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IONCELL™Towards the Development of anew Lyocell Spinning ProcessKTY Seminar, Technopolis Ruoholahti, Helsinki
09-10-19
Herbert Sixta
Fiber Year (2019)
Fiber Year (2019)
Cellulose Gap
2019 - 2030:• 33-37% cellulosics• Cotton: 3.1 kg/capita• MMCFs: 0.8 kg/capita• GAP: 1.7 kg/capitaPredicted 5.6 kg/capita
Hämmerle, F.M. Lenz Ber 89(2011), 12-21
2020 2025 20300,060
80
100
120
140
160
Mio
t Te
xtile
s
Cellulosics: CO+MMCF+BAST
SyntheticsThe “Gap” representsa 35 B€ business
Cellulose GAP
GAP of 14 Mio t in 2030
Commercial Regenerated Cellulose Fibers
1. Viscose fibers: CV, CMD
2. NMMO-based Lyocell (Tencel®)
From Solution as a Derivate: Viscose
Cons:• Polluting: CS2, H2S, COD, salts,…• Low wet-tenacity• High investment costs
Regular Viscose (CV)
Modal® Viscose (CMD)
Pros:• Medium-to-good quality fibers• Modal is “cotton-like”
WET SPINNING
Lenzing AG
From Solution in a direct solvent: Lyocell (CLY)Cons:• High temperature during spinning• Degradation of polysaccharides• Fibrillation upon washing• Unstable solvent
Pros:• Excellent cellulose solvent• Stable spinnability• Environmentally friendly• Efficient recovery system• Excellent fiber strength• Cost-effective
DRYJET-WET SPINNING
1 mm
CLY
Rosenau, T. et al (2001)
Alternatives to NMMO?Ionic Liquids are Salts Liquid at T <100°C
100°
25°
Röder T. unpublished
Dissolution Window for Cellulose
Hauru, L.K.J.et al.. Biomacromolecules 2012, 13, 2896-2905.
KT: Net-basicity Concept
0,0 0,3 0,6 0,9 1,2 1,5-1,0
-0,5
0,0
0,5
1,0
--100
20
[emim]OAc [TMGH]EtCO2
[TMGH]OAc NMMO×H2O NMMO×2H2O LiCl/DMAc
[Pnnnn] [Rmim]MeOHPO2
[eimH]EtCOO DMAPH]EtCOO [HOC2mim] [EMIM] [BMIM]
[DBNH][OAc]
b-a
b
M.J. Kamlet and R.W. Taft: JACS, 98:2, 377-383 (1976)R.W. Taft and M.J. Kamlet: JACS, 98:10, 2886-2894 (1976)M.J. Kamlet, J-L.M. Abboud, MH: Abraham, R.W.Taft, JOGS, 48, 2877-2887 (1983)
0,0 0,5 1,0 1,5
300
320
340
360
Non-Dissolving
Ani
on P
roto
n A
ffini
ty (k
cal/m
ol)
Kamlet-Taft b Value
Cellulose Dissolving
Parviainen, A. et al. ChemSusChem 2013, 6, 2161-2169Alistair King et al. (2017) unpublished results
Anion Proton Affinity
Proton affinity (-ΔHPA) defined as thenegative of the enthalpies of protonation at298K [Avogadro 1.0.0 with MMFF94 forcefield]
Lenz. Ber (2005), 84:71-85 Lenz. Ber (2006), 86:154-161
Imidazolium-based ILs
O,S-dimethylphosphorothioateGreen Chem (2011), 13:2507 Polymers 2019, 11, 845
CATIONS ANIONS
Limitations of imidazolium-based ILs
Ebner, G. et al. Tetrahedron Letters (2008), 49(51), 7322)
• Limited spinnability, cellulose degradation
• Formation of carboxylic acids as a result of pulp degradation
• Accumulation of inorganic salts from the pulp in the IL
1,5-diazabicyclo[4.3.0]non-5-ene (DBN)
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
N,N,N,N,NN,-hexamethyl-phosphorimide triamide (HMPI)
1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (DMP)
N,N,N,N,-tetramethylguanidinium (TMG)
N N
Parviainen, A. et al. ChemSusChem 2013, 6, 2161-2169
Acid Superbase Conjugates
Mikkola, J-P. RSC Adv., 2016, 6, 9194-9208Croat. Chem. Acta 2014, 87, 385–395
7-methyl-1,5,7-triazabicyclo[4.4.0] dec-5-ene (mTBD)
Fiber Line
Textile fibers from Wood
IoncellFiber
Process
PULP MILL
Wood pulp
IL / H2O
Final dope has to be filtrated and degassed
0 30 60 90 1200
50
100
150
Tem
per
atu
re, C
Time, min0
200
400
600
Torq
ue, N
m
dissolved
14
Solubility up to 20 wt%PHK-Pulp, [η] = 424 mL/g
Cellulose Dissolution
Hummel, M. (2013)
• Rg ~101 dry cellulose in [emim][OAc]
Solution structure
Arndt K-F. et al. Macromol. Symp. 2002, 162,pp 109-119Olga Kuzmina et al. Fibers and Textiles in Eastern Europe 2010, 18, 3 (80), 32-37
• Rg ~136 – 204 nm in NMMO (different DPs)
• Fringed micelle• Interpenetrated network
• Rg ~ 20 in Cd-tren
Saalwachter, K. Burchard W. Macromolecules 2000, 33, pp 4094
Elastocapillary properties of cellulose-IL solution
Elongational viscosity
Haward, S.J. et al. Biomacromolecules, 2012Hummel, S. et al. Ann. Transact. of the Nordic Rheology Society,19, 2011
0 50 100 150 2000,01
0,1
1
150 155 160 165 170 1750,01
0,1
1
IV
III
II
diam
eter
(mm
)
time (sec)
I
IV
III
Clasen, Ch. Korea-Australia Rheology Journal (2010), 22 (4), 331-338A. Michud et al. / Carbohydrate Polymers 117 (2015) 355–363
Fiber production
17
Sixta, H. et al (2018) unpublished
Sixta, H. et al. NPPRJ, 30(1), 2015, 43-57Northolt, M.G. Lenzinger Berichte, (1985), 59, 71-79.De Vries. Appl. Sci. Res. A3, 111 (1952).
Fortisan
IONCELL
0 10 20 300,0
0,3
0,6
0,9
1,2
Tens
ile st
ress
(GPa
)
Young's modulus (GPa)
CVCMD
CLY
Tirecord
Fiber properties: Stress vs. E-modulus
Tuula Pöyhönen
2014 2016 2018 2018 2019Fibers: Ioncell™-Team
Dress design: Emma SaarnioTextile Vesa Moilanen
/LehtikuvaFibers: Ioncell™-Team
Akino Kurosawa, MA FaCT FashionPhoto: Sara Riikonen
Fibers: Ioncell™-TeamAnna Semi MA FaCT Fashion
Sofia Ilmonen MA FaCT Fashion
Fibers: Ioncell™-TeamDesign: Anna-Mari
LeppisaariPhoto: Eeva Suorlahti
Textile fibers from Textile Waste
IoncellFiber
ProcessPr
etre
atm
ent
Worn Jeans New Scarf
On the occasion of President Macron’s visit, August 2018
New Fibers from old JeansT2C (Söktas)
T2C (Reima)
Superbase-based IL
> 99%
Elsayed S.; Guizani C. et al. (2019) unpublished results
Kneader: 13%wt cellulose - 50 min – 30 RPM – 80 °C – P: 15 mbar; Spinning: Ve:0.1 m/min – T:80-87 °C – 1 hole – L/D 2 – Spinbath T: 10 °C – IL wt% from spinath 20 wt%;. Thin-filmevaporator 1st: T: 63 °C – P: 20 mbar – 350 RPM – F: 3.6 kg/hr; Thin-film evaporator 2nd: T: 83 °C– P: 17 mbar – 350 RPM – F: 3.6 kg/hr
Solvent Recycling
CONFIDENTIAL
2010 2015 2020 2025 2030123456789 TRL
2010 2015 2020 2025 2030123456789 TRL
PoC
IL
-Rec
over
y
PoC
Fib
er S
pinn
ing
2010 2015 2020 2025 2030123456789 TRL
PoC
Fib
er S
pinn
ing
2010 2015 2020 2025 2030123456789 TRL
Pilo
t pla
nt
PoC
IL
-Rec
over
y
PoC
Fib
er S
pinn
ing
2010 2015 2020 2025 2030123456789 TRL
Dem
o p
lant
Pilo
t pla
nt
PoC
IL
-Rec
over
y
PoC
Fib
er S
pinn
ing
2010 2015 2020 2025 2030123456789 TRL
Com
mer
cial
izatio
n
Dem
o p
lant
Pilo
t pla
nt
PoC
IL
-Rec
over
y
PoC
Fib
er S
pinn
ing
Development of the Ioncell™ Process
Sixta, H (2019)
Thank you for your attention!
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