The initial step in breaking down lignocellulose typically involves traditional pretreatment methods, which can be physical, chemical, a combination of both (physicochemical), or biological.
Physical pretreatments aim to enhance the surface area and biomass pore size without involving chemical agents. Methods include mechanical comminution (size reduction), irradiation, and extrusion. While these methods alone are less effective and costly, they are often combined with chemical pretreatments for better results.
- Mechanical Comminution: Involves processes like chipping or grinding to improve lignocellulosic biomass digestibility. However, it is time-consuming, energy-intensive, and less effective than chemical pretreatments.
- Irradiation: Uses high-energy radiation to modify biomass, but it is slow, energy-intensive, and substrate-specific, making it less cost-effective.
- Extrusion: A more recent method involving continuous heating, mixing, and shearing, improving carbohydrate accessibility for enzymatic action. It has advantages such as lower temperatures and efficient lignin removal.
Chemical pretreatments aim to disrupt and remove lignin and/or hemicellulose from biomass. Acid, alkali, oxidative delignification, and organosolvation are common methods.
- Acid Wash: Involves washing feedstock with acids to degrade hemicellulose, making cellulose more accessible to enzymes. Dilute sulfuric acid is commonly used, but concentrated acid is avoided due to its toxicity and high costs.
- Alkaline Pretreatment: Soaking biomass in alkaline solutions to remove lignin. This process induces partial dissolution of hemicellulose and is milder than other methods.
- Oxidative Delignification: Uses oxidizing compounds like hydrogen peroxide or ozone to break down lignin. While effective, it can be costly and generate inhibitory by-products.
- Organosolvation: Utilizes organic or aqueous solvents to solubilize lignin and hemicellulose. Despite advantages, it is expensive and generates inhibitory by-products.
Physicochemical methods combine conditions and compounds targeting both physical and chemical properties of biomass. Steam explosion, liquid hot water, microwave irradiation, and CO2 explosion are examples.
- Steam Pretreatment: Involves heating biomass at high temperatures and pressures, leading to chemical modifications that enhance enzymatic hydrolysis. It is cost-effective and environmentally friendly.
- Liquid Hot Water Pretreatment: Solubilizes hemicellulose and lignin, improving cellulose accessibility without the need for costly reactors.
- Microwave Irradiation: Alters lignocellulose ultrastructure through internal heating, but it can be costly for large-scale operations.
- CO2 Explosion: Uses supercritical CO2 to alter biomass structure, providing a low-cost alternative with minimal inhibitors.
Biological methods use wood-degrading microorganisms to modify the chemical composition and structure of lignocellulosic feedstock. These methods, including white-rot fungi and bacteria, can be used alone or in combination with other pretreatments.
- White-Rot Fungi: Particularly effective in degrading lignin, cellulose, and hemicellulose.
- Brown-Rot Fungi: Selectively deconstructs cellulose and hemicellulose.
- Soft-Rot Fungi: Works on polysaccharides and may degrade lignin.
Biological pretreatments have low capital costs and mild environmental conditions but suffer from slow hydrolysis rates and feedstock specificity. Current research focuses on combining microbial degradation with other pretreatments or developing genetically modified microorganisms.