine dioxide charge in the Do stage was decreased slightly and the chlorine dioxide charge in the D1 stage was adjusted to reach the desired target brightness. Effects on the color of all bleaching stage effluents were monitored. Effects on bleaching chemical consumption and bleached pulp physical properties were also measured. 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 peroxide charge, i.e. converting the(EO) stage to a (PO) stage, decreased the total color from 4299 units to 3836 units (an 11% reduction). In both the(EPO) and(PO) cases, the attendant decreases in Do kappa factor (C1O2 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 the pulp bleaching effluent and significantly decrease chlorine dioxide consumption. Report: No.2011-054, Fruyn's Island Technical Cent dritz Inc. (August 3, MW 13 Andritz—Alstrom 02 Delig Studies CONFIDENTIAL BUSINESS INFORMATION T9 �4 PRUYN'S ISLAND 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 ' r; =, fl c Allen Turner Pruyn's Island 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-Mo-Eo-D. The 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 C102 Charge HZOZ Charge Pulp and Sequence %ISO mPa•s Kg/BDMT KgBDMT Softwood Mill BS Lab O-Do-Eop-D 88.0 14.3 18.0 5.0 Mill Oz Lab Do Eop-D 88.4 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 88.5 17.1 I6.3 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) CADocuments and SetlingAmarshaffq ocal5euingffemporary Internet Files1OLKAMI-068 Pam 15W Final Repomdoc 1 i .. j 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 Operating Procedures PTTC-P27 Lo-Solids®CookingSimulation(27 Liter CirculatingDigester) PTTC-P6 Wood Chi Size and Thickness Distributions PTTC-P7 Wood Chip Moisture Free Fraction PTTC-P8 General Wood Chip Handling PITC-P9 Pulp Moisture Free Fraction - PITC-P10 Pulp Yield PITC-P11 Pulp Defiberin ,Centrifuge Washing,and Pin-shredding PTTC-P24 Conventional Kraft Cook(5 Liter Swing Digester) Ta22i T205 om-88 Forming Handsheets for Physical Tests of Pulp Tappi T248cm-85 Laboratory Beating of Pulp(PFI Mill Method) Tappi 1227om-94 Freeness of Put Tappi T220s -96 Physical Testing of Pulp Handsheets LaRpi T403om-91 Bursting Strength of Paper Tappi T414om-88 Internal Tearing Resistance of Paper Tappi T494om-88 Tensile Breaking Properties of Paper and Paperboard PTTC-I4 Dirt Count TAPPI 7236 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 TAPPI T230 Viscosity of pulp(capillary viscosity method) HUT Method 23.2.1995 Hexenuronic acid content of Kraft pulps PTTC-B3 Oxygen Deli nification PTTC-134 Chlorination PTTC-135 Acid Hydrolysis(Ahl-stage) PTTC-136 Alkaline Extraction PTTC-$8 Chlorine dioxide bleachin PTTC-B11 Low&medium consistency ozone deli niftcation in fluidizing mixer PTTC-B 12 Hydrogen eroxide bleaching PTTC-B 19 Pulp washing CPPA H.5 Colour of pulp mill effluents PTTC-A18 Carbohydrate content of wood or pulp b HPA C—PAD Standard Methods 3111 Metals by FAA Tappi T525 om-92 ISO brightness(pad formation and testing) CMocumenu and Senings\marshalRLncel SettingATernporary Internet Ftics\OLKA2001•068 Part 1 SW Final Repomdoc 2 F. 5 NI Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part l Alpheretta, GA December 6,2001 Results Table 1-A. Mill P 1p and Filtrate Results Sample Login Kappa Viscosity Brightness Rejects Tappi Dirt Sample Description ID Number % on Area/ppm {mPa s) %ISO pulp (>0.040 mm) SoftwoodsjW , , 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,mg/L 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. Table 1-2. Laboratory Conventional Kraft (CK) Cooking of Softwood- , 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 LS Pulp Table 1-8. Laboratory Two Stage Oxygen Deli gnifications 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 CADocunwrits and SettingslmarshalM ocal Selringffcrnporary Inrerm Files10LMU001-068 Parr 1 SW Final Repomdoc 3 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 1-12. Strength Results for Lab Softwood Lo-Solidso 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 10ocumems and Sertings5marsha]JU"a]SettingsU mporary Internet File510LK412001-0fi8 Pan I SW Final Repon.doc 4 Allen Turner Pruyn's Island Technical Center Andritz Ahistrom Sales Lab Report 2001-068 Part 1 Alpheretta, GA December 6,2001 Table l-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(°C) 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) - --- - --- -- - .- L/W Ratio(Llkg) 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 4 Time at Temperature (min) 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 Co-current: Temperature(°C) 165.3 169.5 170.0 166.4 169.5 163.8 166.4 166.4 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) 1%] 8.3 7.0 12.4 12.0 13.9 12.8 12.7 EA Consumed(%on wood NaOH) e- 15.7 16.3 16.8 17.3 17.4 16.7 17.1 17.2 H-Factor 960 1430 1680 1320 1670 1040 1320 1290 Kappa Number 37.2 27.5 23.7 21.7 18.7 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) 45.0 439 43.0 42.8 41.9 44.4 42.5 43.2 Knots>13 mm(%on wood) 0.61 0.63 --0i94,7' 0-03 0.35 0.42 0.23 0.03 aCK=Conventional Kraft Process bAQ=Anthraquinone `SODA=Soda Process CADocutne s and SettingslmarshaMocal 5ettings\Temporary Internet FkAOLK*2001-M Part I SW Final Reportdoc 5 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part I 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 M on wood NaOH) 10.0 10.0 10.0 Liquor EA(g/L,NaOH) 28.6 28.6 28.6 Liquor Sulftdity(%AA) 27.8 27.8 27.8 L/W Ratio(LJkg) 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 T8 EA Consumed(%on wood NaOH) 7.3 7.3 7.3 Displacement 1: Temperature(°C) 162.4 164.5 •-r 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(%on wood NaOH) 8.0 8.0 8.0 Liquor EA(g/L NaOH) 87.6 87.6 87.6 L/W Ratio(L/kg) 3.5 3.5 3.5 Fresh Liquor Flow(mL/min) 53.0 53.0 53.0 Fresh Liquor Flow Time(min) 60 60 60 Displaced Liquor Flow(mL/min) 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(gll..NaOH) 10.8 10.5 10.5 Displaced Liquor pH 12.9 13.0 13.0 Displaced Liquor Residual EA(g/L NaOH) 6.8 6.8 7.0 EA Consumed(%fl on wood NaOH) 6.3 6.4 6.4 C."Documenis and SeuingsVnwsha]A=al SettinrslTemporary Entemet FilesNOLMU00 1.068 pan 1 SW Final Repomdoc 6 • ris : Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part I 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(L/kg) 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 M on wood NaOH) 1.3 1.4 1.4 Displacement 2: Temperature(OC) 162.4 164.5 165.6 Time at Temperature(min) 180 180 180 EA Charge(% on wood NaOH) 6.9 6.9 6.9 Liquor EA(gJL NaOH) 44.7 44.7 44.7 Liquor Sulfidity(% AA) 27.8 27.8 27.8 LIW Ratio(Ukg) 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(mUmin) 30.0 30.0 30.0 Displaced Liquor Flow Time(min) 190 180 180 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) 29 29 3.0 Final Cooking Results: H-Factor 2400 2870 3150 Kappa Number 31.1 25.4 22.3 Viscosity(m.Pa•s) 41.7 35.2 30.2 Viscosity/Kappa Number Ratio 1.3 1.4 1.4 Total Yield(%on wood) NM 43.3 42.3 Total Rejects(%n 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 C!Mocumenu and SeningsV narshalPlocal5eLlingslTemporary Intema FilesloLMU001.068 Pan 1 SW Final Repon.doc 7 �a l 's P=r t i5 0 n All g 9 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 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 nun. 90°C 80 psi 10% consistency 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 f Filtrate Metals,mg/L Ca=35.8 Fe=0.17 Mg=1.60 Mn=0.70 Do-Stage:50 min.,60°C,mill filtrate added back to 10 % consistent Kappa Factor 0.25 0.25 CIO,charge, °Io 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=I28.24 Fe=1.90 Mg=38.12 Mn=15.10 Eop-Stage:75 min.,77°C,40 Rsi, 10% consistency Sample ID 2001-00 2785 2852 NaOH charge, % 1.3 1.3 HZOZ,charge, % 0.3 0.5 Final pH 11.5 11.7 Consumed H202, % 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-Stage:2.40 min.,74°C, 10 % consistency 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=6.48 Fe=0.15 Mg=1.20 Mn=0.43 Tappi Dirt Area/ppm(a4.o4mn2) 23.99 C: acumemu and SetfingslmarshalnLocat SettingsWemporary lraemet FileslOLMU001-068 pan 3 SW Final Repon.doc - 8 f a ri 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 D-Stage: 50 min. 60°C mill filtrate added back to 10 % consistent Kappa Factor 0.20 0.25 CIO,charge, % 1.03 1.28 Mill Filtrate Colour,C.U. 890 890 Final pH 2.8 2.2 Consumed CIO,, % 1.03 1.28 Brightness, %ISO 49.9 55.6 Filtrate Colour, C.U. No Sample I070 Filtrate Metals, mg/L Ca-174.7 Fe=2.2I Mg=38.28 Mn=14.68 Ca=173.84 Fe=2.31 Mg=40.28 Mn=15.42 - Eop-Stage:75 rnin.,77°C,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 66.4 719 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.,74°C, 10 % 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 C102, % 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 88.4 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 Area/ppm(7.o.o4mm2) OTGcumew and SeuinyArnarshaIM-0cal Serl€ngslTemporary lmerm F-rlsAOLK4\2001-0"Pan t SW Final Repon.doc 9 6! d 1 S q1 Allen Turner Pruyn's Island Technical Center Andrita Ahlstrom Sales Lab Report 2001-068 Part I 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 psi 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 z Do-Stage: 50 min.,60°C,mill filtrate added back to 10 % consistency Kappa Factor 0.25 C102 charge, % 1.20 Mill Filtrate Colour,C.U. 890 Final pH 1.9 Consumed CIO,, % 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 min.,77°C,40 psi010%„consistency Sample ID 2001-00 2903 NaOH charge, % 1.3 H2O2,charge, % 0.5 Final pH 11.5 Consumed H202, % 0.3 Kappa number 2.22 Viscosity, nipa•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 Cl02 charge, % 0.4 0.5 0.6 NaOH, % 0.05 0.08 0.10 H2SOa, % --- --- --- 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=3.44 Mn=0.51 Tappi Dirt Area/ppm(>.0.04mm2) CADocamcnLs and SettingalmarshalRLocal Settingffempamry Internet Filesl0LMUD01.065 Pao I SW Final Repo t.doc 10 uws s. I°off Allen Turner Pruyn's island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6, 2001 Table 1-7. Laboratory O-Do-Eop-D Bleaching of Lab Softwood LS Pulp Sample ID Lab LS Brownstock AL776 2001-002447 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=U 3 Mg=1.60 Mn=0.25 D.-Stage: 50 min. 60°C mill filtrate added back to 10 % consistent Kappa Factor 0,22 C102 charge, % 1.03 Mill Filtrate Colour,C.U. 890 Final pH 2.1 Consumed C102, TO 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 Eop-Stage:75_adn.,77°C,40 psi, 10% consistency Sample ID 2001-00 2855 NaOH charge, % 1.3 H2O2,charge, % 0.5 Final pH 11.5 Consumed H2O2, % 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.,WC, 10 % consistency Sample ID 2001-00 2856 002 charge, % 0.4 0.6 0.8 NaOH, % 0.07 0.55 0.60 H2SO4, % --- --- --- Final pH 3.3 5.6 7.6 Consumed C102, % 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 Area/ppm(>,o.o4mm1) 34.08 CMGcumenu and SettingArnarshaMUcal Seuingffemporary Internet Files%OLK4L200I-068 Pan I SW Final RepDn.4GC E t «3 r34 L Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Pan 1 Alpheretta,GA December 6, 2001 Table 1-8. Lab Two Stage Oxygen Delignifications of Mill Softwood Brownstock Pulp Sample ID Mill Brownstock 2001-002000 Kappa number 21.5 Viscosity, mPa•s 22.0 Brightness,%ISO 29.3 Oxygen Trial O 00 0-0 Sample ID 2001-00 2530 2760 2763 Stage 1 NaOH, % 1.6 2.2 1.0 Time, min 60 30 30 Temperature,°C 90 100 100 Pressure,psi 80 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, %n --- 10 10 Final pH 11.5 11.7 11.5 Kappa number 12.6 9.8 11.3 Viscosity,mPa•s 16.3 14.4 16.2 Brightness, %ISO 34.1 ,38A 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 C-Mocumems and Setiings5marshalN ocal SeningsWemporary lnteMet Files1OLK412001.06a Pan 1 SW Final Repomdoc 12 Al Allen Turner Pruyn's Island Technical Center Andritz AhIsLrom Sales Lab Report 2001-068 Part I Alpheretta, GA December 6,2001 Table 1-9 Strength Results for Selected Mill and Lab Softwood Pulps Burst Tensile Tear LIMS ID Descriptive PF1 CSF Bulk Index Index Index Fold (log,o) 2001- ID (#revs) (mL) (cm3/g) (kPa•m2/g) (N.nVg) (mN•m2/g) 2000 Mill 0 705 1.9 3.1 39.9 22.0 2.07 Brownstock 500 679 1.6 4.4 60,7 14.8 2.70 1500 649 1.5 5.0 72.2 11.3 2.90 4000 494 1.4 6.2 83.9 10.1 3.02 8000 252 1.4 6.4 89.9 8.5 2.92 2003 Mill 0 680 1.8 3.2 40.9 18.8 1.93 Oxygen 500 669 1.6 4.5 60.1 13-5 2.63 1500 586 1.5 5.4 73.5 9.5 2.72 4000 407 1.4 6.4 84.4 8.2 2.94 8000 178 1.3 6.7 93.8 7.4 2.97 2004 Mill 0 676 1.7 3.3 40.2 20.7 2.07 Fully Bleached 500 663 1.5 4.8 65.2 12.9 2.61 1500 601 1.4 5.5 74.8 10.7 2.74 4000 417 1A 6.0 88.1 8.5 2.94 8000 192 1.3 6.5 89.0 8.4 2.79 2853 Mill BS 0 691 1.7 2.4 35.9 24.2 Lab 500 677 1.6 4.1 57.5 14.3 O-Do-Eop-D 1500 630 1.4 5.1 72.2 11.5 4000 460 L4 6.2 94.3 8.9 8000 189 1.3 6.6 92.1 8.3 2447 Lab LS 0 681 1.7 3.7 54.9 20.2 2.71 Brownstock 500 666 1.5 4.9 70.2 16.5 3.11 1500 635 1.5 5-7 85.7 13,8 3.14 4000 507 1.4 7.0 96,8 11.6 3.18 8000 277 1.3 7.7 101.4 10.9 2560 Lab LS 0 671 1.7 3.1 46.8 25.6 Oxygen 500 664 1.5 4.9 68.5 16.6 1500 627 1.4 5.7 81.5 12.8 4000 463 1.4 7.1 92.6 11.5 8000 241 1.3 7.8 100,9 10.2 2856 Lab LS 0 676 1.7 2.4 35.5 29.2 O-Do-Eop-D 500 667 1.5 4.7 59.2 17.4 1500 634 1.4 6.0 75.6 12.9 4000 483 1.4 6.7 87.6 10.7 8000 263 1.3 7.6 94.5 10.3 c.)Documcms and SettingAmarshaffiLocal SettingATemporary Internet Ffts\0LK4X2001-068 Pan I SW Final Repamdoc 13 j Allen Turner Pruyn's Island Technical Center Andritz AhIstrom Sales Lab Report 2001-068 Part I Alpheretta,GA December 6,2001 Table I-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 2001-002853 Mill BS Lab O-Do-Eop-D 86.0 8.8 2001-002447 Lab LS Brownstock 98.9 11.3 2001-002560 Lab LS Oxygen 95.0 11.1 2001-002856 Lab LS O-Do-Eop-D 90.2 10.6 CADocuments and SeftingAmarshalPLocal SeltingsUemporary InLernat Files\OLKA2001-068 Pan I SW Final Repon.doc 14 U" L Af Allen Turner Prayn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part I Alpheretta,GA December 6,2001 Figure 1-1. Total Yield versus Kappa Number for Lab Softwood Cooking 50 49 48 47 - '0 0 46 - 45 0 0 44 - 43 - 42 - 0 CK,EA=19.2%on wood 41 M CK,EA=21.6%on wood 40 A 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 - m CK, EA=21.6% on wood 32 - A LoSolids 30 . E 28 z 26 -- CL 24 -- 22 - 2o -,. 18 16 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 H-factor C:U)ocumc=and 5euingsVnaTshaJl\Local SeningslTemporary Intemet I'lles1OLK620OI-069 Pon 1 SW Final Rzpan,doc 15 � < j # t3 Allen Turner Pruyn's Island Technical Center Andrit2 Ahlstrom Sales Lab Report 2001-068 Part I Alpheretta,GA December 6,2001 Figure 1-3. Viscosity versus Kappa Number for Lab Softwood Cooking 50 45 40 w IL a 35 E °o 30 N O o C- 25 U y _ 20 - 1 ♦CK,E4-19.2%an wood CK,EA=21.6%on wood 10 ♦LDS 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 v21 ®CK,E4=19.2%on wood 20 a CK,EA=21.6%on wood d 19 a Lo-Solids 0 c 18 0 17 V 4) 16 E N 15 c U 14 13 12 16 18 20 22 24 26 28 30 32 34 36 38 Kappa Number C:tiDaewnents alai Saningslmarsha1ALocal Scnings\TenWrnry Inlern<t HeAOLK412001.068 Pus I SW Final Repon.doc 1 I L Ij Allen Turner Pruyn's Island Technical Center Andritz AhIstrom Sales Lab Report 2001-068 Part I 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 Mill Fully Bleached --0—Mill BS Lab O-D-Eoj>-D E 20.0 Lab LS BS E - ■ Lab LS Oxygen X Lab LS O-D-EWD _j W 7 15.0 - (U 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 110.0 'ensile Index(N-m1g) Figure 1-6. Tensile Index very PF1 Revolutions for Selected Mill and Lab Softwood Pulps 110.0- 100.0- pt 80,0- E z Mill BS ; 70.0. Q Mill Oxygen CD 60-0- Mill Fully Bleached 50.0- e Mill BS Lab O-D-Eop-D 40.0 Lab LS BS Lab LS Oxygen 30.0 Lab LS O-D-Eop-D 20.0- 0 1000 2000 3000 4000 5000 6000 7000 BODO 9000 PFI Revolutions CADocurnems and ScminpVrLw-slWrdi3calSettings�Tv.Tnporarylntemei Filci50 MU00 I-M Pan 1 SW Finai Rtwrt.doc 17 A L Allen Turner Pruyn's Island Technical Center Andritz A-histrom Sales Lab Report 2001-068 Part I Alpheretta,GA December 6,2001 Figure 1-7. Mill Softwood Brownstock Pulp 2001-002000 30 150 140 25 130 120 X X -- 110 20 - V 100 E go 12 151— 20 -- 70 10 5D co 40 LL 5 30 - 20 10 01 i, 0 100 20D 300 400 500 600 700 800 900 1000 Canadian Standard Firearms jqjQ Bulk a Tear Index * Burst index 9 PF1 --*—Tensile Index (10, crre/9) (MN-rr?/g) (10' Wa-rrft) (10-2 revs) (N-rrVg) Figure 1-8. Mill Softwood Oxygen Pulp 2001-002003 30 - 150 140 25 130 120 X X 20 100 0- -- 90 z 77� 130 70 60 10 j 50 ir 40 a5 " 30 20 10 T 0 0- 100 200 300 400 500 600 700 800 900 1000 Canadian Standard Freeness(mL) 0 Bulk CM -m—TearIndex k Burst Index PEI1 3/9) —0-4eNilm/g)dex (101 Wa-rnl/g) CADocunwnts and Smiji&sV=hARLDcal SeningATenWrary Internei Filv8N0LK41200l-0U Part I SW Final XcWn.doc 18 Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part I Alpheretta,GA December b,2001 Figure 1-9. Mill Softwood Fully Bleached Pulp 2001-002004 30 150 140 i 130 25 I 120 110 20 i 100 _ ! 90 m � ae 15 ! 70 i € 160m 10 0 ix 5 I i i 40 ai 5 I 30 a i 20 E 10 01 0 100 200 300 400 500 600 700 800 900 1000 Canadian Standard Freeness(mL) —a—Bulk —0 Tear Index Burst Index -- -- - 10' cm3/g) mN•m2/g) (10' kPa•rif/g) Figure 1-10. Mill Softwood BS Lab O-Do-Eop-D Bleached Pulp 2001-002853 30 150 140 25 j I ! 130 120 ' I ! 110 m 20 100 c c0. ! �`a 90 ) m C n 15 I 70 H 3 m 60 m m 10 i 50 I 40 9L 5- I 30 20 j 10 0 0 100 200 300 400 500 600 700 800 900 1000 Canadian Standard Freeness(mL) +Bulk -- -Tear Index - --Burst Index 10' cm31g) mN mil } (101 kPa rrl�lg) C:\DOGnrn=and SeninpXtn shalKLecal SeningslTcnWrary lntcmei Files50LK4%2001.068 Part 1 SW Final Report.dac 19 � 7 1:� n1Sn i!. Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-11. Lab Softwood Lo-Solids° Brownstock Pulp 2001-002447 30 , 150 140 _ 130 25 120 x i 110 X c 20 100 E 90 ) 1 I 80 5 c r 70 �— 10 50 m m j { 40 li 5 i I 30 10 o 0 100 200 300 400 500 600 700 800 900 1000 Canadian Standard Freeness(mL) �—Bulk Tear Index --&---Burst Index 10' ar>31g) mN m21 ) (16; kPa•melg) PEI Figure 1-12. Lab Softwood Lo-Solids` Oxygen Pulp 2001-002560 30 150 140 I 25 130 i I 120 X I 110 m c 20 100 C x ® air 15 a i 80 m aF i i 70 �- m 1050 i m i 40 a 5 i 30 i 20 1 I i 10 0 0 100 200 300 4a0 500 60o 700 Boa 9W I" Canadian Standard Freeness q �—Bulk — —Tear Index Burst Index —®—PFI •—o--•Tensile Index (10' CrrPlg) (mN•rrNg) (10' kPa•rT?lg) (10-1 revs) (N•mlg) C Documents and SeningsXrn=halALocal SmingskTernpo=y Inlemet FileslOLK4\2001-068 Part 15 W Final Rcpon.dac 20 qq P Allen Turner Pruyn's Island Technical Center Andritz Ahlstrom Sales Lab Report 2001-068 Part 1 Alpheretta,GA December 6,2001 Figure 1-13. Lab Softwood Lo-Solidso O-Do-Eop-D Pulp 2001-002856 150 140 130 i € 120 a 20 ! i I 110 a 100 I 3 ' 90 ). m F 166 80 = c 70 60 R2 10 - 50 40 u. EL 30 110 0 0 100 200 300 400 500 600 700 800 900 1000 Caopdi3n _. r. �—Bulk —a—Tear Index --A Burst Index 10' atrplg) mN rr>zlg) (10' kPa-rr?lg) C:Oocum s and ScningslmarshalllLocal ScningsWemporary lntemm Fllea{OLK412001-068 Pan 1 SW Final Rcport.doc 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 Report 2010-081 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-Eo-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 run 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 Procedure Wo D• sseription PITC-P2 Conventional Kraft Cook PITC-P6 Determining size and thickness distributions of wood chips PITC-P7 Wood Chip Moisture Free Fraction PITC-P9 Determining the moisture free fraction of pulp PITC-P 10 Determination of pulp yield PITC-P12 Screening a large amount of pulp TAPPI T230 Viscosity of pulp (capillaryviscosity method TAPPI T236 Kappa#of pulp TAPPIT248 Laboratory beating of pulp (PF1 mill method TAPPI T525 om-92 ISO brightness (pad formation and testing) PITC-B3 Oxygen Defignification PITC-B8 Chlorine Dioxide Bleaching PITC-B6 Oxidative Alkaline Extraction PITC-B 19 Pulp washing NCASI TB#253 Color Determination TappiT227 CSF Tap pi T220 Bulk TappiT403 Burst Tappi T484 Tensile Tappi T414 Tear William Miller Pruyn's Island Technical Center Evergreen Packag . Lab ' -.. , ■ ,: Canton, . . 2011 Photograph #1. Mill supplied furnish from . digester . . , belt. S= )� ��- � � �©s - � ■ _ � � \ �/� . , ' �. . . - . _ 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. t .r if William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Photograph #3. Hand-picked reject chips from mill furnished digester feed belt before PITC laboratory cooking. 1V AP{ � w � d _ ,F i J7 ' i l � ' William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 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 7.0-12.7mm(%) 16.4 Chip Thickness 4-6 mm(%) 37.5 Chip Size 12.7-25.4 mm(%) 59.1 Chip Thickness 6-8 mm(%) 16.7 Chip Size 25.4-45.0 mm(%) 19.2 Chip Thickness 8-10 mm(%) 7.4 Chip Size>45.0 mm(%) 2.4 Chip Thickness>10 mm(%) 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 Report 2010-081 Canton,NC January 31,2011 Table 3 . O-Do-Eo-D Bleaching. Mill Fully Bleached Pulps Lab Cook ID AC3465 Date Received 9/23/10 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 C102, as C12,% 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 -*0 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 C102, as Cl2,% 2.1 2.6 3.2 NaOH,% 0.30 0.45 0.54 Final pH 3.6 3.9 3.8 Residual CI02, 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 C1O2, as Cl2,% 2.4 3.0 Final pH 2.6 2.4 Residual g/L as Cl2 0 0 ISO Brightness, % 63.3 60.1 Filtrate color, C.U. 450 495 Eo Stage: 80°C, 60 min., 35psi 0 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 C1O2, 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 CIO2, g/L 0 0.0004 0.0011 0 0.0007 0.0015 Residual g/L, as Cl2 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's Island Technical Center Evergreen Packaging Lab Report 2010-081 Canton,NC January 31,2011 Table 4. Physical Strength Properties Burst Tensile Tear Tensile Tensile Cond Wt T.E.A. Elongation Stiffness Thicknes Descriptive PFI CSF Bulk Index Index Index Stiffness LIMS ID ID (#revs) (mL) (gm) (cm3/g) (kPa•m2/g) (N•m/g) (mN•m2/g) O/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 7.59 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 Index(&, 400CSF of Selected Softwood Pulps Tensile Tear Descriptive Index Index LIMS ID ID (400 CSFt 400 CSFat 120938 Mill Fully Bleached 9 (rec'd 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 (rec'd 1113111) 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 rn E \ z 80.00 X N C W •y 60.00 mill fully bleach F f O-Do-Eo-D f 00-Do-Eo-D 00-Do-Eo-D 40.00 Jt mill fully bleach#2 20.00 0.00 0 100 200 300 400 500 600 700 800 CSF(ml) 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 E z 80.00 x a c d y 60.00 c d 40.00 mill fully bleach —O-Do-Eo-D -A 00-Do-Eo-D 20.00 t 00-Do-Eo-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 30.00 A\\* 25.00 _rn �£ 20.00 z E X N r 15.00 R m 10.00 ♦mill fully bleach —F O-Do-Eo-D —�00-Do-Eo-D —�00-Do-Eo-D 5.00 f mill fully bleach#2 0.00 0.00 20.00 40.00 60.00 80.00 100.00 120.00 140.00 Tensile Index(N-mlg) William Miller Pruyn's Island Technical Center Evergreen Packaging Lab Report 2010-081 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 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 resistance of the 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 pulp after two oxygen stages consumed 16% less C1O2 than the single-oxygen-stage pulp and had a fully bleached 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 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 levels 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 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 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 Do 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 Do 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 D1 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 min., 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--*0 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 Dl 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,% 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 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 W R Z=2O-Stages ached 25 n Stock O U _N20X,,�Z s 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=5.00x+76.68 y=3.68x+80.13 y=3.12x+79.38 $7 ---------. ........ ................................ .----..... .......---- ---------- ........---- N N N C t 86 01 I m 85 •1 O-Stage ♦2 O-Stages ♦Hi-K+2 O-Stages 84 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 Total C102(Do+D1)as C102i% 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 Pulps Tensile Burst Tear Tensile PFI T.E.A. Elongation Pulp CSF Density Index Index Index Stiffness Index 10-) ID (revs x (mL) (g/cm3) (N•m/g) (Oa-tnYg) (mN•m2/g) G/m2) (nun) Stiffness 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 7.59 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 7.5 321 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 2.51 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 97.49 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 1 � •Mill Bleached ♦OD(EO)D £ 25 ,` ■OOD(EO)D Z x 20 c y 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 Bleached 90 ♦OD(EO)D ■OOD(EO)D £ 80 Hi-K-OOD(EO)D ■ axi 70 c r 60 / N / aCi 50 / / / 40 / / / / 30 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 •Mill Bleached 30 ♦OD(EO)D ■OOD(EO)D NE 25 Hi-K-OOD(EO)D Z E x 20 a y 15 10 5 0.55 0.60 0.65 0.70 0.75 0.80 0.85 Sheet Density, g/cm3 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 A ♦OD(EO)D N 6 ■OOD(EO)D dHi-K-OOD(EO)D 5 // • x x � d / c 4 / 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 a� E �,• ■ x 8 < O y s J C s�♦I (h •Mill Bleached C ♦OD(EO)D n ■OOD(EO)D .y fHi-K-OOD(EO)D 4 0.55 0.60 0.65 0.70 0.75 0.80 0.85 Sheet Density,g/cm3 Figure 7. Tensile stiffness index vs. sheet density 8 Response to Refining As shown in Figure 8, 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. 800 700 . 600 500 J E4 LC 400 M Cn U • Mill Bleached 300 ♦OD(EO)D �. 200 • OOD(EO)D H i-K-OO D(EO)D 100 0 0 1 2 3 4 5 6 7 8 9 PFI Revs x 10-3 Figure 8. Freeness vs. number of revolutions in the PF1 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 ■ M U 0.70 01 0.65 CD •Mill Bleached ♦OD(EO)D N t 0.60 ■OOD(EO)D N Hi-K-OOD(E0)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 •Visc.13.5 30 •Visc.14.6 •Visc.11.6 .Visc.12.1 .Visc.10.3 ■Visc.17.7 ■Visc.12.3 rn 25 ■Visc.14.61 Visc.13.8 N E ♦Mill Bleached 2 E 20 x d 15 m d F- 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 "E z 18 E x m v = 16 y=0.3677z+s.2321 N in C F � 14 O O 16 O x v O _= 12 R m 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 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 11 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