Chemistry of the Viscose Process

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 Cellulose Molecule
Cellubiose

Anhydroglucose

• The primary structure of Cellulose molecule is a long chain of glucose units attached together by β(1,4) linkages.
• The number of glucose units in a chains is the degree of polymerization
• The free hydroxyl groups at position 2, 3, 6 can form intra- and inter-molecular H-bonds, where
• It is the ability of these free hydroxyl groups present in the cellulose chains to hydrogen-bond together into fibres
(microfibrils) that gives cellulose its unique properties of mechanical strength and chemical stability.

Polymeric chains in native cellulose are densely packed in a semi ordered structure. Intramolecular hydrogen bonds
provide chain stiffness, and intermolecular hydrogen bonds allow for the linear polymers to assemble in sheet
structures. The semi-ordered structure is comprised of crystalline/Ordered and non-crystalline
(amorphous/disorder domains..
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 Sources of Cellulose
Cellulose is the main structural component in plants, which is by far the most abundant organic polymer on earth.

https://www.researchgate.net/publication/305318996_E https://www.researchgate.net/publication/275634703_Functionalized_Nanocellu
xtraction_of_cellulose_nanowhiskers_natural_fibers_so loses_in_Wastewater_Treatment_Applications/figures?lo=1
urce_methodology_and_application

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Pulping Processes – Separation of Cellulose from Lignocellulosic Materials
SULPHITE PULPING PROCESS:
Inthe sulfite pulping process, for example, sulfonic groups are introduced into the partially hydrolyzed lignin converting it
into a fully water-soluble lignosulfonate (Figure 4). The reactions are highly dependent on the pH of the reaction medium.
Under acidic pulping conditions, the oxygen of the α-substituent is substituted first by protonation and subsequent
nucleophilic addition. The β-O-4 linkage is cleaved at higher pH, for example, in neutral sulfite pulping.
Cooking condition: pH: 1.2-1.5, 80 % free SO2, -20 % bound SO2, bases of Ca, Mg, Na or NH3 can be used; pre-
heated liquor: 70-80 ºC; dwell temperature130ºC-145 ºC; pressure: 5.5-7 bar; 7 hours; liquor-to-wood ratio 4:1

KRAFT PULPING PROCESS:

In the Kraft process, the lignin is converted into lower molecular weight fragments of thiolignin by the introduction of thiol
groups (Figure 5). This thiolignin is soluble in the strongly alkaline cooking liquor
Cooking condiction: White liquor containing NaOH and Na2S; pre-heating ramp: 85 min up to 80 ºC; cooking
temperature 165-170 ºC; dwell time:95-180 min; 4:1 liquor-to-wood ratio.

SODA PULPING PROCESS: - VERY OLD PROCESS

Soda pulping (Na2CO3 & NaOH) (sulfur-free pulping) causes hydrolytic cleavage of the native lignin into smaller fragments
that are soluble in the strongly alkaline cooking liquor. However, the resultant lignin is sulfur-free and relatively chemically
unmodified when compared to the other lignin types.

ORGANOSOLVE PULPING PROCESS

Organosolv process includes extracting lignin from lignocellulosic biomass using organic solvents. The organosolv process
(S1) consists of the following processing steps: feedstock crushing, screening, solid and solvent storage, organosolv
pretreatment, separation of extracted lignin using centrifuges, solvent recovery using distillation and recycle of solvent to
the storage
9/17/2020 tank, cellulose recovery using centrifuges Samares C Biswas 4
Solubilization of Cellulose (dissolving Grade Pulp) for Spinning to Fiber
To get the cellulose in liquid form for spinning to fiber, it needs to be dissolved or chemically modified into a
homogenious solution format.

Unlike solubilization of simple molecules, polymers, on the other hand, undergo a multistep process going
from solid to dissolved state. Mass transfer is bidirectional as solvent penetrates the polymer network and
swell its outer layer while polymer disentangles from the outermost surface and transfer into the liquid bulk.

Major Challenges of Solubilizing cellulose

• Cellulose is known to be insoluble in water and in many organic solvents
• The insolubility in water is often referred to strong intermolecular hydrogen bonding (intra & inter) between
cellulose molecules and other factors such as amphiphilic nature of cellulose molecule. Crystallinity and
polar groups that may take part in hydrogen bonding play a major role in solubility and reactivity of any
polymer.
• Unlike many petroleum-based polymers, cellulose will not melt but decompose at elevated temperatures.

One of the most successful routes to dissolving and shaping of cellulose is via the viscose process.

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 Cellulose
Solvents

Cuam - cupraammonium hydroxide

Cuen - Cupriethylenediamine
Non- Cadoxen -Cadmium tris(ethylenediamine)
Derivatizing
derivatizing
FeTNa – Ferric (Fe) tartraic acid(TA)
complex in alkaline (NaOH) solution

N,N-dimethylformamide (DMF)/N2O4
Non- CF3COOH/(CF3CO)2
Aqueous O
aqueous

Aqueous inorganic Organic

complexes liquid/inorganic salt
(i) Cuam, (ii) Cuen, CH3CON(CH3)2/LiCl HCOOH
(iii) Cadoxen & (iv) (CH3)2-SO/CaCl2
FeTNa (CH3)2-SO/(C4H9)4NF

Aqueous bases - Organic

liquid/amine/SO2
(i) 10% NaOH,
(ii) NaOH / urea /
(CH3)2-
SO/(C2H5)3N/SO2
CS2/NaOH Viscose Process
water Ionic liquids

Ammonia/ammoni
Mineral acids
um salt
H2SO4; H3PO4
NH3/NH4SCN

Melt of inorganic Oxides of

salt hydrates – tertiary amines
(i) LiClO4 × 4H2O & - NMMO Lyocell Process
9/17/2020 (ii) ZnCl2 × 4H2O Samares C Biswas 6
Xanthation Reaction – Formation of Alkali Salt of Ethoxy Xanthate

C2H5OH + NaOH C2H5O-Na+ + H2O

C2H5O- Na+ + CS2 C2H5OCSS- Na+

The standard procedure for xanthate synthesis comprise of

• Forming an alkoxide ion from reaction of sodium hydroxide with a compound containing an unprotected
hydroxyl group, such as alcohols.
• Once formed, the alkoxide ion adds to carbon disulfide through the nucleophilic addition of an alkoxide
to carbon disulfide.

Xanthates are very unstable molecule; they undergo decomposition on storage

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 Cellulose Dissolution Via Cellulose Xanthate - Viscose

Steepping with alkali

to produce alkcell

Soluble in dilute
alkali solution

The xanthation process of cellulose comprised of the following steps

• Treatment with alkali solution to produce sodium cellulosate/alkcell and squizing out excess alkali followed
by shredding
• Treating the shredded sodium cellulosate with carbon disulphide to produce sodium salt of cellulose
xanthate
• Solubilizing sodium cellulose xanthate in dilute alkali solution

Mechanism of the formation sodium salt of cellulose xanthate

• Treatment of cellulose with caustic soda (NaOH) at high pH deprotonate the hydroxyl groups due to intrinsic
acidic nature of the same & form sodium cellulosate (salt).
• The nucleophile cellulosate anion reacts with the carbon atom of the electrophile, carbon disulfide produce
polymer chains of mono, di and tri-xanthate protected monomers.

Sodium
9/17/2020 cellulose xanthate is very unstable in Samares
nature, it undergoes further reaction on long-term storage
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Regeneration of Cellulose
from Cellulose Xanthate
Solution – Viscose Fiber
During the decomposition of cellulose xanthate,
the production of CS2, H2S, and CO2 as gases
takes9/17/2020
place
• Cellulose xanthate is prepared by first immersing cellulose pulp in aqueous
sodium hydroxide to convert to alkali cellulose. The alkali cellulose is then
depolymerized to control the alkali cellulose degree of polymerization prior to
xanthation in carbon disulfide. The cellulose xanthate is then dissolved in dilute
sodium hydroxide to form the “viscose” solution, which is then wet-spun into a
coagulation bath containing sulfuric acid, sodium sulfate, and zinc sulfate.
Regeneration of cellulose from cellulose xanthate in
non-solvent
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 Steps in Viscose Process
1. Steeping: cellulose pulps in large white sheets are immersed in vats containing 17–20% aqueous sodium hydroxide (NaOH) at a temperature ranging between 18°C
and 25°C. The cellulose sheets are swollen, and cellulose is converted into alkali cellulose.

2. Pressing: the swollen alkali cellulose sheets are pressed so that a press weight ratio of 2.7–3.0 is obtained. This is the ratio of the weight of pressed alkali cellulose
sheet to air-dried pulp.1

3. Shredding: the sheets of alkali cellulose are mechanically shredded in the form of ‘crumbs,’ which are finely divided particles. This process provides increased surface
area to increase the reaction ability of alkali cellulose.

4. Ageing: ageing aims to decrease the polymerization degree of alkali cellulose to the desired level. This process allows the alkali cellulose under controlled humidity and
temperature conditions to obtain the required viscosity for spinning.

5. Xanthation: this step is the reaction of aged alkali cellulose with carbon disulfide to have a resultant mass of cellulose xanthate. The cellulose crumbs become orange in
color at the end of this process.

6. Preparation of the viscose solution: the cellulose xanthate is mixed with an aqueous caustic solution in a stirring tank to form the viscous solution. It is called ‘viscose’
as this solution has a high viscosity. The viscose solution is thoroughly filtered to remove any undissolved material, and then de-aerated for removal of all air bubbles.

7. Ripening: in order to decrease the viscosity of the prepared solution, it is allowed to ripen for a period of time. During this process, the xanthate groups revert to
cellulosic hydroxyls and free CS2.

8. Filtering and degassing: the solution is then filtered once more to prevent the disruption of the spinning process. The air bubbles are removed, as otherwise they may
lead to breaks or weak spots during spinning.

9. Spinning: Viscous rayon filaments are spun by wet spinning process. The viscous fluid is delivered to the spinneret, which is immersed in a spin bath containing sulfuric
acid, sodium sulfate and zinc sulfate. As the rayon filaments rapidly coagulate they are stretched, and cellulose xanthate decomposes to regenerated cellulose.

10. Drawing, washing and cutting: the viscose rayon filaments are drawn to exhibit orientation of molecular chains along the fiber axis. This step is intended to obtain the
required tenacity for use as textile fibers. The impurities and salts are washed away. This is followed by cutting if the filaments are to be converted to staple form.

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 Side Reactions that Affect the Production Process
Carbon disulphide dissolves slowly in aqueous alkali solutions with the formation of carbonate and
trithiocarbonate. A concentrated solution of this kind are stable. But after dilution, they quickly absorb
oxygen from the air with the separation of Sulphur

Na2S + H2SO4 = Na2SO4 + H2S

https://onlinelibrary.wiley.com/doi/abs/10.1002/recl.19280470606#:~:text=Since%20carb
on%20disulphide%20is%20in,into%20trithio%2D%20carbonate%20and%20soda.

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 Thank you

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