Advances in Dissolving Pulp Technology Herbert Sixta, Annariikka Roselli, Michael Hummel & Kyösti Ruuttunen

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1 Advances in Dissolving Pulp Technology Herbert Sixta, Annariikka Roselli, Michael Hummel & Kyösti Ruuttunen Aalto University School of Chemical Technology, Department of Forest Products Technology, Biorefineries 6th ICEP, Colonia del Sacramento, Uruguay, 27/11/2013

2 The key points Dissolving pulp demand increases in the future S 2 -ethanol-water (SEW) pulping, prehydrolysis kraft, and cold caustic extraction (CCE) are methods which are technically feasible for industrial scale processes These methods have certain limitations, however The novel INCELL process has given promising results for Eucalyptus Papermaking Pulp + Ionic Liquid Dissolving Pulp + Xylan

3 utline Introduction Acid processes Alkaline processes INCELL Process 3

4 Paper & board market Structural erosion of paper demand persists over the next years (mainly in Europe and North America) Annual Volume, Mio t Europe Graphic papers Sanitary & Houshold Packaging materials Years 93.7 Annual Volume, Mio t North America Graphic papers Sanitary & Houshold Packaging materials Years UNECE/FA Forest Products Annual Market Review,

5 Market of cellulose products Amount, t/a Ether Acetate Viscose Cotton 2012 Paper MCC Nitrocellulose Film, casings Lyocell Global textile market - Cotton stagnant at Mio t/a - High cotton prices % minimum share of cellulosics in textiles - GAP of 15 Mio t/a of cellulosic fibers in 2030 Growth rates - Viscose, Lyocell > 9%/a - Acetate 1.5%/a - Ethers 3.5%/a - thers 0-5%/a Brice, R., High purity cellulose through 2020, in The Cellulose Gap 2012: Monte Carlo Haemmerle, F.M., The cellulose gap. Lenzinger Berichte, : p

6 Product specification Molar Mass Distribution dm/d(logmm) 1,0 0,5 Acid Sulfite Pulp 1 Pulps, wt% LMM MMM HMM DP<100 Xyl Man Acid Sulfite PHK dm/d(log MM) 3 2 0, ,0 0,5 Log (MM) Prehydrolysis-Kraft (PHK) 3 2 0, Log (MM) HMM-Cellulose, wt% K S K S RAYN K... PHK S... Acid SUlfite ACETATE ETHER 500 (1200) (5100) 2000DP v S Pulp Viscosity, ml/g H. Sixta et al., 2005

7 utline Introduction Acid processes Alkaline processes INCELL Process 7

8 S 2 -ethanol-water (SEW) Base of an acid sulfite cook is replaced by EtH (55% v/v) Improved impregnation faster cooking Improved solubility of lignin Simple recovery: distillation of ethanol and unreacted S 2 55% EtH 45% H mole S 2 /L 150 C, 60 min M. Iakovlev, Ph.D. thesis, Aalto University (2011)

9 Spruce rayon pulp L:W Total yield B Vis. R18 Hemicell. Xyl Man % odw % IS ml/g % Total % % % SEW-1 6: SEW-2 3: MgS 3.2: Sugars, kg/t odw Dissolved Sugars aldonic acid XylA ManA MgS C-5 C-6 Furf Ara Xyl Gala Glu Man SEW + 40kg/t Compared to AS, SEW gives Comparable pulp properties Lower viscosity Lower degree of sulfonation (DS) of lignin Better sugar recovery (practically no aldonic acids or furfural) Flexibility in raw material selection (SW, HW, annual plants) H. Sixta et al., Cellulose (2013)

10 utline Introduction Acid processes Alkaline processes INCELL Process 10

11 Process concepts Purification Processes 1. Autohydrolysis 2. Hot alkali treatment 1. Hot alkali treatment 2. Cold alkali treatment 1. Autohydrolysis 2. Hot alkali treatment 3. Cold alkali treatment

12 Wood Purification vs. yield Process P-factor NaH(CCE) Bleached yield Xylan R18 g/l %odw % % Birch PHSAQ Birch K-CCE E.glob PHSAQ E.glob K-CCE Cell-Yield, % od w E. globulus CCE PHK Xylan, % od p Cellulose, II, % Viscose filterability Viscose Dope Quality very good good 600 excellent satisfactory poor Birch P1000SAQ E. globulus KCCE100 KCCE100 EBeam KXCCE70EG Particle volume, ppm

Dissolution behavior of pulps of different reactivity Dissolution in 0.

PH-Kraft Low reactivity pulp Euca Kraft-CCE100 0 s Complete dissolution by

dissolution Ballooning, formation of collars The better reactivity of the

of the cell wall better accessibility due to decreased swelling resistance

13 Dissolution behavior of pulps of different reactivity Dissolution in 0.5 M cupriethylen diamine at room temperature High reactivity pulp Euca PH-Kraft Low reactivity pulp Euca Kraft-CCE100 0 s Complete dissolution by left handed untwisting of cellulose fibrils 45 s Increased swelling, no dissolution Ballooning, formation of collars The better reactivity of the prehydrolysis pulp is due to the acidic treatment degrading the outer layers of the cell wall better accessibility due to decreased swelling resistance Schild, G, H. Sixta, Cellulose (2011) Gehmayr, V., Potthast, A., H. Sixta, Cellulose (2012) 13

14 Summary: alkaline processes Prehydrolysis kraft Technically feasible water prehydrolysis processes platform chemical from the hydrolysate Wood species with low xylan content (e.g. E. globulus) give dissolving pulps of decent quality & yield e.g. birch (B. pendula) requires very high P- factors, decreasing the viscosity & yield Kraft CCE CCE does not affect the cellulose yield polymeric xylan extracted High molecular mass alkali-resistant xylan decreases the pulp quality CCE converts cellulose I partly to cellulose II decreased reactivity Rigid outer cell walls decreased reactivity H. Sixta et al., Cellulose (2013)

15 utline Introduction Acid processes Alkaline processes INCELL Process 15

fused salts with a melting point below 100 C Ionic Liquid (IL) (<

16 Ionic liquid (IL) conventional salt melt (> 100 C) 100 C is a salt in its liquid state liquid that consists exclusively of ions fused salts with a melting point below 100 C Ionic Liquid (IL) (< 100 C) 25 C Subclass: Room Temperature Ionic Liquid (RTIL) (< 25 C)

17 Nomenclature 1,3-dimethylimidazolium = [MMIM] = [C 1 mim] 1-ethyl-3-methylimidazolium = [EMIM] = [C 2 mim] 1-methyl-3-propylimidazolium = [PMIM] = [C 3 mim] 1-butyl-3-methylimidazolium = [BMIM] = [C 4 mim] 1-allyl-3-methylimidazolium = [AMIM] 1-benzyl-3-methylimidazolium = [BnMIM]

18 Appropriate anions In terms of cellulose processing 1 st generation: Halide containing N N ILs N R 1 R 2 interact Rwith cellulose but: high melting N points corrosive N N toward metal R 1 R 2 N R 1 R 2 R 1 R 1 NR to overcome this problems 2 R 1 N R 2 R 1 P R 2 R 1 R R 1 2 N NR 2 development of 2 nd generation Cl Br Ts BF 4 PF 6 CN SCN Tf Tf 2 N (CN) 2 N CH 3 C 2 CF 3 C 2 N 3 Cl 4 FeCl 4 AlCl 4 Al 2 Cl 7 HS 4 Alkyl F BF 3 (Alkyl F ) 3 PF 3 (Me)S 3 (Me)S 2 (Me) 2 P 2 (Me) 2 P B

19 Solvent properties: Kamlet Taft parameters S CF 3 S Me sulfates Ionic liquid BMIM Cl AMIM Cl P Me SMe P Me Me phosphates EMIM (Me) 2 P EMIM Ac P Me H P Me Me phosphonates EMIM (Me)MeP EMIM PF water H H 3 C carboxylates for cellulose dissolution: high -value role of and * disputed

$Heterogeneous fractionation of pulp 1,0 0,5 dm/dlog(mm)1,5 0,0 3 4 5 6 7 log MM Hemi-rich Kraft pulp CNCEPT IL + Cosolvent dm/d(log MM) 1,5 1,0 0,5 0,0 3 4 5 6 7 log MM pure Hemi dm/d(log MM) 1,5 1,0$

20 Heterogeneous fractionation of pulp 1,0 0,5 dm/dlog(mm)1,5 0, log MM Hemi-rich Kraft pulp CNCEPT IL + Cosolvent dm/d(log MM) 1,5 1,0 0,5 0, log MM pure Hemi dm/d(log MM) 1,5 1,0 0,5 0, log MM pure Cellulose I Addition of co-solvent reduces solvent quality of the ionic liquid Cellulose not soluble while hemicellulose remains still soluble Selective extraction of hemicellulose from paper-grade pulp Cellulose fraction upgraded to high-quality dissolving pulp Cellulose fraction e.g. for lyocell process for manufacturing regenerated cellulose products

21 INCELL process Separate solubility tests of Cotton Linters and pure Xylan (from Birch) in [emim][ac]-water mixtures 0,8 [emim]ac 0,7 0,6 0,5 0,5 0,4 Cellulose Xylan 0,3 Polymer 0,2 0,9 0,1 1,0 0,0 0,0 0,1 0,2 0,3 0,4 0,5 Water Clear gap for the selective dissolution of xylan? 21

Birch kraft paper pulp paper pulp dissolving pulp extracted

0,6 0,4 Xyl > 90% Xyl 65% Xyl < 50% 47% Cell 0,3 Pulp 0,2 0,1 1,0

% od [ ] ml/g Birch-Kraft 25.4 808 Birch-INCELL-P 1.

94 US provisional US61/646383 Froschauer C. et al.

22 Birch kraft paper pulp paper pulp dissolving pulp extracted hemicelluloses calculated sum BIRCH 0,5 0,5 0,7 0,8 0,9 [emim]ac 0,6 0,4 Xyl > 90% Xyl 65% Xyl < 50% 47% Cell 0,3 Pulp 0,2 0,1 1,0 0,0 0,0 0,1 0,2 0,3 0,4 0,5 Water Treatment Log(MM) Xylan % od [ ] ml/g Birch-Kraft Birch-INCELL-P Quantitative precipitation of Xylan at H2 = 0.94 US provisional US61/ Froschauer C. et al. Biomacromolecules 2013, 14, Hauru, L.K.J et. al. Biomacromolecules 2012, 13, XYLAN 31.1 kda Log MM

23 Tested ionic liquids Abbreviation Ionic liquid 1. [emim][ac] 1-ethyl-3-methylimidazolium acetate 2. [emim][dmp] 1-ethyl-3-methylimidazolium dimethylphosphate 3. [emim]cl 1-ethyl-3-methylimidazolium chloride 4. [mdbn][dmp] 1-methyl-1,5-diazabicyclo[4.3.0]non-5-enium dimethylphosphate 5. Novel 1 Not disclosed 6. Novel 2 Not disclosed 7. NMM N-methyl-morpholine N-oxide A selection of ionic liquids was chosen to identify the effect of different cations and anions on the extraction efficiency Adapted from A. Roselli, 17th IWFPC conference, June 12-14, 2013, Vancouver BC

24 Xylan removal efficiency & selectivity using birch kraft pulp Xylan in Residue, % Dissolved Cellulose, % [C 2 C 1 im][ac] 0 0,4 0,5 0,6 0,7 0,8 Water, [mdbn][dmp] Xylan in Residue, % Dissolved Cellulose, % NMM 0 0,4 0,5 0,6 0,7 0,8 0 0,4 0,5 0,6 0,7 0,8 Water, Xylan in Residue, % Dissolved Cellulose, % Water, Xylan in Residue, % Dissolved Cellulose, % [emim][dmp] 0 0,4 0,5 0,6 0,7 0,8 Water,

25 Business case: Conversion of E. urograndis paper pulp (EK) into acetate-grade pulp Xylan Viscosity DP<100 PDI wt% ml/g wt% EK-pulp dm/d(logmm) 1,0 0,5 PaperPulp Peak 1: 22.6% Peak 2: 63.1% Peak 3: 14.3% 1 0, Log (MM) 3 Target XYLAN < 2.0 %

26 Adjustment to final quality 1. INCELL (I) - Acid treatment (A) 2. Xylanase (X) INCELL (I) Acid treatment (A) 3. Cold caustic extraction (CCE) Acid treatment (A) rigin Sequence Xylan Viscosity R18 DP<100 PDI % ml/g % wt% Commercial EK n.d Laboratory EK-I-A Laboratory EK-X-I-A Laboratory EK-CCE-A Commercial EPHK-CCE-A Yields Eucalyptus urograndis Sequence Kraft_bl PHK_ubl BL-Y X INCELL CCE A Total EK-I-A EK-X-I-A EK-CCE-A EPHK-CCE-A

27 Molar mass distributions EK EK-I*0.83 Extr Xylan*0.17 Calculated sum o K-CCE is less efficient and selective than the INCELL-P process INCELL DP adjustment log (MM) EK-CCE-A EK-X-I-A E-PHK-CCE (commercial) o Commercial PHK-CCE pulp has a higher proportion of low and high MM fractions. 3,7 4,0 4,3 4, log (MM)

Triacetate quality rigin Sequence Yellowness Transmittance - % Lab EK-I-A 0.226 78.6 Lab EK-X-I-A 0.174 81.1 Lab EK-CCE-A 0.302 61.7 Commercial EPHK-CCE-A 0.

28 Triacetate quality rigin Sequence Yellowness Transmittance - % Lab EK-I-A Lab EK-X-I-A Lab EK-CCE-A Commercial EPHK-CCE-A Excellent properties as acetate-grade pulp, exceeding those of a commercial pulp Future focus lies on the development of an appropriate recovery concept

process Cell-Y, % od w 40 35 CCE PHK 30 2 4 6 8 1821 Xylan, % od p 0,5 0,5 0,6 0,7 0,8 0,9 0,4 0,3 0,2 0,1 1,0 0,0 0,1 0,2 0,3 0,4 0,0 0,5

29 Summary S 2 -Ethanol- Water?! Promising Biorefinery for Rayon pulp and sugar-based Products Alkaline pulping and refining Tunable solvent system: IL+CoSolv INCELL process Cell-Y, % od w CCE PHK Xylan, % od p 0,5 0,5 0,6 0,7 0,8 0,9 0,4 0,3 0,2 0,1 1,0 0,0 0,1 0,2 0,3 0,4 0,0 0,5 [emim]ac Water Acetate-grade pulp Pulp Log (MM) High cellulose yield, narrow MMD, but inferior dissolution properties Selective solubility window for any type of hemicelluloses KR23 Easy conversion of hemi-rich paper to pure cellulose acetategrade pulp 29

30 Diapositiva 29 KR23 Is this really true? Is there sufficient data from SW? Ruuttunen Kyösti, 17/11/2013

31 Thank you for your attention! Funding from Finnish Funding Agency for Technology and Innovation (Tekes) and FiBiC as apart of the Future Biorefinery programme is gratefully acknowledged June, 2013 AALT University, Biorefineries Research Group

WOBAMA. Wood based materials and fuels. Monica Ek Project coordinator KTH Royal Institute of Technology

WOBAMA. Wood based materials and fuels. Monica Ek Project coordinator KTH Royal Institute of Technology WOBAMA Wood based materials and fuels Monica Ek Project coordinator KTH Royal Institute of Technology A PROJECT COORDINATED BY KTH WORKPACKAGES COORDINATED BY THE ACADEMIC PARTNERS A European Project The