ASH DEPOSITION CHARACTERISTICS OF INDUSTRIAL WASTE

FROM PETROLEUM CRUDE PROCESSING PLANT AND PALM OIL

MILL

Tang Jin Han1,a, Noorfidza Yub Harun1

1Universiti Teknologi PETRONAS, Perak, Malaysia

atjhan0206@hotmail.com

Abstract
In this experimental study, ash deposition characteristics of industrial waste from natural gas
processing plant (PGB) and palm oil mill (POME) have been analyzed. Implementation of industrial
waste as thermal source is an effective way to transform the unwanted scheduled waste into renewable
energy. Thus, both innovative sludge feedstocks are aimed to produce significant amount of thermal
energy through combustion. However, the effective utilization of sludge biomass is evaluated based on
its ash content, chemical composition and its ash slagging and fouling tendency. PGB and POME are
evaluated to have energy content about 21.35 MJ/kg and 15.238 MJ/kg respectively. Moreover, PGB
sludge is obtaining ash content around 30.0% where POME sludge is about 38.0%. To illustrate the
realistic combustion condition under different temperature, the effect of ashing temperatures that are
525oC, 575oC and 625oC to the ash deposition characteristics is also examined. This variation of
ashing temperature will also deflect the chemical composition especially the heavy metal element in the
sludge ash. Furthermore, the physical ash deposition and deformation characteristics are observed by
ash fusion test. Conclusively, PGB and POME biomass are both feasible to produce sufficient thermal
energy as well as stable at high temperature with their distinct chemical composition and also the
influence of actual ashing temperature.

1. Introduction
Due to the depletion of non-renewable energy, alternatives of green energy are intensively researched
to counter this issue. In this project study, PGB and POME industrial sludge biomass is selected as the
chemical feedstock to produce significant amount of thermal energy in power generation. Typically,
power generation from biomass is taken place by combustion. The combustion of biomass fuel will form
ashes from its chemical composition. This ash will cause ash deposition issues like slagging and
fouling that act as heat insulation that can deform the heating efficiency of equipment[1].

During ash deposition, the chemical composition of the solid biomass is a major factor to determine the
effective utilization of biomass. The elements that are mostly found in biomass are alkali metal, silica
and halogen component. For industrial waste, higher amount of inorganic compound and heavy metal
is perceived as compared to agricultural waste[2]. During biomass combustion, metal oxide is formed as
the remaining ash after complete removal of organic and volatile compound. Then, fusion between this
metal oxide with component like Chloride, Fluoride and Sulfide will occur and cause ash deposition.

For biomass ashing, PGB and POME are ashed under three different temperatures which are 525 oC,
575oC and 625oC based on National Renewable Energy Laboratory (NREL) standard[3]. Previous study
has stated that the different in ashing temperature will differentiate the ash fusion properties. Then, this
variation of ash fusion characteristics is qualitatively analyzed by using Ash Fusion Tester (AFT)
machine. AFT machine is applied to observe the deformation stage of ash in different fusion
temperature. Generally, the qualitative analysis of industrial biomass is referred to its ash deposition
characteristics which are closely depending of the physical and chemical nature of the biomass itself.
Hence, an optimal biomass combustion is to be achieved based on the ash content, elemental
composition, ashing temperature as well as the slagging and fouling deposition of biomass utilization.

2. Material and method

2.1. Sample preparation

Raw sludge waste from the industrial waste treatment facility which are PGB and POME are collected
as biomass feedstock. The raw biomass is stored in a chilled room for preservation purpose. Fig. 1
shows the raw sample of PGB and POME biomass placed in a dried crucible.

Fig. 1: Raw PGB (left) and POME (right) biomass.

2.2. Biomass ashing

Programmable furnace is implemented to perform biomass ashing. Biomass is ashed under 525oC,
575oC and 625oC according to the ramping phase. Initially, 2.0 grams of biomass sample are ashed to
determine the relative ash contant. Table 1 shows the required ramping phase for biomass combustion.

Table 1: Ramping phase for biomass combustion[3].

Ramping 525oC 575oC 625oC
1st Hold o
105 C for 12 minutes
1st Ramp o o
220 C at 8 C/min 250oC at 10oC/min 280oC at 12oC/min
2nd Hold Hold for 30 minutes
2nd Ramp o o
525 C at 20 C/min 575oC at 20oC/min 625oC at 20oC/min
3rd Hold Hold for 180 minutes
4th Phase Naturally cool down to 105oC

2.3. Biomass qualitative analysis

2.3.1. Calorific value determination
Bomb calorimeter is applied to determine the thermal energy value in term of MJ/kg of raw biomass. In
this analysis, 0.5 gram of PGB and POME biomass are analyzed. This analysis is important to ensure
that the industrial biomass species is feasible to produce sufficient thermal energy.

2.3.2. Ash content

Eq. (1) is applied to calculate the ash content out of 2.0 grams of raw biomass.
Weightinitial  Weightash
Ash content(%)   100% (1)
Weightinitial
2.3.3. CHNS analysis
Basic organic compound like Carbon (C), Hydrogen (H), Nitrogen (N) and Sulphur (S) is determined by
using CHNS analyzer. Besides, the H/C ratio is also obtained to justify the acquired calorific value from
Section 2.3.1. Eq. (2) is applied to calculate the H/C ratio of biomass.
H (wt%) 1 gmole -1
H / C ratio  (2)
C (wt%) 12 gmole -1

2.3.4. Heavy metal analysis

Inductively coupled plasma optical emission spectrometry (ICP-OES) is implemented to determine the
volatile and heavy metal composition in the biomass ash. The biomass ash is digested with 9.0 ml Nitric
Acid, 2.0 ml Hydrochloric Acid and 1.0 ml of Hydrogen Peroxide according to EPA 3052 Standards. The
metal composition is used to determine the base/acid ratio as well as ash fouling propensity by using
Eq. (3) and Eq. (4) respectively.
( K  Na  Ca  Fe  Mg) wt%
B / A ratio  (3)
( Al  Si  Ti) wt%

Fouling propensity  B A  Na (wt%) (4)

2.3.5. Ash fusion test

Ash fusion test is vital to evaluate the thermal stability of biomass ash under high temperature condition
up to 1500oC. Four phases of ash fusion temperatures that are initial deformation (IDT), sintering (ST),
Hemispherical (HT) and flow (FT) are determined.

2.3.6. Ash surface morphology

Field emission scanning electron microscope (FESEM) is used to observe the surface morphology of
PGB and POME biomass ash.

3. Results and findings

3.1. Calorific value

Raw PGB and POME biomass have been tested for their heating calorific value. In this experiment,
calorific value refers to the actual energy production of the biomass species during complete
combustion. Table 2 tabulates the results acquired from bomb calorimeter.

Table 2: Calorific value (MJ/kg) for PGB and POME.

Trial PGB (MJ/kg) POME (MJ/kg)
1 21.350 15.238
2 21.341 15.233
3 21.347 15.241
Average 21.346 15.237

PGB is obtaining higher energy value which is 21.346 MJ/kg than POME which is 15.237 MJ/kg. This
might because of in PGB effluent, residual heavy hydrocarbon composition from natural gas processing
facility has provided it with high energy value. However, both species have met the expected calorific
value from common industrial sludge that is about 15 MJ/kg [4].
3.2. Ash content
PGB and POME biomass are combusted under three different ashing temperatures. Fig. 2 shows the
biomass ash after complete combustion. For ash content determination, Fig. 3 is shown.

Fig. 2: PGB ash (left) and POME ash (right).

From Fig. 2, PGB ash is found to be in orange color. This is abnormal from the common biomass ash
color which is white after the complete removal of hydrocarbon. As an early justification, this might due
to the existing of mineral like Ferum Oxide in the biomass composition [5].

Ash content of PGB and POME

40.000
Ash content (%)

35.000
30.000
25.000
20.000
PGB POME
525oC 29.960 36.836
575oC 28.641 37.569
625oC 28.698 36.408

Fig. 3: Ash content of PGB and POME.

As per histogram chart in Fig. 3, ash content of POME is always higher than PGB. Nonetheless, both
biomass species are still obtaining higher ash content for conventional biomass utilization [2].

3.3. Organic composition

C, H, N and S elements are analyzed to determine the H/C ratio in the biomass. A higher H/C ratio in
the raw biomass is referred to a higher calorific value in the species [6]. Table 3 tabulates the organic
composition with the H/C ratio in PGB and POME biomass.

Table 3: Organic composition and H/C ratio in PGB and POME.

Element PGB (wt %) POME (wt %)
Carbon (C) 32.66 13.68
Hydrogen (H) 5.38 2.12
Nitrogen (N) 3.94 4.43
Sulphur (S) N.D. N.D.
H/C ratio 1.977 1.859

As shown in Table 3, H/C ratio of PGB biomass species which is 1.977 is higher than the ratio in POME
that is 1.859. This has justified the higher calorific value of PGB which is 21.346 MJ/kg as compared to
POME in Section 3.1. Besides, Sulphur content is not detectable in both species. The absence of
Sulphur content is advantageous as this will avoid the presence of ash slagging issue[1].
3.4. Volatile and heavy metal composition
Table 4: Volatile and heavy metal composition in ash for different ashing temperatures.
525oC (wt%) 575oC (wt%) 625oC (wt%)
Element
PGB POME PGB POME PGB POME
K 1.81 5.83 1.40 4.58 1.23 3.95
Na 0.58 0.24 0.41 0.28 0.18 0.16
Ca 0.50 16.90 0.43 12.80 0.57 12.37
Fe 32.23 3.21 28.59 2.45 12.76 2.76
Mg 1.27 3.83 1.57 3.06 1.26 3.75
Al 18.67 8.10 21.24 5.98 24.34 6.29
Si 9.88 10.88 11.21 12.43 11.44 13.60
Ti 0.01 0.02 0.03 0.02 0.02 0.02
Fouling Propensity
B/A 1.274 1.580 0.997 1.257 0.447 1.155
Fouling 0.739 0.374 0.405 0.353 0.081 0.181

In Table 4, the volatile metal components that are K, Na, Ca, Fe and Mg decrease when ashing
temperature increases. This is due to the reason that at higher temperature combustion, more volatile
metal especially the K and Na are vaporized[7]. For the alkali earth metals which are Ca and Mg, the
composition of these metal is always more abundant in POME species than PGB biomass. This
chemically stable alkali earth metal can help in increasing the ash fusion temperature of biomass [6].

For acidic metal which are the Si, Al and Ti, the metal composition has reflected the effect of ashing
temperature towards their composition. As for Silica which is a good binding agent, its composition has
increased when the ashing temperature increases. This situation is caused by the abundancy of silicate
crystal formation from the silica metal and the fused volatile metal during the high temperature
combustion[6]. For Ti which is a transition heavy metal, the minuscule composition in the ash has the
least effect to the ash fusion temperature[8]. Moreover, ash fouling is normally caused by volatile fly
ash[9].. Hence, POME biomass ash has always obtained a lower fouling propensity due to its lower Na
composition in the ash. Furthermore, when the ashing temperature increases, the fouling index and
base/acid ratio are decreased because of the massive vaporization of volatile metal to the
atmosphere[10].

3.5. Ash fusion temperature

Ash fusion temperatures describe the thermal stability of biomass species. The biomass with higher
ash fusion temperature shows a lower possibility of ash deposition that is caused by ash melting [8].

Table 5: Ash fusion temperatures of PGB and POME biomass ash.

Temperature (oC) Species IT (oC) ST (oC) HT (oC) FT (oC)
PGB 962.5 1187.5 1270.0 1362.5
525
POME 1202.5 1287.5 1352.5 1490.0
PGB 985.0 1217.5 1280.0 1377.5
575
POME 1210.0 1295.0 1372.5 1515.0
PGB 1047.5 1197.5 1285.0 1400.0
625
POME 1212.5 1320.0 1407.5 1515.0

In Table 5, effect of ashing temperature is clearly explained by the difference in ash fusion temperature.
By taking initial deformation temperature (IT) as discussion, IT for POME has increased gradually from
1202.5oC to 1212.5oC when the ashing temperatures are varied from 525oC towards 625oC. At the
same time for PGB, the trend of increasing ash fusion temperature is followed. Nevertheless, the ash
fusion temperature for PGB is always lower than POME. This situation can be discussed through the
difference in chemical composition of the biomass ash. From literature study, the increase in ash fusion
temperature could due to the higher amount of alkali earth metal such as Ca and Mg [11]. Furthermore,
the abundancy of Si as the ash binding agent can leverage the melting point of biomass ash too [7].

3.6. Ash surface morphology

Fig.4 and Fig. 5shows the surface morphology of PGB and POME ash.

Fig. 4: SEM image of PGB ash. Fig. 5: SEM image of POME ash.
As referred to Fig. 4 and Fig. 5, the physical distribution of PGB and POME ash is kindly similar as the
surface texture is formed by crystalline particle with regular shape. Nonetheless, the crystallized
structure for POME biomass ash is more obvious n a “pile-like” shape as shown in Fig. 5. This could be
due to the higher composition of Si element in the biomass ash particle as per discussion in Section
3.4[11]. This effective binding agent form metal silicate with uniform shape with the alkali base metal like
K, Na and Mg. Besides, the “flake-like” shape in PGB ash could be due to the abundancy of Fe element
too.

4. Conclusion
PGB and POME biomass are eligible to act as a feasible biomass fuel by producing sufficient energy
that are 21.346 MJ/kg and 15.237 MJ/kg respectively. However, the higher ash content as compared to
the conventional biomass is an issue to be encountered. With its distinct relationship between ashing
temperature and ash composition, PGB and POME are claimed to be stable at high temperature.
Moreover, the increased in ashing temperature is determined to be effective in reducing the ash
slagging and fouling tendency.

Acknowledgements
Deepest gratitude to Chemical Engineering Department, Universiti Tenologi PETRONAS that has
provided sufficient facility support in conducting this experimental study. Besides, research funding
from Yayasan Universiti Teknologi PETRONAS and Faculty of Engineering is also highly appreciated.

References
1. C. H. Pang, B. Hewakandamby, T. Wu, and E. Lester, "An automated ash fusion test for
characterisation of the behaviour of ashes from biomass and coal at elevated temperatures," Fuel,
Vol. 103, pp. 454-466, (2013).
2. S. Werle and M. Dudziak, "Analysis of organic and inorganic contaminants in dried sewage sludge
 and by-products of dried sewage sludge gasification," Energies, Vol. 7, No. 1, pp. 462-476, (2014).
3. A. Sluiter, B. Hames, R. Ruiz, C. Scarlata, J. Sluiter, and D. Templeton, "Determination of ash in
biomass. Laboratory Analytical Procedure (LAP)," NREL, Golden, CO, 2008.
4. S. K. Sansaniwal, M. A. Rosen, and S. K. Tyagi, "Global challenges in the sustainable
development of biomass gasification: An overview," Renewable and Sustainable Energy Reviews,
Vol. 80, pp. 23-43, (2017).
5. J. B. Thacker, D. D. Carlton, Z. L. Hildenbrand, A. F. Kadjo, and K. A. Schug, "Chemical analysis of
wastewater from unconventional drilling operations," Water, Vol. 7, No. 4, pp. 1568-1579, (2015).
6. S. K. Loh, "The potential of the Malaysian oil palm biomass as a renewable energy source,"
Energy Conversion and Management, Vol. 141, No. Supplement C, pp. 285-298, (2017).
7. X. Fang and L. Jia, "Experimental study on ash fusion characteristics of biomass," Bioresource
Technology, Vol. 104, pp. 769-774, (2012).
8. Y. Niu, H. Tan, and S. e. Hui, "Ash-related issues during biomass combustion: Alkali-induced
slagging, silicate melt-induced slagging (ash fusion), agglomeration, corrosion, ash utilization, and
related countermeasures," Progress in Energy and Combustion Science, Vol. 52, pp. 1-61, (2016).
9. L. Li, C. Yu, F. Huang, J. Bai, M. Fang, and Z. Luo, "Study on the Deposits Derived from a
Biomass Circulating Fluidized-Bed Boiler," Energy & Fuels, Vol. 26, No. 9, pp. 6008-6014, (2012).
10. T. Yan, L. Kong, J. Bai, Z. Bai, and W. Li, "Thermomechanical analysis of coal ash fusion
behavior," Chemical Engineering Science, Vol. 147, pp. 74-82, (2016).
11. T. Ma, C. Fan, L. Hao, S. Li, W. Song, and W. Lin, "Fusion characterization of biomass ash,"
Thermochimica Acta, Vol. 638, pp. 1-9, (2016).
12. R. PÖYKIÖ, M. MÄKELÄ, G. Watkins, H. Nurmesniemi, and D. Olli, "Heavy metals leaching in
bottom ash and fly ash fractions from industrial-scale BFB-boiler for environmental risks
assessment," Transactions of Nonferrous Metals Society of China, Vol. 26, No. 1, pp. 256-264,
(2016).