Available online at www.sciencedirect.

com

ScienceDirect
Availableonline
Available onlineatatwww.sciencedirect.com
www.sciencedirect.com
Energy Procedia 00 (2017) 000–000

ScienceDirect
ScienceDirect
www.elsevier.com/locate/procedia

Energy
EnergyProcedia 142
Procedia 00(2017)
(2017)3240–3243
000–000
www.elsevier.com/locate/procedia

9th International Conference on Applied Energy, ICAE2017, 21-24 August 2017, Cardiff, UK

Influence of Oxy-fuel Atmosphere on Microscopic Physical-

The 15th International Symposium on District Heating and Cooling
Chemical Properties of High-alkali Ash at Softening Temperature
Assessing
Chang’an Wang, Hanqing the feasibility
Li, Chenzhaoof Zhu,using the heat
Tao Han, Yinhedemand-outdoor
Liu, Lei Deng, Defu Che*
temperature function for a long-term district heat demand forecast
State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering,
Xi'an Jiaotong University, Xi'an 710049, China
I. Andrića,b,c*, A. Pinaa, P. Ferrãoa, J. Fournierb., B. Lacarrièrec, O. Le Correc
Abstract
a
IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
The utilization
c
of high-alkali
Département coals
Systèmes in Zhundong
Énergétiques coalfield -with
et Environnement oxy-fuel 4combustion
IMT Atlantique, technology
rue Alfred Kastler, has aFrance
44300 Nantes, great potential,
however, the ash fusion properties of high-alkali coals are still unclear. Here, we studied the influence of oxy-fuel
atmosphere on the microscopic properties of high-sodium ash. The change from air to oxy-fuel condition has a
negligible influence on ash fusion temperatures, but exhibits certain impact on physical-chemical properties of high-
Abstract
alkali ash. Oxygen content presents a primary effect on the microscopic morphology of ash at softening temperature.
© 2017 The Authors. Published by Elsevier Ltd.
©District
2017 Theheating networks
Authors. are commonly
Published by Elsevier addressed
Ltd. in the literature as one of the most effective solutions for decreasing the
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.
greenhouse under
Peer-review gas emissions from of
responsibility thethe
building sector.
scientific These systems
committee of the 9threquire high investments
International Conferencewhich are returned
on Applied Energy.through the heat
sales. Due to the changed climate conditions and building renovation policies, heat demand in the future could decrease,
Keywords: high-alkali coal; oxy-fuel combustion; CO2 capture; microscopic properties; SEM
prolonging the investment return period.
The main scope of this paper is to assess the feasibility of using the heat demand – outdoor temperature function for heat demand
forecast. The district of Alvalade, located in Lisbon (Portugal), was used as a case study. The district is consisted of 665
1.buildings
Introduction
that vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district
renovation scenarios were developed (shallow, intermediate, deep). To estimate the error, obtained heat demand values were
Coal is with
compared the principal energy
results from resource
a dynamic worldwide
heat demand andpreviously
model, accountsdeveloped
for a primary contribution
and validated by the to electricity generation
authors.
[1-2]. Zhundong coalfield is one super-huge coalfield newly discovered in China and will
The results showed that when only weather change is considered, the margin of error could be acceptable for occupy an some
ever-increasing
applications
position
(the errorininpower
annualgeneration
demand was andlower
chemical industry
than 20% ofweather
for all China in future. considered).
scenarios However, the utilization
However, afterofintroducing
Zhundongrenovation
coals in
power plants
scenarios, the has
errorcaused serious ash-related
value increased up to 59.5%issues mainly
(depending on due to its high-alkali
the weather feature
and renovation [3-6].combination
scenarios Oxy-fuel combustion
considered).
Therealize
can value of slope coefficient
large-scale increased
CO2 capture andonlow
average
NOx within the range
emission of 3.8% uppower
from coal-fired to 8% plants
per decade,
[7-10].thatThe
corresponds to of
utilization the
decrease in coals
high-alkali the number of heatingcoalfield
in Zhundong hours of 22-139h during the
with oxy-fuel heating season
combustion (depending
technology hasona the combination
great potential of weather
and primaryand
renovation in
possibility scenarios
the nearconsidered). On the other
future. However, onlyhand, function
limited intercept increased
investigations for 7.8-12.7%
were reported for theperash
decade (depending
fusion behaviorson of
the
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
high-alkali coals under oxy-fuel condition. Little work was conducted on the influence of oxy-fuel atmosphere on
improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
* Corresponding author. Tel.: +86-029-82668703; fax: +86-029-82668703
Cooling.
E-mail address: [email protected]
Keywords: Heat demand; Forecast; Climate change
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the scientific committee of the 9th International Conference on Applied Energy.
10.1016/j.egypro.2017.12.497
 Chang’an Wang et al. / Energy Procedia 142 (2017) 3240–3243 3241
2 Chang’an Wang/ Energy Procedia 00 (2017) 000–000

characteristics of high-alkali ash, and the volatility behavior of ash as the ash fuses is still unclear. In addition, the
possible change of microscopic physical-chemical properties of high-alkali ash has yet to be fully understood. Here,
we aimed at experimentally elucidating the influence of oxy-fuel atmosphere on physical-chemical features of high-
alkali ash at softening temperature (one frequently-used index to judge the slagging tendency of coal).

2. Experimental

A typical Zhundong coal was selected for the present study, and the corresponding coal properties were shown in
Table 1 and Table 2. Here, the ash was prepared at 815 oC according to Chinese standard “Test Method for Analysis
of Coal Ash (GB/T1574)”. The ash fusion temperatures were measured in an ash melting point apparatus (HR-8)
with controlled atmosphere. The ash volatility experiments were conducted using a Setaram simultaneous thermal
analyzer (Labsys Evo). The microscopic physical-chemical properties were analyzed using an analytical scanning
electron microscope (JEOL JSM-6390A) with energy dispersive X-ray spectroscopy (EDX) technique.
Table 1. The proximate and ultimate analyses of coal sample from Zhundong coalfield (%)
Vdaf Mad Mar Aar Car Har Oar Nar Sar
ZD 31.84 10.42 30.7 3.05 53.84 2.68 8.86 0.50 0.37

Table 2. The ash composition analysis of coal sample from Zhundong coalfield (%)
SiO2 Al2O3 TiO2 Fe2O3 CaO MgO K2O Na2O SO3 MnO2
ZD 13.54 14.79 1.13 5.68 32.74 3.59 0.70 4.63 22.45 0.08

3. Results and Discussion

3.1. Influence of oxy-fuel atmosphere on fusion and volatility of high-alkali ash

The influence of atmosphere on ash fusion temperatures is shown in Fig. 1, where DT corresponds to
deformation temperature, ST corresponds to softening temperature, HT corresponds to hemispherical temperature,
and FT is the fluid temperature. As illustrated in Fig. 1 that the ash fusion temperatures show almost no difference
among pure CO2, air, and oxy-fuel atmospheres. The replacement of N2 by CO2 has a negligible influence on the
content of various mineral matters in high-alkali ash. Although the ash fusion temperatures in various atmospheres
in the present study were almost the same, the weak reducing medium is more likely to exist under oxy-fuel
condition due to the increase of CO content locally, which will most probably lead to a decrease of ash fusion
temperatures and then serious local slagging. It also can be observed from Fig. 1 that the difference between DT and
ST is within 30 oC, and thus the slag of Zhundong coal belongs to short slag.

Fig. 1. Influence of oxy-fuel atmosphere on ash fusion temperatures

3242 Chang’an Wang et al. / Energy Procedia 142 (2017) 3240–3243
Chang’an Wang/ Energy Procedia 00 (2017) 000–000 3

TG-DSC analysis was employed to probe the ash volatility when ash fuses and deforms with temperature using
the same heating procedure as the ash fusion tests. It can be observed from Fig. 2 that both TG and DSC curves in
various atmospheres exhibit similar evolution tendency and the mass losses are increased with temperature. The
reduction rate is increased significantly as the temperature is above 1200 oC, while it slows down at deformation
temperature (DT). A small endothermic peak is also present on DSC curves nearby the temperature of DT. Oxy-fuel
atmosphere has a certain influence on the volatility of high-alkali ash in the present study. The ash sample under the
condition of pure CO2 presents the maximum mass loss. In addition, the change from air condition to oxy-fuel case
leads to a slight reduction of ash volatility if the O2 content is the same. The increase of O2 content in oxy-fuel
atmosphere results in more mineral matter releasing into gaseous phase.

Fig. 2. Effect of atmosphere on ash volatility as ash fuses and deforms with temperature: (a) the case of 100% CO2;
(b) the case of 21% O2/79%CO2; (c) the case of 50% O2/50%CO2; (d) the case of 21% O2/79%N2.

3.2. Influence of oxy-fuel atmosphere on the microscopic physical-chemical properties of high-alkali ash

The softening temperature (ST) is one frequently-used index to judge the slagging tendency during thermal
conversion of coal. The microscopic physical and chemical features of high-sodium ash at softening temperature are
shown in Fig. 3. It can be seen from Fig. 3 that the white spots distribute on surfaces of the softened ashes, which
are in the most rich distribution under the condition of 21% O2/79% CO2 atmosphere. The EDX analysis indicated
that these white spots were most likely to be principal BaSO 4. The regions outside the white spots in Fig. 3 are rich
in sodium, calcium, and silicon, but lack of sulphur and without barium. Obviously physical differences among
various ash samples could be observed from SEM analysis. The surfaces of softened ash in air and 21% O 2/79%
CO2 atmosphere are both flocculent and rough as shown in Fig. 3. The ash surface under the condition of 50% O2/50%
CO2 atmosphere was smooth, while some columnar particles were present on surface of softened ash obtained in
100% CO2 atmosphere. It might be deduced that the microscopic morphologies of Zhundong coal ashes obtained at
softening temperature were chiefly influenced by the oxygen content in local atmosphere.
 Chang’an Wang et al. / Energy Procedia 142 (2017) 3240–3243 3243
4 Chang’an Wang/ Energy Procedia 00 (2017) 000–000

Fig. 3. The microscopic physical properties of high-sodium ash at softening temperature under various atmospheres

4. Conclusion

The influence of oxy-fuel atmosphere on microscopic properties of high-alkali ash from Zhundong coalfield was
experimentally investigated in the present study. The change from air to oxy-fuel condition has a negligible
influence on ash fusion temperatures, but presents certain impact on the physical-chemical properties of high-alkali
ash. Oxygen content is likely to exhibit a primary effect on the microscopic morphology of ash here. The reduction
rate of ash during heating process is obviously increased when the temperature is above 1200 oC, while it begins to
diminish near the deformation temperature. In addition, oxy-fuel atmosphere also shows a certain influence on the
ash volatility of high-alkali coal.

Acknowledgements

The authors acknowledge financial supports from the National Natural Science Foundation of China (51506163)
and the National Key Technology Research and Development Program of China (2015BAA04B02).

References

[1] Mathews JP, Krishnamoorthy V, Louw E, Tchapda AHN, Castro-Marcano F, Karri V, Alexis DA, Mitchell GD. A review of the correlations
of coal properties with elemental composition. Fuel Process Technol 2014; 121:104-113.
[2] Mathews JP, Miller BG, Song CS, Schobert HH, Botha F, Finkleman RB. The EBB and flow of US coal research 1970-2010 with a focus on
academic institutions. Fuel 2013;105:1-12.
[3] Li G, Wang C, Yan Y, Jin X, Liu Y, Che D. Release and transformation of sodium during combustion of Zhundong coals. J Energy Inst 2016;
89(1):48-56.
[4] Wang C, Jin X, Wang Y, Yan Y, Cui J, Liu Y, Che D. Release and transformation of sodium during pyrolysis of Zhundong coals. Energy
Fuels 2015; 29(1):78-85.
[5] Yao YX, Jin J, Liu DY, Wang YZ, Kou XS, Lin YY. Evaluation of vermiculite in reducing ash deposition during the combustion of high-
calcium and high-sodium Zhundong coal in a drop-tube furnace. Energy Fuels 2016;30(4):3488-3494.
[6] Song GL, Song WJ, Qi XB, Lu QG. Transformation characteristics of sodium of Zhundong coal combustion/gasification in circulating
fluidized bed. Energy Fuels 2016; 30(4):3473-3478.
[7] Wang C, Han T, Du Y, Liu Y, Che D. Diffusional effects on differences of coal char reactivity between air and oxy-fuel combustion in TGA
experiments. J Therm Anal Calorim 2016; 125(2): 897-904.
[8] Wang C, Du Y, Che D. Reactivities of coals and synthetic model coal under oxy-fuel conditions. Thermochim Acta 2013; 553:8-15.
[9] Stanger R, Wall T, Spoerl R, Paneru M, Grathwohl S, Weidmann M, Schefflmecht G, McDonald D, Myohanen K, Ritvanen J, Rahiala S,
Hyppanen T, Mletzko J, Kather A, Santos S. Oxyfuel combustion for CO2 capture in power plants. Int J Greenhouse Gas Control 2015;
40:55-125.
[10] Chen L, Yong SZ, Ghoniem AF. Oxy-fuel combustion of pulverized coal: Characterization, fundamentals, stabilization and CFD modeling.
Prog Energy Combust Sci 2012; 38(2):156-214.