Name: Levina Ayu Arastika

Identity Number: 4301415095

Group: 4
RESULT AND DISCUSSION

Pyrolysis is a relatively simple thermochemical route to break down lignin into low
molecular weight compounds in absence of oxygen (air). However, due to the physico-
chemical characteristics of lignin as a thermoplastic, thermally stable and often powder-like
material, and due to the non-spesific nature of the pyrolisis process itself, industrial lignin
pyrolysis processes are rare, although in the former USSR, hydrolysis lignins from wood
saccharification are considered to the valueable material for the production of phenolic
compounds and activated lignin carbon. Yields of mono-phenols up to 10% of the lignin were
obtained by pyrolysis of hydrolysis lignin in bio oil under reduced pressure and temperatures
of 300-400oC. (Mcdonald et al., 2014)

Pyrolysis bio-oil is a complex mixture of sugar, lipid and phenolic

derived compounds. Therefore examining functional groups of compounds
and monitoring these changes upon upgrading is a way to examine the
hydrogenation reaction. Methoxyls (-OCH3), phenol hydroxyls (Ar-OH) and
aldehydes (-C=O) are three main oxygen-containing functional groups in
bio-oil. Feasible routines to deoxygenate these groups are
demethoxylation, dehydration and hydrogenation, respectively. To simplify
the system and to examine the effect of catalyst on select functional
groups model compounds were used. (Madan, 2010)

In literature on the gas phase pyrolysis lignin for the production of chemicals, yields
of mono-phenolic compounds are reported that rarely exceed 5-6%, based on lignin. For
example 5 wt% phenolics were obtained from the vacuum distillation of coniferous wood
sawdust. To enhance the yield of monomeric phenols, several thermochemical processing
approaches have been persued such as pyrolysis of lignin in the presence of a hydrogen-donor
agent like tetralin (1, 2, 3, 4-tetrahydronaphtalene), Fe 2O3 catalysed lignin liquefaction in the
presence of solvents and in an hydrogen atmosphere, pyrolysis of lignin with cresol in an
hydrogen atmosphere, ZnCl2 catalysed pyrolysis of lignin with and without tetralin and etc.
(Rover, 2013). But in this experiment, the pyrolysis was done using Ru/C and NiMo/ Al 2O3
catalyst.
 Figure.1 Figure.2

This figure is showing that the pyrolitic lignin was analyzed by relative molecular
size distribution (RID) (Figure.1) and UV spectrometry (Figure.2). This experiment was the
second step of hydrotreating, there was various variables in this experiment, such as
temperature and exposure time. The experiment was done by 5 treatments which were the
initial state of pyrolytic lignin, PL stabilized 300 oC with 2 hours of exposure time, PL (375 oC,
2 hours), PL (400oC, 2 hours), and PL (400oC, 4 hours).

The RID and UV-spectrometry are the same detector to detect relative molecular size
distribution, this is done to compare the result of each other. We know that the pyrolysis
lignin is described by straight curves line in figure.1 and figure.2 but the different result was
obtained from different detector. In the figure.1, Mw < 200 (g/ mole) increasing constantly
and reaches top point in Mw > 300 (g/mole) and decreasing constantly at Mw > 500 (g/mole).
On the other hand, the figure.2 shows that there is peak point at M w < 200 (g/mole) and same
as the RID, UV spectrometry shows that pyloytic lignin reaches top point in M w > 300
(g/mole) and decreasing constantly at Mw > 500 (g/mole). Generally, it means that the size of
molecular weight on the left side of the graph is small yet the intensity to passing the
chromatography colomn has bigger value rather than the size of molecular weigh on the right
side of the graph (the intensity to passing the chromatography colomn has smaller value).

The result of pyrolytic lignin treatments in the figure.1 shows that generally has
bigger value at Mw < 200 (g/mole) rather than the initial state of pyrolytic lignin itself but still
the initial state has bigger value when RID intensity at 1000 au. PL stabilized at 400 oC with 2
and 4 hours of exposure time, only reaches the top point at M w <100 (g/mole) and decreasing
constantly afterward. This is very different when compare to another treatments pyrolytic
lignin and the initial state of pyrolytic lignin which are have top point at Mw > 300 (g/mole).

Another various result occurs when it was analyzed by UV-Spectrometry (figure.2).

Generally the treatments of PL have smaller molecular weight value that distributed into
chromatography column rather than initial state ones. All the PL treatments have top point in
Mw > 300 (g/mole) but only in 100 au of VWD intensity. On the other hand, the initial state
have top point in Mw > 300 (g/mole) but the value of VWD intensity almost 250 au. There is
a big gap between initial state and special treatment of pyrolytic lignin. It concluded that
initial state of pyrolytic lignin had bigger value of UV intensity compared to the treatment
ones by using VWD-Spectrometry.

Figure.3

This graph is showing that the pyrolytic lignin was analyzed by UV-fluoresence
spectra at a constant energy of -2800 cm-1. Similar to the experiement before, there was
various variables of temperature and exposure time. The experiment was done by 5
treatments which were the initial state of pyrolytic lignin, PL stabilized 300 oC with 2 hours of
exposure time, PL (375oC, 2 hours), PL (400oC, 2 hours), and PL (400oC, 4 hours).

The UV-flouresence is to detect the aromatic ring structure. Generally, PL has highest
value of molecule ring that fused. Because the response of UV-fluorescence is linear with the
concentration of products, the height of the peaks (intensity) can be considered as a semi-
quantitative measure of their yield. As we seen, the pyrolytic lignin is shown by straight
curves line with intensity peak is 20 au and at wavelength is almost 325nm. The curve shows
increasing constantly starts at > 250 nm until > 300nm but then starts decreasing constantly
until > 400nm.

Generally, the treatments of pyrolytic lignin has bigger value of intensity yet the
wavelength is < 250nm. But it only reaches peak at almost 13 au of intensity compare to 20
au of initial state PL intensity. Except for stabilized PL 400oC (4 hours), the peak is almost 17
au of intensity. Polymerization reactions are confirmed by an increase in formation of large
aromatic ring structures (>370 nm) whereas the intensity of smaller ring structures around
270-350 nm decreases, as shown by UV-Fluorescence spectra.

References

Madan, A. (2010) This presentation does not contain any proprietary, confidential, or
otherwise restricted information, Contractor, 6, pp. 126.

Mcdonald, A., Mcilroy, D., Han, Y. and Kengne, B. (2014) PYROLYSIS BIO-OIL
UPGRADING TO RENEWABLE Final Report, (January).

Rover, M. R. (2013) Analysis of sugars and phenolic compounds in bio- oil by.