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Effect of Na2O in Ash Composition on Petroleum Coke Ash Fusibility Jiazhou Li, Jiansheng Zhang, Jiantao Zhao, and Yitian Fang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b02317 • Publication Date (Web): 30 Aug 2019 Downloaded from pubs.acs.org on August 30, 2019
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Energy & Fuels
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Effect of Na2O in Ash Composition on Petroleum Coke Ash Fusibility
2
Jiazhou Li,a, Jiansheng Zhang,*, a Jiantao Zhao,b Yitian Fangb
3
a
4 5 6
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084, China
b
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China
7
ABSTRACT: Petroleum coke (petcoke) ash fusibility is closely related to the ash-
8
related fouling and slagging, which have significant effects on the clean and efficient
9
utilization of petcoke. Sodium (Na) element in petcoke ash is considered as an
10
inducement for ash fouling and slagging. In this paper, we investigate the effect of Na2O
11
on the petcoke ash fusibility from the perspectives of atmosphere, Na2O content, and
12
temperature. The crystalline minerals and surface morphologies of high-temperature
13
ashes were determined by X-ray diffraction (XRD) and scanning electronic microscopy
14
(SEM), respectively. Thermodynamic software FactSage was applied to calculate the
15
ash melting process. The results show that ash fusion temperature (AFT) of petcoke ash
16
exhibits the continuous decline with the addition of Na2O at both oxidizing and
17
reducing atmospheres, which is ascribed to the mineral transformation behaviors of
18
high-temperature ashes. Under oxidizing atmosphere, the low-melting Na-bearing
19
albite (NaAlSi3O8) formed at high-temperature ash with the addition of Na2O decreases
20
the AFT, and the decomposition of high-melting anorthite (CaAl2Si2O8) and quartz
21
(SiO2) further leads to the decline of AFT. Under reducing atmosphere, another low-
22
melting Na-bearing nepheline (NaAlSiO4) is found in high-temperature ash. Moreover,
23
mullite and anorthite disappear with Na2O content increasing, which can both
24
contribute to the progressive decline of AFT. The high-temperature ash samples with 1
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high Na2O content have higher melting extent at oxidizing and reducing atmospheres.
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These ash particles present more smooth surface and denser layer structure.
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1. INTRODUCTION
28
With industrialization process of the world, the demands for crude oil and oil-
29
related products increase continuously. Petcoke, as a primarily waste by-product
30
produced during crude bitumen or heavy oil refining, its production is steadily
31
expanding [1-3]. The advantages of high carbon content, high heat value, low ash
32
content, and abundant availability make petcoke a very attractive raw material.
33
Although petcoke has a remarkably low level of ash, it plays an important role in the
34
process of thermal conversion. The ash behaviors at high temperatures can cause many
35
key issues in boilers and gasifiers such as fouling, slagging, and deposition. Ash fouling
36
and deposition lower not only the efficiency of heat exchangers but also the lifetime of
37
equipments [4,5]. Furthermore, ash fusion behaviors impact the continuous slag tapping
38
process [6]. Therefore, it is imperative to deeply understand the ash fusion behaviors.
39
Many experimental methods such as ash fusion temperature test, sintering strength test,
40
thermomechanical analysis (TMA), and high-temperature processing microscope
41
(HTPM) have been developed to investigate the ash fusibility [7-11]. Ash fusion
42
temperature defined by the certain shape of an ash cone is most widely used to evaluate
43
the ash fusion behaviors. AFT gives an indication of ash softening and melting
44
behaviors. Moreover, it also provides an information of the progressive melting of ash
45
to slag [12].
46
The ash fusibility has been correlated with the ash chemical composition and
47
mineral transformations. van Dyk [13] found that the acidic components SiO2, Al2O3,
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TiO2, as well as the SiO2-Al2O3 ratio all have a significantly increasing effect on the
49
coal ash flow temperature. Liu et al. [14] studied the influences of ash composition CaO, 2
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Fe2O3, K2O, and SiO2/Al2O3 (S/A) ratio on coal ash fusion temperature. It was found
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that AFT decreased with increasing Fe2O3 content and S/A ratio, but showed no
52
significant change as K2O content varied. For the effect of CaO, AFT reached a
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minimum value and then followed an increase. Vassilev et al. [15] pointed out that the
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addition of SiO2, Al2O3, and TiO2 increased the AFT, whereas CaO, MgO, and Fe2O3
55
resulted in the decline of AFT. van Dyk [16] studied the variation of AFT via three-
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component Al2O3-Na2O-SiO2 system. The liquid temperature dropped from above 1500
57
oC
58
indicated that AFT initially decrease to a minimum value and then began to increase
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with the addition of CaO, Fe2O3, and MgO. Besides, AFT increases with S/A ratio
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increasing. Chen et al. [18] found that Na2O had a positive effect on the decrease of
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AFT because of the formation of fusible Na-bearing aluminosilicates. These researches
62
mentioned above are focused on the relationships between ash fusion temperature and
63
coal ash chemical composition.
to 1200 oC when the Na2O content increased from 0.5 to 10%. Song et al. [17]
64
The ash chemistry of petcoke indicates that the ash composition resembles coal
65
except for the presence of V and Ni whose concentrations, in some case, account for
66
above 20 wt.% and 10 wt.% respectively [19]. These differences between petcoke ash
67
and coal ash may lead to the different and unpredictable behaviors of mineral in ash at
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high temperatures [20]. The effects of ash composition V2O5, NiO, Fe2O3, CaO, and
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S/A and (SiO2+Al2O3) ratios have been investigated in many works [21-25]. However,
70
the influence of Na2O in petcoke ash components has not drawn enough attention. Na
71
is considered as one of the most concerned elements because it can cause ash-related
72
corrosion and fouling problems of boilers firing petcoke. The condensation of Na2SO4
73
decreases the melting temperature of solution by forming vanadates [26]. Thus, this
74
work mainly investigates the effect of Na2O on petcoke ash fusibility under different 3
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atmospheres. In general, the AFT obtained at oxidizing (air) and reducing (CO/CO2
76
volume ratio=6/4) atmospheres is considered to be valuable guides for the ash slagging
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of combustion and gasification, respectively [27].
78
Many researchers have attempted to simplify the ash system by using synthetic
79
ash rather than real ash because of the presence of complex phases and impurities in
80
ash [14,28-31]. The property of synthetic ash at high temperatures might resemble that
81
of real ash [28]. Therefore, the synthetic ash composed of primary oxides SiO2, Al2O3,
82
V2O5, CaO, Fe2O3, NiO, and Na2O is selected as the experimental samples in this work.
83
The four characteristic temperatures including initial deformational temperature (DT),
84
softening temperature (ST), hemispherical temperature (HT), and flow temperature (FT)
85
are measured by automatic analyzing system. The mineral composition and
86
microstructure of high-temperature ash samples are identified by XRD and SEM.
87
Moreover, thermodynamic software package FactSage is applied to analyze the
88
potential multiphase equilibria during the ash melting process.
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2. EXPERIMENTAL SECTION
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2.1. Synthetic Ash Samples.
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Five petcoke samples (Shanxi local oil refinery, Wuhan Petrochemical Co.,
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Zhenhai Petrochemical Co., Zibo Qilu Petrochemical Co., Ltd., and Daqing Oilfield)
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were ashed at 700 oC for 24 h [32]. The chemical composition of five petcoke ashes is
94
listed in Table 1. Based on these ash compositions, synthetic ash samples were prepared
95
by V2O5, NiO, SiO2, Al2O3, Fe2O3, CaO, and Na2O. These seven constituents account
96
for more than 95 wt.% of petcoke ash. The Na2O content ranges from 0 to 9.0 wt.%.
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Note that, Na2CO3 was selected in synthetic ash rather than Na2O because Na2CO3 was
98
more thermodynamically stable. Also, it should decompose into Na2O and CO2 at high 4
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temperature [33]. Seven analytical reagents were blended evenly by ball milling for 1
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h. The chemical composition of synthetic ash samples is shown in Table 2.
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2.2. AFT Test.
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The AFT of synthetic ash samples was measured by an AFT automatic analyzer
103
from KY Company, China following the Chinese standard procedure GB/T219-2008
104
[34]. The measurements were performed under an oxidizing (air) atmosphere and a
105
reducing (CO/CO2 volume ratio=6/4) atmospheres, which were widely used as the
106
guides for ash slagging of combustion and gasification, respectively [27]. The ash cones
107
were heated initially to 900 °C at 15 °C/min and then decreased to 5 °C/min. The four
108
characteristic temperatures were identified and recorded automatically in the heating
109
process.
110
2.3. Quenching Experiments.
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The quenched high-temperature ashes were prepared in a horizontal electronic
112
furnace with the maximum temperature of 1600 oC. Figure 1 shows the schematic
113
diagram of furnace apparatus. About 1.0 g synthetic ash was filled in corundum crucible
114
and then heated to the target temperature under oxidizing and reducing atmospheres.
115
The thermal profile is set according to the AFT test. When the sample reached the
116
scheduled temperature and then kept for 15 min, it was quickly taken out and quenched
117
in ice-water.
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2.4. Characterization and Testing.
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The petcoke ash chemical composition was analyzed by X-ray fluorescence (XRF)
120
spectrometry (XRF-1800, Shimadzu, Japan) with a Rh target X-ray tube (50 kV, 40
121
mA). The X-ray power diffractometer (RIGAKU D/max-rB) with Cu Ka radiation (40
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kW, 100 mA, Ka1=0.15408 mm) was used to identify the mineral components of
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quenched ash. The ash sample was scanned over the 2θ range of 10°-80° with a step 5
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size of 0.01° at 4° 2θ/min scanning speed. In addition, the surface morphologies of
125
minerals and the microanalysis of ash particle were observed by JSM-7001F scanning
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electron microscope.
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2.5. Thermodynamic Equilibrium Calculations
128
Thermodynamic software FactSage 6.4 based on the Gibbs free energy
129
minimization can be used to analyze multiphase equilibria, proportions of liquid and
130
solid phases, and phase transitions under specified atmospheres and temperatures
131
conditions. In this work, the multiple components system of SiO2-Al2O3-V2O5-CaO-
132
Fe2O3-NiO-Na2O was established in Equilib to calculate the mineral transformations of
133
ashes with different Na2O content at high temperatures. FToxid and FactPS database
134
were selected for the possibly formed solution species. The calculations were
135
performed under 0.1 MPa at oxidizing (air) and reducing (CO/CO2 volume ratio=6/4)
136
atmospheres, respectively. According to the theory of Gibbs free energy, all
137
homogeneous and heterogeneous reactions with negative Gibbs energy may occur.
138
Moreover, the lower Gibbs free energy indicates that the reaction has the higher priority
139
[35].
140
3. RESULTS AND DISCUSSION
141
3.1. Effect of Na on Ash Fusibility.
142
The experimental AFT of synthetic ash samples with different Na2O content under
143
oxidizing atmosphere is given in Figure 2a. It can be seen that AFT shows a staged
144
decline with the addition of Na2O. It decreases sharply as the Na2O content increases
145
up to 1.5 wt.%, which indicates that the formation of low-melting fluxing minerals
146
occurs under oxidizing atmosphere. AFT drops slightly in the Na2O content range of
147
1.5-7.0 wt.%, while it follows a rapid decrease with the Na2O content further increasing. 6
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Figure 2b shows the AFT of synthetic ash samples with different Na2O content
149
under reducing atmosphere. The ash without Na2O has a higher AFT compared to that
150
at oxidizing atmosphere. The reasonable explanation may be as follows: the high-
151
melting V2O3 (1940 oC) is the stable form of V at reducing atmosphere, which plays a
152
key role for the high AFT. However, V is present mainly as the low-melting V2O5 (690
153
oC)
154
almost unchanged. With the Na2O content further increasing, it follows a continuous
155
and impressive decline, of which DT decreases from 1430 oC (Na2O content is 1.0 wt.%)
156
to 1185 oC (Na2O content is 9.0 wt.%). Apparently, the low-melting minerals and
157
eutectics are formed under an appropriate Na2O content at high temperatures, which
158
leads to the decline of AFT.
159
3.2. Effect of Na on Mineral Transformations at Oxidizing Atmosphere.
at oxidizing atmosphere. When the Na2O content is less than 1.0 wt.%, AFT keeps
160
The interactions among minerals in high-temperature ash can influence the
161
mineral composition, and then change the variation trend of AFT. Therefore, the
162
mineral components of high-temperature ash were identified by XRD to investigate the
163
variation mechanism of AFT. Figure 3 shows the XRD patterns of synthetic ashes with
164
varying Na2O content at different temperatures under an oxidizing atmosphere.
165
According to the variation trend of AFT (Figure 2a), the heating temperature of ash
166
with 0.5 wt.% Na2O is between 1000 and 1300 oC, and that of ash with 1.5, 3.0 and 9.0
167
wt.% Na2O is from 1000 to 1200 oC. When Na2O content is 0.5 wt.%, as shown in
168
Figure 3a, the major crystalline minerals are anorthite (CaAl2Si2O8), calcium
169
pyrovanadate (Ca2V2O7), quartz (SiO2), and spinel (NiAl2O4) at 1000 oC. These
170
minerals keep thermodynamically stable until the temperature reaches up to 1300 oC,
171
where the diffraction peaks of calcium pyrovanadate disappear due to its relatively low
172
melting point of 1288 oC. A small amount of Na may form amorphous minerals at high 7
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temperatures. Both anorthite and spinel have high melting point (>1500 oC), but the
174
molten V2O5 and calcium pyrovanadate may decrease the AFT effectively.
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When Na2O content is 1.5 wt.% (Fig. 3b), the diffraction peaks of anorthite,
176
calcium pyrovanadate, quartz, and spinel are found in XRD patterns at 1000 oC. Also,
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the formation of Na-bearing species albite (NaAlSi3O8) occurs in ash. However, albite
178
melts at 1200 oC because of its low melting point of 1118 oC, which may be responsible
179
for the decline of AFT, as shown in Figure 2a. Other four crystalline minerals anorthite,
180
calcium pyrovanadate, quartz, and spinel are stable in the temperature range of 1000
181
oC-1200 oC.
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mineral phases of ash with 3.0 wt.% Na2O basically resemble those of ash with 1.5
183
wt.% Na2O. The existing difference between two ashes is that the diffraction peaks of
184
quartz are not found in ash with 3.0 wt.% Na2O. The formation of anorthite and albite
185
may contribute to the disappearance of quartz following the reactions:
As Na2O content increases to 3.0 wt.% (Fig. 3c), it can be seen that the
186
CaO+Al2 O3 +2SiO 2 =CaAl2Si 2 O8
(1)
187
Na 2 O+Al2 O3 +6SiO 2 =2NaAlSi3O8
(2)
188
When Na2O content is 9.0 wt.% (Figure 3d), calcium pyrovanadate, spinel, and albite
189
are the main crystalline minerals between 1000 and 1100 oC. The diffraction peaks of
190
albite disappear at 1200 oC. Both quartz and anorthite are not generated within the
191
whole ash melting process, which may be ascribed to the following reaction [29]:
192
Na 2 O+CaAl2Si 2 O8 +4SiO 2 =2NaAlSi3O8 CaO
(3)
193
This reaction consumes a large amount of high-melting anorthite and quartz. In contrast,
194
the content of low-melting albite increases to some extent with increasing Na2O content.
195
All these can lead to the further decrease of AFT.
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In order to verify the crystalline minerals formed in high-temperature ash slag, the
197
phase assemblage of synthetic ashes with varying Na2O content at different
198
temperatures is calculated by thermodynamic equilibrium calculations FactSage, as
199
shown in Figure 4. When Na2O content is 0.5 wt.%, the minerals spinel, calcium
200
pyrovanadate, quartz, calcium metavanadate, anorthite, and albite are predicted to form
201
at low temperature (1200 oC),
202
calcium metavanadate, anorthite, and albite begin to disappear. The predicted minerals
203
in ash slag include spinel, calcium pyrovanadate, quartz, and vanadium dioxide.
204
However, according to the XRD patterns, the formations of calcium metavanadate and
205
vanadium dioxide do not occur between 1000 and 1300 oC. As Na2O content increases
206
from 0.5 to 9.0 wt.% in phase assemblage, the content of low-melting albite and calcium
207
pyrovanadate increases progressively, while that of high-melting quartz and spinel
208
declines accordingly, which may contribute to the decrease of AFT (Fig. 2a).
209
3.3. Effect of Na on Mineral Transformations at Reducing Atmosphere.
210
The XRD patterns of four synthetic ash samples (Na2O content is 0.5, 1.5, 3.0, and
211
7.0 wt.%, respectively) heated from 1200 to 1500 oC in a reducing atmosphere are
212
shown in Figure 5. When Na2O content is 0.5 wt.% (Fig. 5a), the high-melting minerals
213
mullite (1850 oC) and vanadium trioxide (1940 oC) are formed, and can keep
214
thermodynamically stable within the whole ash melting process. Also, the diffraction
215
peaks of anorthite and quartz appear at 1200 oC until the temperature reaches up to 1500
216
oC,
217
coulsonite (FeV2O4) is found between 1200 and 1300 oC. In comparison to the
218
crystalline minerals of ash with 0.5 wt.% Na2O obtained under an oxidizing atmosphere
219
(Fig. 3a), Ni is present in the form of elemental nickel (Ni) under a reducing atmosphere
220
rather than spinel (NiAl2O4) between 1200 and 1300 oC. As Na2O content increases to
where both minerals are converted into amorphous. Another V-bearing species
9
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1.5 wt.% (Fig. 5b), the diffraction peaks of high-melting mullite do not appear from
222
1200 to 1500 oC, which may be ascribed to the formation of albite (Eq. 2). Albite may
223
transform into amorphous since its melting point is 1118 oC. The formations of
224
anorthite, quartz, coulsonite, vanadium trioxide, and nickel occur between 1200 and
225
1300 oC. The diffraction peaks of coulsonite and nickel disappear at 1400 oC. With
226
temperature further increasing to 1500 oC, vanadium trioxide is the only crystalline
227
mineral. No Na-bearing crystalline species are formed from 1200 to 1500 oC.
228
When Na2O content is 3.0 wt.% (Fig. 5c), another Na-bearing species nepheline
229
(NaAlSiO4) is formed at 1200 oC in comparison to the crystalline minerals of ash with
230
1.5 wt.% Na2O content (Fig. 5b). The formation of nepheline may follow the reactions
231
[27]:
232 233
Na 2 O+Al2 O3 +2SiO 2 =2NaAlSiO 4 NaAlSi3O8 +CaAl2Si 2 O8 +Na 2 O=3NaAlSiO 4 CaO+2SiO 2
(4) (5)
234
Nepheline disappears at 1300 oC due to its low melting point of 1254 °C. Also, it is
235
found that the diffraction peaks of quartz do not appear in XRD patterns. Apparently,
236
the formation of low-melting nepheline and the disappearance of high-melting quartz
237
can lead to the decrease of AFT. With Na2O content increasing to 7.0 wt.% (Figure 5d),
238
another high-melting mineral anorthite does not form in high temperature ash slag,
239
which may effectively verify the Eq. 5. The content of nepheline increases with the
240
addition of Na2O, all of which further decrease the AFT, as shown in Figure 2b.
241
Figure 6 shows the phase assemblage of synthetic ashes with different Na2O
242
content at reducing atmosphere. When Na2O content is 0.5 wt.%, albite, wollastonite,
243
coulsonite, anorthite, nickel, and vanadium trioxide are the dominant minerals at high
244
temperatures, which are basically consistent with the crystalline minerals in XRD 10
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patterns. As Na2O content increases to 1.5 wt.%, albite is converted into nepheline.
246
With Na2O content further increasing, the content of low-melting nepheline increases
247
gradually, while that of high-melting anorthite, coulsonite, and vanadium trioxide
248
declines progressively. Anorthite disappears when Na2O content is 7.0 wt.%. All the
249
minerals transformations mentioned above can validate the variation trend of AFT (Fig.
250
2b).
251
3.4. Effect of Na on Surface Morphologies of High Temperature Ash Samples.
252
In addition to mineral transformations, the variations in surface morphologies of
253
high-temperature ash also reflect the ash fusibility [36,37]. The quenched ash is
254
considered to keep the morphology of high-temperature ash well and prevent the crystal
255
segregation [27]. Figure 7 shows the SEM photomicrographs of synthetic ashes with
256
different Na2O content, which were quenched in ice water from 1200 oC at oxidizing
257
atmosphere (Fig. 7a) and 1400 oC at reducing atmosphere (Fig. 7b), respectively. All
258
the high-temperature ashes are magnified 3700 times. It is well known that the high
259
melted ash particles have the smooth surface and dense layer structure [14]. When the
260
addition of Na2O is 0.5 wt.%, the high-temperature ash samples consist of irregular and
261
fine particles at both oxidizing and reducing atmospheres. These particles have rough
262
surface and loose structure. With the addition proportion increasing to 3.0 wt.%, it is
263
found that some fine particles have been agglomerating into large particles. When Na2O
264
content reaches to 9.0 wt.% (Fig. 7a) and 7.0 wt.% (Fig. 7b), respectively, the ash
265
particles have been further agglomerated and have molten surface. Moreover, some
266
protuberances are formed on the molten surface. The ashes have more smooth surface
267
and denser layer structure. Therefore, it is concluded that the ash with high Na2O
268
content has the high melted extent at both oxidizing and reducing atmospheres, which
269
is consistent with the variations of AFT (Fig. 2). 11
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4. CONCLUSIONS
271
The effect of Na2O on petcoke ash fusion characteristics was investigated in this
272
work from different perspectives including atmosphere change, Na2O content variation,
273
and temperature rising. The main conclusions could be summarized as follows.
274
(1) The AFT of petcoke ash samples is closely related to the addition of Na2O
275
content. AFT shows continuous decline with increasing Na2O content at both oxidizing
276
and reducing atmospheres.
277
(2) The mineral transformations during ash fusion process contribute to the
278
variations of AFT. With Na2O content increasing, the formations of low-melting albite
279
at oxidizing atmosphere and nepheline at reducing atmosphere decrease the AFT
280
markedly. Moreover, the decomposition of high-melting anorthite and quartz further
281
leads to the decline of AFT.
282
(3) Under oxidizing and reducing atmospheres, the high-temperature ash samples
283
with high Na2O content have higher melting extent. These ash particles present more
284
smooth surface and denser layer structure.
285
AUTHOR INFORMATION
286
Corresponding Author
287
E-mail address:
[email protected] 288
ACKNOWLEDGEMENTS
289
The authors gratefully acknowledge the financial support of the National Key
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Research and Development Project (No. 2017YFB0602602).
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Energy & Fuels
Table 1. Ash Composition of Five Real Petcoke (wt.%) Petcoke
V2O5
NiO
SiO2
Al2O3
Fe2O3 CaO
MgO
TiO2
SO3
K2O
Na2O
P2O5
Shanxi
33.89 7.55
13.92 1.18
0.83
0.75
0.76
1.74
0.54
Shengli
33.89 10.92 16.11 8.84
5.92
15.92 3.03
0.85
0.75
0.76
3.20
0.55
Zhenhai
29.82 12.37 25.44 7.60
10.12 8.79
1.21
0.35
1.35
0.96
0.98
0.32
Daqing
32.35 9.75
17.74 7.04
5.35
21.35 0.74
0.64
0.97
1.35
1.05
0.61
Yangzi
27.32 11.87 21.32 9.72
9.43
8.84
0.46
0.98
0.83
5.75
0.46
20.20 10.54 7.40
1.53
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Table 2 Chemical Composition of Synthetic Ash Samples composition (wt.%) sample
SiO2
Al2O3
V2O5
CaO
Fe2O3
NiO
Na2O
1
22.60
11.30
34.00
13.10
8.00
11.00
0.00
2
22.54
11.27
33.80
13.02
7.95
10.92
0.50
3
22.48
11.24
33.60
12.94
7.90
10.84
1.00
4
22.40
11.20
33.45
12.85
7.84
10.76
1.50
5
22.30
11.15
33.30
12.78
7.78
10.69
2.00
6
22.00
11.00
33.00
12.69
7.71
10.60
3.00
7
21.50
10.75
32.20
12.49
7.61
10.45
5.00
8
21.00
10.50
31.40
12.31
7.51
10.28
7.00
9
20.40
10.20
30.70
12.15
7.43
10.12
9.00
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Figure 1. The schematic representation of the furnace apparatus.
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Figure 2. Effect of Na2O content on AFTs at different atmospheres (a) air; (b) CO/CO2 volume ratio=6/4.
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Energy & Fuels
Figure 3. XRD patterns of synthetic ashes with different Na2O content at oxidizing atmosphere (a) 0.5 wt.% Na2O; (b) 1.5 wt.% Na2O; (c) 3.0 wt.% Na2O; (d) 9.0 wt.% Na2O
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Figure 4. FactSage calculation of synthetic ashes with different Na2O content at oxidizing atmosphere (a) 0.5 wt.% Na2O; (b) 1.5 wt.% Na2O; (c) 3.0 wt.% Na2O; (d) 9.0 wt.% Na2O
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Energy & Fuels
389
390
Figure 5. XRD patterns of synthetic ashes with different Na2O content at reducing atmosphere (a) 0.5 wt.% Na2O; (b) 1.5 wt.% Na2O; (c) 3.0 wt.% Na2O; (d) 7.0 wt.% Na2O
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Figure 6. FactSage calculation of synthetic ashes with different Na2O content at reducing atmosphere (a) 0.5 wt.% Na2O; (b) 1.5 wt.% Na2O; (c) 3.0 wt.% Na2O; (d) 7.0 wt.% Na2O
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Energy & Fuels
0.5 wt.% Na2O
0.5 wt.% Na2O
3.0 wt.% Na2O
3.0 wt.% Na2O
9.0 wt.% Na2O
7.0 wt.% Na2O
(a)
(b)
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Figure 7. SEM photomicrographs of synthetic ashes with different Na2O content (a) 1200 oC at oxidizing atmosphere; (b) 1400 °C at reducing atmosphere
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