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FOREST PRODUCTS BIOTECHNOLOGY/BIOENERGY GROUP The influence of prehydrolysis and cold caustic extraction on dissolving cellulose properties: Is it better to remove hemicellulose before or after pulping? Xiaoli (Emily) Dou, Richard Chandra, and Jack Saddler Department of Wood Science, Faculty of Forestry, University of British Columbia E-mail: [email protected] 3. Methodology and Mechanism 1. Background Abstract: The high costs and environmental impacts of cotton growth have contributed to an increased production of dissolving pulps which differ from “paper grade pulps” in requiring high cellulose content, uniform molecular weight distribution and a high reactivity. One response to this demand has been to convert conventional Kraft pulp production to produce dissolving pulp. However, some Kraft pulp characteristics that enhance their papermaking properties, such as high hemicellulose retention and cellulose degree of polymerization (DP) are detrimental to dissolving pulp. Therefore, a repurposed Kraft pulping operation requires several extra steps to remove hemicellulose and tailor the cellulose to these more “speciality pulp” applications. In this work, we compared the ability of prehydrolysis and alkaline extraction processes to remove hemicellulose and assessed their effects on the resulting dissolving grade pulp (cellulose accessibility and reactivity). 5. Conclusions Dissolving pulp is one of the most important raw materials for the manufacture of cellulose esters and ethers that can be subsequently converted to products like rayon and thermoplastics such as cellulose acetate. Due to the requirement for a homogeneous, pure cellulose polymer, dissolving pulp is characterized by high cellulose content, reactivity to downstream derivatization reagents and a uniform molecular weight distribution. To meet these criteria, Prehydrolysis (PHK) and Cold Caustic Extraction (CCE) are used to convert Kraft pulp to dissolving pulp. This work differentiated the effects of removing hemicellulose by either the PHK and CCE on the pulp characteristics. References: Randy Moores, et al. 1998. “Arrangement of fibrils, microfibrils, and cellulose in cell walls.” (http://www.bio.miami.edu/dana/226/226F07_3print.html) Objectives: Understand the impact of PHK and CCE on pulp characteristics and enzymatic digestibility Figure out why CCE compromises cellulose accessibility and enzymatic digestibility Substrates Hemicellulose % Fibril aggregate size nm AFS % Kraft pulp (KP) 19.9 16.7 13.3 5% CCE KP 12.8 21.1 10.5 7% CCE KP 8.9 25.3 8.8 9% CCE KP 4.6 28.3 7.9 Converting traditional Kraft pulp to dissolving grade/specialty pulp Pre- hydrolysis Kraft pulping Bleaching step Dissolving Pulp Alkaline Extraction 3. Objectives 2. Hypotheses PHK and CCE can both be used to remove hemicellulose but vary in their impact on pulp properties CCE compromises cellulose accessibility and reactivity with chemicals and enzymes by decreasing the accessible fibril surface and increasing the size of cellulose microfibrils (Reference ) CS 2 NaOH Table 1. Properties of different alkaline treated Kraft pulp Figure 3. CP/MAS 13 C NMR spectra of PHK dissolving pulp The acidic approach of PHK preserves cellulose reactivity while alkaline CCE limits cellulose accessibility/reactivity Dissolving pulps obtained from PHK and CCE have similar hemicellulose content, but the residual hemicellulose from a PHK process helps to prevent the aggregation that occurs between cellulose microfibrils. Figure 2. Dissolving pulp manufacture and derivatization process Figure 1. Composition of trees 4. Results: Hemicellulose content and Reactivity

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FOREST PRODUCTS

BIOTECHNOLOGY/BIOENERGY GROUP

The influence of prehydrolysis and cold caustic extraction on dissolving cellulose

properties: Is it better to remove hemicellulose before or after pulping? Xiaoli (Emily) Dou, Richard Chandra, and Jack Saddler

Department of Wood Science, Faculty of Forestry, University of British Columbia E-mail: [email protected]

3. Methodology and Mechanism 1. Background

Abstract: The high costs and environmental impacts of cotton growth have contributed to an increased production of dissolving pulps which differ from “paper grade pulps” in requiring high

cellulose content, uniform molecular weight distribution and a high reactivity. One response to this demand has been to convert conventional Kraft pulp production to produce dissolving pulp.

However, some Kraft pulp characteristics that enhance their papermaking properties, such as high hemicellulose retention and cellulose degree of polymerization (DP) are detrimental to dissolving

pulp. Therefore, a repurposed Kraft pulping operation requires several extra steps to remove hemicellulose and tailor the cellulose to these more “speciality pulp” applications. In this work, we

compared the ability of prehydrolysis and alkaline extraction processes to remove hemicellulose and assessed their effects on the resulting dissolving grade pulp (cellulose accessibility and reactivity).

5. Conclusions

Dissolving pulp is one of the most important raw materials for the

manufacture of cellulose esters and ethers that can be subsequently

converted to products like rayon and thermoplastics such as

cellulose acetate. Due to the requirement for a homogeneous, pure

cellulose polymer, dissolving pulp is characterized by high

cellulose content, reactivity to downstream derivatization

reagents and a uniform molecular weight distribution.

To meet these criteria, Prehydrolysis (PHK) and Cold Caustic

Extraction (CCE) are used to convert Kraft pulp to dissolving pulp.

This work differentiated the effects of removing hemicellulose by

either the PHK and CCE on the pulp characteristics.

References: Randy Moores, et al. 1998. “Arrangement of fibrils, microfibrils, and cellulose in cell walls.” (http://www.bio.miami.edu/dana/226/226F07_3print.html)

Objectives:

• Understand the impact of PHK and

CCE on pulp characteristics and

enzymatic digestibility

• Figure out why CCE compromises

cellulose accessibility and

enzymatic digestibility

Substrates Hemicellulose

%

Fibril aggregate

size nm AFS %

Kraft pulp (KP) 19.9 16.7 13.3

5% CCE KP 12.8 21.1 10.5

7% CCE KP 8.9 25.3 8.8

9% CCE KP 4.6 28.3 7.9

Converting traditional Kraft pulp to dissolving grade/specialty pulp

Pre-

hydrolysis

Kraft

pulping Bleaching

step

Dissolving

Pulp

Alkaline

Extraction

3. Objectives

2. Hypotheses

• PHK and CCE can both be used to remove hemicellulose but

vary in their impact on pulp properties

• CCE compromises cellulose accessibility and reactivity with

chemicals and enzymes by decreasing the accessible fibril

surface and increasing the size of cellulose microfibrils

(Reference )

CS2

NaOH

Table 1. Properties of different alkaline treated Kraft pulp

Figure 3. CP/MAS 13C NMR spectra of PHK dissolving pulp

• The acidic approach of PHK preserves cellulose reactivity while

alkaline CCE limits cellulose accessibility/reactivity

• Dissolving pulps obtained from PHK and CCE have similar

hemicellulose content, but the residual hemicellulose from a

PHK process helps to prevent the aggregation that occurs

between cellulose microfibrils.

Figure 2. Dissolving pulp manufacture and derivatization process

Figure 1. Composition of trees

4. Results: Hemicellulose content and Reactivity