Appendix-I

Explorative studies performed in the initial stage of research work

It is difficult to explain many things in such type of works in which a lot of time and
efforts are spent but inclusion of those hard earned experiences in the core of the thesis are
beyond any scope. In the work a lot of efforts were given in the initial period of development.
The most challenging part of the initial stage of the research was to build a gasifier (because a
gasifier is not a common equipment to find in Assam) to practically understand the process.
The only option remained open was to follow an explorative path. A brief revelation of the
experiences gained is presented here.

A. Thermal Flexible-draft Gasifier:

Fig. A.1.1 Photograph showing the gasifier in different stages of explorative work

The objective of the first explorative work was to acquire first-hand experience of
producing combustible gas from biomass. Going through the literatures on fixed bed
gasifiers, an idea of a gasifier was conceived. The first fabricated device was roughly a model
of an up-draft gasifier operating in natural draft mode. The gasifier was fabricated in the
Mechanical Engineering Department’s workshop of P.O.W. Institute, Jorhat using metal
scraps and other discarded materials to minimize cost. An old unserviceable blower in the
laboratory was repaired and used for supplying primary air necessary for the gasification
process. Truly speaking the initial experience was quiet discouraging. The gasifier failed to
produce any combustible gas while trying to gasify dry wood chips derived from old

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furniture. After rigorous investigation the problems were sorted out. After a lot of trials and
modifications it was ultimately possible to produce combustible gases. A forced draft gasifier
was built. However continuous operation was disrupted due to fuel bridging problem in the
hopper which was a regular cylinder (a piece of mild steel pipe). Later in the development of
the flexible-draft gasifier this problem was overcome by using a tapered hopper.
Nevertheless, the extent of success motivated for further exploration.

The next stage of the development was to produce gas in the T-LUD mode. The
earlier gasifier was modified. The hopper was insulated by using a mixture of ash and cement
for converting it to a reactor in the T-LUD operation. Of course the gas leakage from the
gasifier could not be totally contained due to some defects in the joints. However the device
was run by taking certain amount of risk. The problems found at this stage were rectified and
the gasifier could be operated successfully for a considerable period.

Considering the success of both the operational modes the gasifier was modified to
operate in the cross-draft mode. Success came after a lot of efforts. A flexible-draft gasifier
was thus successfully conceived in practice.

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Appendix-II

Thermo Gravimetric Analysis and Kinetic Parameters:

The kinetics of biomass decomposition is of interest among the researchers as

biomass is made of complex chemical composition with varying proportions for different
biomass species. The kinetics of biomass pyrolysis is used for modeling the process of
pyrolysis and gasification of biomass. The thermal decomposition is a complex process that
involves a large numbers of different reactions due to the chemical complexity of biomass.
Thermogravimetry provides a rapid method for determining the temperature-decomposition
profile of a material and the kinetics of its thermal decomposition. The test method covers
determination of kinetic parameters such as Arrhenius activation energy and pre-exponential
factor based on assumption that the decomposition obeys the first order kinetics.

Some related terms:

a) Activation energy: It is the minimum energy required to start a chemical reaction.

The activation energy is usually denoted by ‘E’ or ‘Ea’ and its unit in SI system is kJ/mole.
For a chemical reaction to proceed at a reasonable rate there must exists an appreciable
number of molecules with energy equal to or greater than the activation energy.

b) Pre-exponential factor: Pre-exponential constant or pre-exponential factor is an

empirical relationship between temperature and reaction rate co-efficient. For a first order
reaction it has unit of s-1.The frequency factor depends on how often molecules collide when
all concentrations are 1 mole/l and whether the molecules are properly oriented when they
collide.

c) Reaction rate constant: Reaction rate constant k or λ quantifies the speed of a

chemical reaction.

For a chemical reaction, say A+B→C

Where, : reaction rate constant that depends on temperature.

: Concentration of substance ‘C’

m, n: orders and depends on the reaction mechanism.

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d) Arrhenius Equation: This equation gives the basis of the relationship between the activation
energy and the rate at which a reaction proceeds. From the Arrhenius equation, the activation
energy can be expressed as:

/
=

Where,

A: Frequency factor or pre-exponential factor

R: Universal gas constant

T: Temperature (K)

k= Reaction rate co-efficient

Thermo Gravimetric Analysis:

Thermo Gravimetric Analysis or TGA is a type of testing that is performed on

samples to determine changes in weight in relation to change in temperature. Such analysis
relies on a high degree of precession in three measurements: weight, temperature and
temperature change. As many weight loss curves look similar, the weight loss curve may
require transformation before results may be interpreted. A derivative weight loss curve can
be used to tell the point at which weight loss is most apparent.

The analyzer usually consists of a high precession balance with a pen (generally
platinum) loaded with the sample. The pen is placed in a small electrically heated oven with a
thermocouple to accurately measure the temperature. The atmosphere may be purged with an
inert gas or dry air and the analysis is carried out at constant heating rate by raising the
temperature gradually. Curves are obtained by plotting weight against temperature. The
temperature in many testing methods routinely reaches 600-1000 °C, but the oven is so
highly insulated that heat loss from the oven may be considered as negligible.

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Appendix-III

TGA Experimental data on Ipomoea and Ipomoea char:

Table A1. TGA Data on Ipomoea carnea (experimental and derived data)

(dw/dt)
Temp Temp.Diff. Wt. Wt.
(% s-1)
(°C) (°C) (mg) %

26.2128 0.945548 29.998 100 0.000778868

37.3603 -5.47149 30.023 100.0833389 -0.015717559
53.3407 -7.31894 29.5185 98.4015601 -0.035276495
70.9889 -7.5132 28.3862 94.62697513 -0.037700333
89.2265 -7.11579 27.1761 90.59303954 -0.019664862
108.198 -1.82855 26.5449 88.48889926 -0.005190377
109.563 -0.440011 26.3783 87.9335289 -0.000797561
109.933 -0.0701415 26.3527 87.84818988 -0.000439282
110.091 0.088538 26.3386 87.80118675 -0.000277277
110.131 0.131223 26.3297 87.7715181 -0.000208737
110.144 0.144817 26.323 87.74918328 -0.000186928
110.157 0.160942 26.317 87.72918195 -0.000155774
110.168 0.157239 26.312 87.71251417 -0.000124619
110.165 0.158941 26.308 87.69917995 -0.000121503
110.153 0.162441 26.3041 87.68617908 -0.000127734
110.149 0.152531 26.3 87.6725115 -0.000124619
110.171 0.172414 26.296 87.65917728 -0.000112157
110.167 0.164462 26.2924 87.64717648 -9.34642E-06
110.17 0.211434 26.2921 87.64617641 0.009224914
110.876 0.865024 26.5882 88.63324222 0.000679173
110.975 0.972845 26.61 88.70591373 0.000133965
110.99 0.988537 26.6143 88.72024802 0.001984556
115.897 -1.43935 26.678 88.93259551 -0.000847409
134.024 -1.14353 26.6508 88.84192279 -0.001034337
152.012 -0.992166 26.6176 88.73124875 -0.001264882
170.002 -0.828285 26.577 88.59590639 -0.001682355
188.019 -0.656467 26.523 88.41589439 -0.003897456
206.025 -0.478761 26.3979 87.99886659 -0.010692302
224.158 -0.17795 26.0547 86.85479032 -0.02245321
242.52 0.349187 25.334 84.45229682 -0.061156725
261.857 1.85582 23.371 77.90852724 -0.17967553
284.972 7.1569 17.6038 58.68324555 -0.159792584
306.479 10.8008 12.4748 41.58543903 -0.052009698
321.19 7.68965 10.8054 36.02040136 -0.033960519

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 336.844 5.5047 9.71534 32.38662578 -0.030805792
353.492 4.31851 8.72654 29.09040603 -0.034017533
371.489 4.49766 7.63465 25.45053004 -0.08308934
395.429 10.6449 4.96766 16.55997066 -0.029935017
405.027 2.36907 4.00681 13.35692379 -0.029876135
427.962 7.4385 3.04785 10.16017735 -0.027987536
439.089 0.767276 2.14951 7.165511034 -0.012107038
455.622 -0.551477 1.7609 5.870058004 -0.007988383
471.467 -2.53893 1.50449 5.01530102 -0.002724792
487.57 -4.26214 1.41703 4.72374825 -0.00039878
504.411 -5.25896 1.40423 4.681078739 -8.97256E-05
521.412 -6.08484 1.40135 4.671478099 -4.20589E-05
538.433 -6.89977 1.4 4.666977799 -9.34642E-05
555.451 -7.719 1.397 4.656977132 -0.000123373
572.389 -8.6107 1.39304 4.643776252 -0.000155151
589.317 -9.51895 1.38806 4.627175145 -0.000206556
606.174 -10.4912 1.38143 4.605073672 -0.000369495
623.008 -11.4964 1.36957 4.565537703 0.000836639

Table A2. TGA Data on Ipomoea char (Experimental and derived data)

(dw/dt)
Temp. Tem.Diff. Wt. Wt.
(% s-1)
(°C) (°C) (mg) (%)

26.466 1.19649 26.2961 100 0.001215489

38.3242 -4.50217 26.3303 100.1300573 -0.014820434
55.5473 -5.12114 25.9133 98.54427082 -0.023193802
73.5064 -4.98527 25.2607 96.06253399 -0.014802664
92.0705 -4.26575 24.8442 94.47864893 -0.006973068
110.539 0.51088 24.648 93.73253068 -0.00270464
110.756 0.762967 24.5719 93.44313415 -0.000316311
110.696 0.704994 24.563 93.40928883 -0.000309203
110.739 0.741223 24.5543 93.37620408 -0.000255892
110.745 0.745894 24.5471 93.34882359 -0.000213244
110.748 0.746735 24.5411 93.32600652 -0.000191919
110.739 0.744006 24.5357 93.30547115 -0.000174149
110.738 0.74307 24.5308 93.28683721 -0.000188365
110.753 0.748748 24.5255 93.26668213 -0.000159933
110.725 0.733318 24.521 93.24956933 -0.000177703
110.741 0.746166 24.516 93.2305551 -0.000149271
110.737 0.743881 24.5118 93.21458315 -0.000170595
110.75 0.742559 24.507 93.19632949 -0.000156379

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 110.74 0.741803 24.5026 93.17959697 -0.000163487
110.739 0.740064 24.498 93.16210389 -0.000142162
110.745 0.74775 24.494 93.1468925 -0.000174149
110.763 0.751841 24.4891 93.12825856 0.012062483
116.227 -1.09438 24.8285 94.41894425 0.001403854
135.102 -0.0707373 24.868 94.56915664 -0.001162178
153.431 0.431319 24.8353 94.4448036 -0.000956042
171.801 0.970413 24.8084 94.34250706 -0.000771231
190.269 1.60361 24.7867 94.25998532 -0.001833895
208.791 2.28537 24.7351 94.0637585 -0.0056012
227.577 3.24851 24.5775 93.46443009 -0.019536673
246.951 4.78582 24.0278 91.37400603 -0.101294293
270.183 10.2149 21.1777 80.53551667 -0.176906941
292.522 14.6887 16.2001 61.60647396 -0.067793714
308.701 13.0233 14.2926 54.35254658 -0.050357491
324.951 11.4528 12.8757 48.96429509 -0.046295199
342.208 10.8707 11.5731 44.01070881 -0.051743574
360.642 11.4879 10.1172 38.47414636 -0.104785803
382.353 15.3809 7.16886 27.26206548 -0.059793167
397.579 12.7507 5.48647 20.86419659 -0.042965754
412.72 10.0568 4.27755 16.26686087 -0.03134362
430.426 9.89752 3.39564 12.91309358 -0.033427365
447.545 9.20435 2.4551 9.336365469 -0.018629322
462.578 6.41231 1.93093 7.343028054 -0.006873909
477.576 3.57746 1.73752 6.607519746 -0.002243679
492.151 0.311402 1.67439 6.367446123 -0.00100189
506.433 -3.23334 1.6462 6.260243914 -0.000828452
522.544 -4.95874 1.62289 6.171599591 -0.000526712
539.172 -6.15887 1.60807 6.115241424 -0.000320221
555.969 -7.20227 1.59906 6.080977788 -0.000282548
572.847 -8.14896 1.59111 6.050745168 -0.000286457
589.71 -9.12298 1.58305 6.020094235 -0.000232791
606.597 -10.0749 1.5765 5.995185598 -0.000246652
623.404 -11.0981 1.56956 5.968793852 0.001093787

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