towardsthedevelopmentof a newlyocellspinning process · 2020. 12. 12. · newlyocellspinning...
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IONCELL™Towards the Development of anew Lyocell Spinning ProcessKTY Seminar, Technopolis Ruoholahti, Helsinki
09-10-19
Herbert Sixta
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Fiber Year (2019)
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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
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Commercial Regenerated Cellulose Fibers
1. Viscose fibers: CV, CMD
2. NMMO-based Lyocell (Tencel®)
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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
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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)
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Alternatives to NMMO?Ionic Liquids are Salts Liquid at T <100°C
100°
25°
Röder T. unpublished
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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]
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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
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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
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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)
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Fiber Line
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Textile fibers from Wood
IoncellFiber
Process
PULP MILL
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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)
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• 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
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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
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Fiber production
17
Sixta, H. et al (2018) unpublished
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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
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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
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Textile fibers from Textile Waste
IoncellFiber
ProcessPr
etre
atm
ent
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Worn Jeans New Scarf
On the occasion of President Macron’s visit, August 2018
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New Fibers from old JeansT2C (Söktas)
T2C (Reima)
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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
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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)
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Thank you for your attention!