Transcript FIXED-BED SLOW PYROLYSIS OF RAPE SEED O. Onay, S.H. …

Anadolu University
TURKEY
Co-pyrolysis of lignite and biomass in a fixed-bed reactor
O. Onay, E.Atabay, S.H. Beis and O. M. Kockar
Department of Chemical Engineering, Faculty of Engineering Anadolu University, 26470,
Eskisehir, Turkey
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
ABSTRACT

In this study, investigations into the product yields during co-pyrolysis of
coal/biomass blends prepared at different ratios have been conducted using a
fixed-bed pyrolysis reactor.

The effects of blend ratio for pyrolysis of coal/safflower seed
The final pyrolysis temperature on the pyrolysis products yield
Mixture composition on the chemical compositions of the oil have been
investigated .


World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
INTRODUCTION

The world energy demand is currently mainly met by conventional fossil energy
sources such as coal, crude oil and natural gas. The volume of these reserves is
limited and fossil fuels are the source of Greenhouse Gases. Attention is now
turning towards renewable energy sources. such as solar, wind, tidal energy and
biomass.

The co-processing of biomass with coal offers a number of advantages. The
thermal utilization of biomass can contribute to the reduction of CO2 emissions
as the same amount of CO2 is extracted from the atmosphere during the growth
period of the plants as is released by combustion (CO2 balance), as well as
beneficial effect on the reduction in SO2 emissions.

The utilization of a variety of poor coal including, low grade coal and refuse coal
as a primary energy source is becoming a subject of utmost importance in many
countries, like Turkey, where there is a substantial reserve of such materials.
Unlike poor coal, biomass has a low ash and sulphur content, a high volatile
matter yield and fixed carbon with high reactivity. Therefore, it could potentially
be attractive from the economical, environmental and social points of view that
poor coal would be utilized for oil production to make use of expected
synergistic effects of mixing biomass waste to it in a co-pyrolysis thus enhancing
the added value of the final product.
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
……INTRODUCTION

Pyrolysis is considered one way for low-rank coal valorization since highvalue gas and liquid products and good quality chars are obtained. An
additional improvement of pyrolysis products can be achieved when coal is
co-pyrolyzed together with some selected materials. Co-pyrolysis process
could have potential for the environmentally friendly transformation of
biomass and coal to valuable products.

Consequently, the treatment of biomass-coal is a challenge for the future.
Pyrolytic processes are suitable to convert coal and biomass materials into
valuable feedstock and the specific benefits of this method potentially
include: the reduction of the volume of biomass; the recovery of chemicals
and the replacement of fossil fuels.
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
EXPERIMENTAL

The safflower seed (Carthamus tinctorius L.) and lignite sample investigated in
this study has been taken from vicinity of Eskisehir and Kutahya-Seyitömer
region, was located in central Anatolia, respectively.

Prior to use, the sample was air dried, grounded in a high-speed rotary cutting
mill. Particle size range was between 0.5-1.0 mm for lignite and 1.25-1.8 mm
for safflower seed.

The proximate analysis

Elemental analysis (Fisons EA 1108)
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
Pyrolysis
.........EXPERIMENTAL

Safflower seed, lignite and their mixtures were pyrolysed in a Heinze retort. The
experiments performed in the Heinze reactor were carried out in two groups.

In the first, to determine the effect of pyrolysis temperature on the product
yields,
four different pyrolysis temeperature of either 400, 500, 550 or 700°C
and the heating rate was taken as 7 °Cmin–1. For these experiments %50
blending ratio of safflower seed (weight of safflower seed in (weight of
safflower seed in the blend expressed as a percentage of the total sample weight)
was used.

In the second group of the experiments, order to establish the effect of blending
ratio on the pyrolysis yields,
a range of blending ratios between 0% and 100% (w/w)
The final pyrolysis temperature and the heating rate were 550°C and 7°Cmin-1,
respectively.
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
.........EXPERIMENTAL
……..Characterization
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Chemical class compositions of the oils were determined by liquid column
chromatographic fractionation.
The oil was separated into two fractions as n-pentane soluble and insoluble
compounds (asphaltenes) by using n-pentane. The n-pentane soluble material
was further separated on activated silica-gel (70-230 mesh). The column was
eluted successively with n-pentane, toluene and methanol to produce aliphatic,
aromatic and polar fractions, respectively. Each fraction was dried and
weighed.

The fractions were analyzed by Fourier transform infrared spectroscopy to
determine the efficient separation of the chemical class.

In addition, n-pentane fraction was analyzed by GC/MS (HP 6890 GC/MS 30
m  0.25 mm i.d.; 0.25 m film thickness, HP-5MS column).
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
RESULTS AND DISCUSSION
Table 1. Main characteristics of the safflower seed and lignite
Ch Characteristics
Proximate analysis
(wt.%,as received)
Moisture
Volatile
Fixed C
Ash
Elemental analysis
(wt%, daf.basis)
Carbon
Hydrogen
Nitrogen
Sulphur
Oxygen
(by difference)
Empirical formula
H/C molar ratio
O/C molar ratio
Calorific value(MJ/kg)
Lignite
Safflower seed
11.2
32.7
16.5
39.6
5.7
80.8
11.3
2.2
35.6
3.1
0.6
60.7
61.1
9.2
2.8
26.9
CH1.05N0.0O1.28
1.05
1.28
6.6
CH1.82N0.04O0.33
1.81
0.33
26.8
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
..........RESULTS AND DISCUSSION
60
Conversion
Char
Oil
Pyrolytic Water
Gas
Yield(wt.%)
50
40
30
20
10
400
450
500
550
600
650
700
0
Pyrolysis Temperature( C)
Fig.1. Effects of pyrolysis temperature on the co-pyrolysis
products at 50%( w/w) blending ratio of safflower seed
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
..........RESULTS AND DISCUSSION
80
70
Yield(wt.%)
60
conversion
char
oil
gas
50
40
30
20
10
0
20
40
60
80
100
Blending ratio of safflower seed (%w/w)
Fig.2. Effects of blending ratio of coal and safflower seed on the production of the copyrolysis products at pyrolysis tempera-ture of 550°C. The dashed lines represent the
theoretical additive evolutions of the products.
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
..........RESULTS AND DISCUSSION
A
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A b u n d a n c e
T IC : E G 3 6 .D
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Fig.4 GC/MS of the n-pentane fraction for coal (a),
coal/biomass (b) and biomass (c) pyrolysis oils
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy
CONCLUSION

In the present work, mixtures of safflower seed and coal can be radically
converted to liquid products by pyrolysis under self pyrolysis atmosphere in
Heinze retort.

At pyrolysis temperature of 550°C the maximum yield of oil is watched.

At this temperature, the most important parameter for the oil production is the
blending ratio in feedstocks.

For the experiments with coal less than 33wt.%, additive phenomena occur,
leading to higher oil production.

The yield of oil goes to a maximum of about 35wt.% for 10% blending ratio of
coal in the experimental conditions used.
World Renewable Energy Congress IX and Exhibition, 19-25 August 2006, Florence-Italy