LAAN-J-MS-E094
GC-MS
Gas Chromatograph Mass Spectrometer
GC-MS Analysis of Catalytic Reaction
Products of Glucose in Biomass Research
94
When converting biomass resources into energy or raw chemical materials, it is essential to improve the conversion
yield and analyze the reaction process. This sort of analysis requires identifying volatile components; therefore, GCMS systems, with their excellent qualitative capabilities, are useful.
This report presents results obtained by adding a solid acid catalyst to an aqueous glucose solution, heating the
solution, and then directly analyzing the resulting reaction solution using GC-MS without pretreatment.
At present, in the utilization of woody biomass, the cellulose that comprises approximately 60 % to 70 % of the
material can be converted to glucose. The analysis of the catalytic reaction presented in this report revealed that
primarily hydroxymehylfurfural is further generated from glucose used as a raw material. Hydroxymehylfurfural is a
compound with considerable added value as a raw material for pharmaceuticals and chemicals. The analysis also
revealed the existence of lactic acid and other low-grade organic acid compounds.
In addition, utilizing the GCMS-QP2010 Ultra, which features a differential vacuum system, enabled acquisition of
favorable results even when directly injecting the sample aqueous solution into the GC-MS.
Reaction Sequence
Fig. 1 shows how glucose is converted to hydroxymehylfurfural via a solid acid catalyst.
Skeletal
isomerization
-3H2O
Desiccation
reaction
Fig. 1: Catalytic Reaction of Glucose
Analysis Conditions
Table 1: Analysis Conditions
GC-MS:
Column:
Glass Insert:
[GC]
Injection Unit Temp.:
Column Oven Temp.:
Injection Mode:
Carrier Gas Control:
Injection Volume:
GCMS-QP2010 Ultra
Stabilwax (30 m long, 0.25 mm I.D., df = 0.25 m)
Split insert with wool (P/N: 225-20803-01)
230 C
50 C (5 min)  (10 C/min)  250 C (10 min)
Split (split ratio 10)
Linear velocity (50.0 cm/sec)
0.5 L
[MS]
Interface Temp.:
Ion Source Temp.:
Measurement Mode:
Scan Event Time:
Scan Mass Range:
Scan Speed:
250 C
230 C
Scan
0.30 sec
m/z 15 to 550
2,000 u/sec
94
Analysis Results
Figs. 2 and 3 show the results obtained by adding a solid acid catalyst to an aqueous glucose solution, heating
the solution, and then injecting the resulting reaction solution directly into the GC-MS to measure it without
pretreatment. In addition to 5-hydroxymethylfurfural, Peak 10, which is the main reaction product, formic acid,
acetic acid, lactic acid, and other low-grade organic acid compounds were also confirmed. Compounds were
surmised from the results of a similarity search using the NIST library.
8
9
10
(10,000,000)
1.25 TIC
1 2-Propanone, 1-hydroxy2 Acetaldehyde, hydroxy3 Acetic acid
1.00
4 Furfural
5 Formic acid
6 2-Furanmethanol
0.75
7 Glyceraldehyde
8 Dihydroxyacetone
9 Lactic acid
0.50
10 5-Hydroxymethylfurfural
7.5
7
6
5
43
1
2
0.25
10.0
12.5
15.0
17.5
20.0
22.5
(×1,000,000)
7
5
3
1
2
1.25
4
1.00
6
0.75
0.50
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
Fig. 2: Total Ion Current Chromatogram for the Reaction Solution
Peak No. 10: 5-Hydroxymethylfurfural
Peak No. 9: L-Lactic acid
100
100
45
19 29 43
55
50
0
100
75
90
100
150
45
200
29
0
43
55
50
69
15
0
29
50
200
150
200
O
126
O
OH
150
100
97
50
0
109
81
41
75 90
100
53
0
100
OH
O
50
0
126
50
50
0
97
41
15
0
29
69
53
50
81
109
100
OH
150
200
Fig. 3: Mass Spectra (Top: Mass Spectra for Peaks 9 and 10; Bottom: Library Search Results)
Note: Professor Michikazu Hara of the Materials & Structures Laboratory at the Tokyo Institute of Technology provided the sample.
First Edition: December 2013
 Shimadzu Corporation, 2013