Sugarcane Factory Sucrose Production of Organic acids and Furanics

from Sugarcane Bagasse

Bagasse Darryn W. Rackemann, John P. Bartley and William O.S. Doherty
Queensland University of Technology, Brisbane, Australia

INTRODUCTION BAGASSE – EG CO-SOLVENT
Introduces additional reaction pathways (Scheme 1)

Sugarcane waste (i.e. bagasse) is an abundant and relatively low
Formate, acetate and levulinate acids and EG mono/di- esters
No co-solvent

Levulinic acid yield (mol%)

cost carbohydrate resource. Platform chemicals such as levulinic 90
EG co-solvent (50%)
acid and furanics can be produced through acid-catalyzed 80 Glucose
Levulinic acid Formic acid
H OH HMF
dehydration and hydrolysis of carbohydrates. 70 O O O O
HO
HO H
H O OH +
H
Commercial production of levulinic acid and furfural suffers from 60 H OHOH HO H H3C
H OH
O
the use of corrosive mineral acid catalysts such as sulfuric acid 50 OH
O

HO OH
(H2SO4) which increase equipment and operating costs and can 40 EG H O
O EG-levulinate
OH
lead to waste disposal issues associated with non-recovery of the 30 H
O
O EG-formate
HO H O +
catalyst [1,2]. Research is currently being undertaken with green 20
HO H H H3C OH
H OH
H OH O
acids and co-solvents such as glycols in an effort to improve the 10 EG-glycoside
O
OH
overall process of producing the compounds. EG-di-levulinate
0
O O
20 min 40 min 60 min 0.1 M 0.3 M 0.5 M
EXPERIMENTAL 0.3 M MSA catalyst 40 min residence time H3C
O
O
CH3

Feed - Glucose/xylose mixtures (equivalent in proportion to Fig. 2 – Levulinic acid yields from acid-catalyzed (MSA) reaction of O O

different types of lignocellulose) and sugarcane bagasse bagasse at 180ºC Scheme 1 – Possible reaction pathways with EG

Strong sulfonic acid catalysts (pKa<-1.8) of low corrosivity
Harsh condi>ons ↑ yield of levulinic acid (Fig. 1 & 2)
Ratio of esters to acid dependent on EG concentration

Methanesulfonic (MSA), ethanesulfonic (ESA) and
Total levulinates (lev acid + mono/di -esters) increased with
Levulinate esters 24-55% of total levulinates
p-toluenesulfonic acid (TSA) co-solvent concentration and harsher reaction conditions
Acetate esters 10-30% of total acetates

Ethylene glycol (EG) co-solvent (high boiling point lignin solvent)
Carbon yield increased by up to ~20%
Formate esters 2-8% of total formates

Operating conditions  160-200ºC (heat up time <2 min);
EG reduced amount of solid residue
8-75 min; 0.1-0.8 M acid; 0-90% co-solvent; 1-7 wt% feed
90
SUGARS – CATALYSTS No co-solvent CONCLUSIONS
Furfural yield (mol%)

80
EG co-solvent (50%)
70 70
Process conditions selected to optimise product yields
H2SO4 MSA ESA TSA
60
First stage  furfural and acetic acid production
Product yields (mol%)

60
50
Rapid heating, short time, low temperature, low acid conc.
50
Levulinic acid 40
Flash recovery to remove products and concentrate acid
40 30
Second stage  formate and levulinate production
20
Higher temperature and longer reaction time
30
Furfural
10
Recovery steps for products, solvent and catalyst
20
0
20 min 40 min 60 min 0.1 M 0.3 M 0.5 M ACKNOWLEDGEMENTS
10
0.3 M MSA catalyst 40 min residence time
0
Sugar Research and Development Corporation
Fig. 3 – Furfural yields from acid-catalyzed (MSA) reaction of
Temp. (ºC) 160 180 180 160 180 180 Queensland University of Technology
Acid conc (M) 0.25 0.1 0.5 0.25 0.1 0.5
bagasse at 180ºC
REFERENCES

Mild condi>ons (& less reactants) ↑ yield of furfural (Fig. 1 & 3)
Fig. 1 – Product yields from acid-catalyzed reaction (30 min) of sugars [1] Fitzpatrick, S.W., 1997, US Patent 5,608,105.

EG improved yields of furfural produced under mild conditions

Selectivity among catalysts not significantly different (Fig. 1)
Formic acid to levulinic acid ratio ~1.2 for bagasse (no co-solvent) [2] Rackemann, D.W. and Doherty, W.O.S., 2011,

Activity linked to acid strength
Acetic acid (yields of 8-10 wt% for all conditions for bagasse Biofuels, Bioproducts & Biorefining, 5, 198-214.