Operational Challenges in Energy and Chemical Recovery in Kraft Pulp Mills

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1 Operational Challenges in Energy and Chemical Recovery in Kraft Pulp Mills Honghi Tran University of Toronto Toronto, ON, CANADA Roberto Villarroel Eldorado Brazil Sao Paulo, BRAZIL The 7 th International Colloquium on Eucalyptus Pulp Vitoria, Brazil, May 28, 2015 Brief Overview Presentation Outline Energy & Chemical Recovery from Black Liquor Operational Issues Operational Challenges in Modern Eucalyptus Pulp Mills 2 1

2 Kraft Pulping Process Uses sodium hydroxide (NaOH) and sodium sulfide (Na 2 S) as cooking chemicals Predominant pulping process ~130 million metric tons/year globally 77% of all wood pulp (>90% in Brazil) Advantages High versatility High pulp strength Favorable economics (high chemical and energy recovery efficiency) 3 A 1000 t/d Kraft Pulp Mill produces 1500 t/d BL d.s t/d weak black liquor 3000 t/d Chemicals Wood Chemicals Dissolved Organics Black Liquor (dry) 500 Fibre Pulp 0 4 2

3 Black Liquor Recovery Wood Chips Digester (Courtesy of Valmet) Recovery Boiler Power Boiler Waste Water Treatment Slaker Green Liquor Na 2 CO 3, Na 2 S 5 Common Operating Problems Evaporator Fouling/scaling Corrosion Poor efficiency Low solids in product liquor Recovery Boiler Fouling/plugging Corrosion/cracking/tube leakage Low steam production Poor sootblowing efficiency Poor water circulation Gaseous/particulate emissions Tube damage by falling deposits Unstable combustion/blackouts Jelly roll smelt/smelt run offs Low reduction efficiency Smelt water explosions Dissolving tank explosions High dregs in smelt Recausticizing and Lime Kiln Overliming Poor causticizing efficiency Poor green liquor filterability Poor mud settling/low solids Corrosion High kiln fuel consumption Ring/ball formation Refractory damage Chain damage Gaseous/particulate emissions High residual carbonate Poor lime quality/availability Liquor Cycle Non process elements High deadload Na and S imbalance High sulphidity operation Corrosion 6 3

4 RB Fouling RB Superheater Corrosion 7 Lime Kiln Ring Formation Ball Formation 8 4

5 Recovery Boiler Capacity Year Capacity t/d d.s. (25.6 million lbs/d d.s.) (Courtesy of Valmet Power) 9 Technological Advancements Recovery Boilers High firing capacity High solids (80+%) firing High steam temperature/pressure (515 o C/130 bar, 960 o F/1885 psig) High heat recovery efficiency Sootblowing technology NCG burning Cl and K removal systems 10 5

6 Technological Advancements Evaporators/Concentrators High solids (80 + %) Falling film (tube type & plate type) Reynolds enhanced crystallizers Recaust and Lime Kilns Pressurized filters Lime mud dryers and product coolers Multi fuel burners Alternative fuel burning Improved Process Control and Metallurgy 11 Technological advancements have alleviated many problems, but have also made some problems worse and have led to new problems 12 6

7 Problems in Modern Pulp Mills Evaporator Fouling/scaling Corrosion Poor efficiency Low solids in product liquor Recovery Boiler Fouling/plugging Corrosion/cracking/tube leakage Low steam production Poor sootblowing efficiency Poor water circulation Gaseous/particulate emissions Tube damage by falling deposits Unstable combustion/blackouts Jelly roll smelt/smelt run offs Low reduction efficiency Smelt water explosions Dissolving tank explosions High dregs in smelt Recausticizing and Lime Kiln Overliming Poor causticizing efficiency Poor green liquor filterability Poor mud settling/low solids Corrosion High kiln fuel consumption Ring/ball formation Refractory damage Chain damage Gaseous/particulate emissions High residual carbonate Poor lime quality/availability Liquor Cycle Non process elements High deadload Na and S imbalance High sulphidity operation Corrosion 13 Challenges in Modern Eucalyptus Mills Non Process Elements (NPEs) Low lime mud solids and poor green liquor filterability Cl and K accumulation and control Na and S balance (or imbalance) 14 7

8 Non Process Elements (NPEs) Elements that do not participate in the pulping process Commonly referred NPEs: Cl and K (most K actually exists as a process element, not an NPE) Mg, Si, Al, P, Mn, Fe V, Cr, Ni, Zn, Pb, Cu, Ti, Ba, etc. (amounts typically too small to be significant) Can be problematic if present in large amounts 15 Sources of NPEs Sources Wood Makeup lime Makeup chemicals Makeup water Additives Refractory bricks Corrosion products Biosludge Petcoke Elements K, Cl, Mg, P, Si, Al, Mn, Fe, etc. Mg, Si, Al, P, Fe Cl Cl, P Mg, Si Si, Al Fe, Ni, Cr Si, Cl, Mg, K, P, Mn, Fe, Al V, Ni 16 8

9 Whether or not an NPE accumulates in the recovery cycle depends on the solubility of its compounds in the liquor 17 Solubility of NPE Compounds Elements Solubility in Liquor Consequences Cl, K, P, B, V High Accumulate in the liquor cycle Si, Al Medium Accumulate in liquor & lime cycles Mg, Mn, P, Fe, Ni, Cr, Si, Al Low Accumulate in the lime cycle Removed from the system with grits, dregs, mud and lime dust 18 9

10 Accumulation Factors Accumulation Factor LIQUOR CYCLE Mill 1 Mill 2 Mill 3 Mill 4 Accumulation Factor LIME CYCLE Mill 1 Mill 2 Mill 3 Mill 4 0 Mg Mn Al Si K Cl 0 Mg Mn Al Si S K Cl Richardson et al, 1998 ICRC 19 Problems and Contributing NPEs Operational Problems Recovery boiler fouling Recovery boiler SH corrosion Evaporator scaling Poor green liquor filterability Poor mud settling/dewatering Low lime availability/reactivity Contributing NPEs Cl, K K, Cl Si, Al, Ca, Fe Si, Mg Si, Mg, Al, Fe S, Mg, Si, P, Mn, Fe, Al 20 10

11 Mud Solids (wt%) Effect of SiO 2 on Mud Solids Content 100 Kiln A1 90 Kiln A2 80 Kiln B Kiln C 70 Arpalahti et al. (1999) SiO 2 Content in Lime (wt%) 21 Problems with of SiO 2 Reacts with Na 2 CO 3 to form Na 2 SiO 3 in the recovery boiler Na 2 SiO 3 reacts with lime in the causticizing plant to form Calcium Silicate Hydrate gel (xcao ysio 2 nh 2 O) CSH Gel A small amount of Si or SiO 2 can result in a large amount of CSH gel Filter clogging 22 11

12 Poor Green Liquor Filterability Experienced in a number of Brazilian mills equipped with pressurized filters Possible Causes High suspended solids in green liquor (char/dregs from RB and suspended solids from weak wash) Large amount of Si and/or Mg gel like particles Overliming Tight filter cloth 23 Green Liquor Filter Cloth Clean Clogged Deposit 100 µm 100 µm 24 12

13 Cl and K Accumulation in Ash (No Purging) Conc. in Ash (wt%) K Cl Days 25 Factors Affecting Cl and K Accumulation Input Output (Degree of mill closure) Chemical losses Ash purging/ash treatment Recovery boiler operation Sulphidity (Cl only) 26 13

14 Control Targets for Cl and K Contents in Precipitator Ash Chloride (wt% Cl) Potassium (wt% K) Very low < 0.4 < 1.8 Low Typical High Very high > 8.5 > 9 27 Precipitator Ash Amount produced: Typically about 75 kg/adt pulp Enriched in Cl and K Cl enrichment factor = 2.5 K enrichment factor = 1.5 Ash purging is the easiest/most effective way to control Cl and K accumulation Amount purged: 10 to 30% of the total ash Disadvantage: High Na and S losses 28 14

15 Cl and K Accumulation (with Ash Purging) Conc. in Ash (wt%) K Cl Start Purging 0% 10% 20% 40% 10% 20% 40% Days Takes 1 to 2 months to reach steady state Precipitator Ash Treatment Various technologies available Ash treatment helps remove Cl and K but also recover some Na and S Most technologies rely on effective separation of solids from ash water slurries Separation is difficult when Slurry concentration: > 1 kg/l H 2 O Ash carbonate content: > 6 wt% CO

16 Effect of CO 3 on Liquid Solids Separation 0.3 wt%co wt%co 3 Ash with High CO 3 Contents Poor solids liquid separation Low Cl and K removal efficiency Low Na and S recovery efficiency CO 3 may be neutralized with sulfuric acid Add more S into the system, resulting in Na and S imbalance (high sulphidity) 32 16

17 Effects of High Sulphidity Bad Increases propensity for corrosion in RB and liquor cycle and for RB superheater fouling and plugging Increases TRS/SO 2 emissions Lowers steam production Good Lowers lime requirement Increases smelt fluidity Lowers Cl content in ash and liquor Lowers carbonate content in ESP ash Bad effects outweigh good effects 33 Causes of Na/S Imbalance High RB Capacity Low TRS Emissions High BL Solids, >75% High Bed Temperature Low Cl content in liquor High Cl/K removal effi. Improve in NCG collection; Burning NCG in Rec. boilers Keep S in the system High CO 3 Content in Ash Low Cl/K removal effi. Increased use of sulfuric acid to neutralize CO 3 Add more S to liquor system High TTA High sulfidity Increased NaOH consumption to control sulfidity 34 17

18 Summary There are many problems in energy and chemical recovery in kraft pulp mills Technological advances have alleviated many problems, but have also made some worse and have led to new challenges Problems in modern eucalyptus mills are mainly those associated with non process elements and Na/S imbalance 35 Acknowledgements 18

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