Structure of lignocellulose biomass

Lignocellulosic biomass is typically nonedible plant material, including dedicated crops of wood and grass, and agro-forest residues. Lignocellulosics are mainly composed of cellulose, hemicellulose, and lignin.

Cellulose is a homopolysaccharide composed of P-D-pyranose units, linked by P-1, 4- glycosidic bonds. Cellobiose is the smallest repetitive unit and it is formed by two glucose monomers. The long-chain cellulose polymers are packed together into microfibrils by hydrogen and van der Waals bonds. Hemicellulose and lignin cover the microfibils (Fig.1). Hemicellulose is a mixture of polysaccharides, including pentoses, hexoses and uronic acids. Lignin is the most complex natural polymer consisting of a predominant building block of phenylpropane units. More specifically, p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol are the most commonly encountered alcohols (Harmesen et al., 2010). Lignocellulosic materials also contain small amounts of pectin, proteins, extractives (i. e. no — structural sugars, nitrogenous material, chlorophyll and waxes) and ash (Kumar et al., 2009).

The composition of the biomass constituents can vary greatly among various sources (Table 1). Accurate measurements of the biomass constituents, mainly lignin and carbohydrates, are of prime importance because they assist tailored process designs for the maximum recovery of energy and products from the raw materials.

Since 1900, researchers have developed several methods to measure the lignin and carbohydrates content of lignocellulosic biomass. Globally recognized Organizations, such as American Society for Testing and Materials (ASTM), Technical Association of the Pulp and Paper Industry (TAPPI) and National Renewable energy and Laboratory (NREL) have developed methods to determine the chemical composition of biomass, based on modifications of the two main procedures developed by Ritter (Ritter et al., 1932) and by Seaman (Saeman et al., 1954), (Table 2).

image037

LIGNIN

Fig. 1. Lignocellulosic materials: composition of major compounds (Kumar, 2009)

Lignocellulosic materials

Cellulose

(%)

Hemicellulose

(%)

Lignin

(%)

Coastal bermudagrass

25

35.7

6.4

Corn Cobs

45

35

15

Cotton seed hairs

80-95

5-20

0

Grasses

25-40

35-50

10-30

Hardwoods steam

40-55

24-40

18-25

Leaves

15-20

80-85

0

Newspaper

40-55

25-40

18-30

Nut shells

25-30

25-30

30-40

Paper

85-99

0

0-15

Primary wastewater solids

8-15

NA

24-29

Softwoods stems

45-50

25-35

25-35

Solid cattle manure

1.6-4.7

1.4-3.3

2.7-5.7

Sorted refuse

60

20

20

Swine waste

6.0

28

NA

Switchgrass

45

31.4

12.0

Waste papers from chemical pulps

60-70

10-20

5-10

Wheat straw

30

50

15

Table 1. Composition of some common sources of biomass (Sun and Cheng, 2002)

TAPPI

ASTM

NREL

Method

Title

Method

Title

Title

T 13 os 54; Later T222 om-06

Lignin in Wood (original) Acid — Insoluble Lignin in Wood and Pulp (later)

D 1106-96 (2007)

Standard Test Method for Cromatographic Analysis of Chemically Refined Cellulose (1996)

Determination of Structural Carbohydrates and Lignin in Biomass

T249 cm-00

Carboydrate Composition of Extractive — Free Wood and Wood Pulp by Gas-Liquid Chromatography

ASTM D1915- 63 (1989) withdrawn, replaced by D5896

Standard Test Method for Chromatographic Analysis of Chemically Refined Cellulose (1996)

AST D5896-96

Standard Test Method for Carbohydrate Distribution of Cellulosic Material

E1721

Standard Test Method for Determination of Acid-Insoluble Residue in Biomass

E1758

Determination of Carbohydrates in Biomass by High Performance Liquid Chromatography

Table 2. Methods provided by globally recognized organizations for the chemical composition of biomass (Sluiter et al., 2010)