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Röder T. unpublished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 (2017) unpublished results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

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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

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Dem

o p

lant

Pilo

t pla

nt

PoC

IL

-Rec

over

y

PoC

Fib

er S

pinn

ing

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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!