materials
Article
A New Process of Direct Zinc Oxide Production by
Carbothermal Reduction of Zinc Ash
Jianjun Gao 1,2 , Hong Wang 3,4 , Jie Wang 3 , Yingyi Zhang 3, * , Feng Wang 1,2 , Shuang Yang 3 and Shinan Li 3
Citation: Gao, J.; Wang, H.; Wang, J.;
Zhang, Y.; Wang, F.; Yang, S.; Li, S.
A New Process of Direct Zinc Oxide
Production by Carbothermal
Reduction of Zinc Ash. Materials
2022, 15, 5246. https://doi.org/
10.3390/ma15155246
Academic Editor: Dinesh Agrawal
Received: 6 July 2022
Accepted: 27 July 2022
Published: 29 July 2022
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4.0/).
Materials 2022, 15, 5246. https://doi.org/10.3390/ma15155246
1 Research and Development Department, Gangyan Shenghua Engineering & Research Co., Ltd.,
Beijing 100081, China; gaojianjun2085@163.com (J.G.); flywise@126.com (F.W.)
2 State Key Laboratory for Advanced Iron and Steel Processes and Products,
Central Iron and Steel Research Institute, Beijing 100081, China
3 School of Metallurgical Engineering, Anhui University of Technology, Maanshan 243002, China;
wanghong0531@126.com (H.W.); mrwang0101@ahut.edu.cn (J.W.); yangshuang20031003@163.com (S.Y.);
lishinan031103@163.com (S.L.)
4 Beijing Metallurgical Equipment Research Design Institute Co., Ltd., Beijing 100029, China
* Correspondence: zhangyingyi@ahut.edu.cn; Tel.: +86-173-7507-6451
Abstract: Zinc ash is a by-product of the hot-dip galvanizing process and the electrolytic zinc
process, which is classified as a hazardous waste consisting predominately of zinc oxide that could
be recovered as the useful main resource for ZnO preparation. In this work, in order to reduce
the energy consumption of the direct reduction process and improve the resource-recovery rate.
A new technology for zinc oxide production, by a carbothermal reduction of zinc ash, is proposed.
This process includes two steps: high-temperature roasting of zinc ash for dechlorination and
a carbothermal reduction of dechlorination ash. Zn in zinc ash is mainly presented in the form of
zinc oxide (ZnO), basic zinc chloride (Zn5 (OH)8 Cl2 H2 O), and metallic zinc (Zn). Basic zinc chloride
can be roasted and decomposed to reduce the chlorine content in zinc ash. The results of a chloride
ion removal test show that the optimal roasting temperature is 1000 ◦ C, with a holding time of
60 min. Under the modified conditions, the chloride content in the roasted zinc ash is reduced to
0.021 wt.%, and the dechlorination rate is more than 99.5%, which can meet the requirements of zinc
oxide production. The best process conditions for zinc oxide production by carbothermic reduction
are as follows: reduction temperature of 1250 ◦ C, reduction time of 60 min, and reduction agent
addition of 22 wt.%. Under the best reduction process, the purity of zinc oxide product is 99.5%, and
the recovery of zinc is more than 99.25%. Needle-like zinc oxide obtained by carbothermic reduction
has high purity and can replace zinc oxide produced by an indirect process.
Keywords: zinc ash; carbon-bearing pellet; roasting dechlorination; direct reduction; zinc oxide
1. Introduction
Zinc oxide as one of important basic raw chemicals, which is widely used in rubber,
paints, ceramics, and other chemical industries [1–9]. In China, the consumption of zinc
oxide is 0.3~0.5 million tons per year, accounting for 5%~10% of the total amount of
zinc [10,11]. The preparation of ZnO can be divided into the direct process, indirect process,
and wet-chemical method (active zinc oxide). As raw material in the indirect process, metal
zinc ingot or zinc slag is converted into zinc vapor in a graphite crucible at high temperature
and then oxidized by pumped air. The obtained zinc oxide particles are transported via
a cooling duct and collected, with a purity of 99.7%. The direct process involves the
reduction of zinc ash or zinc oxide ore (raw material) by heating with coal in an open-
hearth furnace, followed by the oxidation of zinc vapor and the bag collection of ZnO with
a purity of 95%~99% [12]. For the wet-chemical method (active zinc oxide), secondary zinc
oxide or zinc containing dust ash is used as a raw material to be leached out by ammonium
bicarbonate and ammonia, to dissolve zinc oxide to form zinc-ammonium complex; then,
https://www.mdpi.com/journal/materials
Materials 2022, 15, 5246 2 of 10

the solution is purified and roasted to obtain the active zinc oxide with a purity of about
95%. Since hydrometallurgy will produce a large amount of wastewater containing heavy
metal ions, pyrometallurgy is widely used to recover zinc oxide in China.
At present, an open-hearth furnace (OHF, also called a W-Zinc-Oxygen-Furnace)
is used to recover zinc oxide from electric furnace ash. This smelting equipment has
the following advantages: simple equipment, low investment, short construction period,
and convenient operation. However, the traditional process has a long smelting cycle,
intermittent operation, high fuel consumption, low energy efficiency, and serious pollution,
which seriously restrict its popularization and application. Therefore, it is urgent to develop
a new zinc oxide recovery technique [13–17]. In order to solve the above technical problems,
the Central Iron and Steel Research Institute proposed a new technology, of direct zinc oxide
production by carbothermal reduction. This technology has the following characteristics:
energy saving, environmental protection, high efficiency, and automation. Compared with
the conventional OHF, its specific coal consumption per ton of zinc oxide products could be
reduced by more than 50%, the zinc recovery rate increases by over 5%, and the ZnO purity
is up to 99%. In this work, the effects of direct reduction temperature, time, and reductant
content on reduction rate of zinc oxide were analyzed and discussed. In addition, the phase
composition and microstructure of zinc oxide products recovered by direct reduction were
also investigated.

2. Experimental
2.1. Materials
The experimental raw material is zinc dust produced by hot-dip galvanizing, and
the chemical composition of zinc ash is shown in Table 1. It can be seen that the contents
of ZnO, Cl, and SiO2 are 87.91 wt.%, 4.44 wt.%, and 1.27 wt.%, respectively, while the
contents of other impurities are low. It is worth noting that volatile Cl elements should be
removed, otherwise, Cl will enter ZnO products in the form of ZnCl2 , affecting the product
quality. Figure 1 shows the XRD pattern of zinc ash. It can be seen that zinc ash is mainly
composed of Zn (Ref. code 01-087-0713) and ZnO (Ref. Code 01-089-0511), with a small
amount of Zn5 (OH)8 Cl2 H2 O (Ref. Code 01-077-2311). The Zn5 (OH)8 Cl2 H2 O is formed by
the combination of Cl with zinc oxide and trace metal zinc. TG-DSC analysis of zinc ash
(Figure 2) indicates that during the temperature-rising period, considerable mass loss of
zinc ash occurs twice, with the first at about 130 ◦ C and the second at about 500 ◦ C. The
total mass loss reaches 6.34%, as the temperature rises up to 1300 ◦ C. Anthracite is used as
the reducing agent, with a size of under 74 µm. As listed in Table 2, the fixed carton of
Materials 2022, 15, x FOR PEER REVIEW coal
3 of 11
powder is 78.73%, and the ash and volatile content are 10.16% and 8.55%, respectively. In
addition, small amounts of S (0.28%) and P (0.023%) are also detected in anthracite.
3500
1
3 1-ZnO
3000
2-Zn5(OH)8Cl12H2O
2500 3-Zn

1 1
Intensity

2000

1500

1000 11 1
1
1
500 22 3 1
2 2 22 2 2 2 2
3 2
0
20 30 40 50 60 70 80 90

Position(°2Theta)

Figure
Figure 1.
1. XRD
XRD pattern
pattern of
of zinc
zinc ash.
ash.

120 1.0

115 0.5

110 0.0

-0.5
·mg-1)

105
ss/%

-1.0
100
-3.66% -1.5
 5 8 12 2

2500 3-Zn

1 1

Intensity
2000

1500
Materials 2022, 15, 5246 3 of 10
1000 11 1
1
1
500 22 3 1
2 2 22 2 2 2
2of zinc
Table 1. Chemical composition
3 ash, wt.%.
2
0
20 30 40 50 60 70 80 90
Component ZnO Cl Fe2 O3 SiO2 CaO MgO Al2 O3
Position(°2Theta)
Content 87.91 4.44 0.26 1.27 0.49 0.23 0.50
Figure 1. XRD pattern of zinc ash.

120 1.0

115 0.5

110 0.0

-0.5

DSC/(mW·mg-1)
105
Mass loss/%

-1.0
100
-3.66% -1.5
95
-2.0
Quality change -6.34%
90
-2.5
85 -3.0
80 -3.5

75 -4.0
0 200 400 600 800 1000 1200
Temperature/℃

Figure2.2.TG-DSC
Figure TG-DSCanalysis
analysisof
ofzinc
zincash.
ash.

Table2.2.Chemical
Table Chemicalcomposition
compositionofofpowder
powdercoal,
coal,wt.%.
wt.%.

Component
Component C C Ash Ash Volatiles
Volatiles S S PP H22O
H O
Content
Content 78.73 78.73 10.16 10.16 8.55 8.55 0.28 0.28 0.023
0.023 2.56
2.56

2.2. Thermodynamic Basis for Reduction

2.2. Thermodynamic Basis for Reduction
Znisismainly
Zn mainlypresented
presentedininthe
theforms
formsofofZnO,
ZnO,Zn
Zn(OH)
5(OH)8Cl2H2O, and metallic Zn. Due
5 8 Cl2 H2 O, and metallic Zn. Due
to a certain Zn 5(OH)8Cl2H2O in zinc ash, Cl needs to be removed by high-temperature
to a certain Zn5 (OH)8 Cl2 H2 O in zinc ash, Cl needs to be removed by high-temperature
roastingwith
roasting withthe
thefollowing
followingchemical
chemicalreactions.
reactions.
Zn5(OH)8Cl2H2O = 4Zn(OH)2 + ZnCl2 + H2O(g) (1)
Zn5 (OH)8 Cl2 H2 O = 4Zn(OH)2 + ZnCl2 + H2 O(g) (1)
Zn(OH)2 = ZnO + H2O(g) (2)
Zn(OH)2 = ZnO + H2 O(g) (2)
ZnCl 2 =2 ZnCl
ZnCl = ZnCl
2(g)2(g) (3)
(3)
As
Asindicated
indicatedin inTG-DSC
TG-DSCanalysis
analysis(Figure
(Figure2),2),the
the first
first mass
mass loss
loss occurs
occurs in in Reactions
Reactions (1) (1)
and (2), where Zn (OH) Cl
and (2), where Zn5 5(OH)88Cl22H22 H O is decomposed to Zn(OH)
decomposed to Zn(OH)22, ZnCl22, , ZnCl , and H O, and, at
H22 and, at the the
same ◦ C.
same time,
time, Zn(OH)22 further
furtherbreaks
breaksintointoZnO
ZnOand and H2HO,2 O,
withwith 3.66%
3.66% mass mass
lossloss at 130
at 130 °C. The
The second
second massmass
lossloss happens
happens in Reaction
in Reaction (3)(3) because
because ofofthethe volatilizationofofZnCl
volatilization ZnCl , witha
2, 2with
aboiling
boilingpoint
pointatat732
732°C ◦ C in standard conditions. During the actual operation, ZnCl starts
in standard conditions. During the actual operation, ZnCl22 starts
to
to volatilize
volatilize at
at aa temperature
temperature less less than
than the
the boiling
boiling point,
point, due
due toto its
its lower
lower vapor
vapor partial
partial
pressure than that in the normal standard conditions, and, with the
pressure than that in the normal standard conditions, and, with the rising temperature, rising temperature,
ZnCl in the
ZnCl22 in thezinc
zincashashvapors
vaporsinto
into
thethe flue
flue gasgas to reduce
to reduce the the Cl content
Cl content in theinzinc
the ash.
zincAfter
ash.
After dechlorination, Zn in zinc ash is presented mainly in the form of ZnO. Zinc ash is
mixed with coal powder to prepare the carbon-containing pellets with reactions at high
temperatures, as follows:

ZnO + C = Zn(g) + CO(g) ∆Gθ = 363,841 − 297T (4)

Under standard conditions, the reduction between ZnO and carbon could be fulfilled
at above 1225 K, so the higher temperature is, the quicker the reaction. To speed up the
reaction and improve Zn recovery, direct reduction temperature could be increased. The
reduced zinc vapor goes, along with flue gas, into oxidation room and is oxidized into
ZnO by the blasted air. Since the oxidization of zinc vapor is exothermic reaction, the
Materials 2022, 15, 5246 4 of 10

temperature of flue gas in the oxidation room is intensely high, requiring special cooling
device to decrease the flue temperature so that bag collector could be adopted to gather
ZnO products.

2.3. Experimental Method

As shown in Figure 3, the zinc oxide was produced by carbothermic reduction in
an experimental silicon carbide heating furnace. The preparation process of zinc oxide
includes four steps: zinc ash direct reduction, zinc vapor oxidization, surface cooling of
ZnO flue gas, and bag collecting of ZnO products. To recover the immense amount of
oxidization heat caused by zinc vapor and reduced CO oxidization and cut down the
reduction energy consumption, the oxidation room is designed at the top of preheating area
of zinc ash pellets to utilize the oxidation heat for preheating the pellets through radiation.
The dechlorinated zinc ash is evenly mixed up with reduction agent at the presumed ratio,
ground to −74 µm. The industrial syrup (5% of the mixture weight) is used as a binder,
and then pressed into oval pellets with a size of 35 mm × 20 mm × 15 mm by briquetting
machine. After being dried in drying box for one hour under 150 ◦ C, the pellets are charged
into a refractory sagger trolley with the stacking height of 50 mm and slowly pushed into
the reduction furnace from the charging end. The pellets, after entering the reduction
area through preheating area, are heated for a certain period at the set temperature before
discharging. Under negative pressure, the reduced zinc vapor goes into oxidation room for
ZnO oxidization by the blasted air. The resulting zinc oxide flue gas is cooled by surface
cooler under 200 ◦ C, and then ZnO products are gathered by bag collector. By weighing
the reduced residue and ZnO product, analyzing Zn content to calculate the Zn-reduction
rate, and by investigating the effects of reduction temperature, reduction time, reduction
Materials 2022, 15, x FOR PEER REVIEW 5 of 11
dosing, and other factors in zinc recovery, the optimal process parameters for the direct
reduction of zinc ash to recover high-purity zinc oxide were finally determined.

Figure 3. Experimental installation diagram of carbon thermal reduction of zinc ash.

Figure 3. Experimental installation diagram of carbon thermal reduction of zinc ash.

3. Results
3. Results
3.1. Zinc Ash Dechlorination Experiment
The aim of zinc ash dechlorination is to remove Cl to obtain low-Cl zinc ash for the
production ofof high-grade
high-gradeZnO.
ZnO.According
According toto
thethe results
results fromfrom TG-DSC
TG-DSC analysis
analysis of zinc
of zinc ash,
ash, a roasting
a roasting chloride-removal
chloride-removal duration
duration of 60ismin
of 60 min is set.
set. The The influences
influences on zinc on
ashzinc ash
dechlo-
dechlorination by different roasting temperatures (600 ◦ C, 700 ◦ C, 800 ◦ C, 900 ◦ C, and
rination by different roasting temperatures (600 °C, 700 °C, 800 °C, 900 °C, and 1000 °C)
1000 ◦ C) are investigated, as shown in Figure 4. In addition, the corresponding XRD results
are investigated, as shown in Figure 4. In addition, the corresponding XRD results are
presented in Figure 5. It can be seen that no other impurities are observed in the zinc oxide
products obtained at different temperatures, which is due to the low content of chloride.

2.0
 3. Results
3.1. Zinc Ash Dechlorination Experiment
The aim of zinc ash dechlorination is to remove Cl to obtain low-Cl zinc ash for the
production of high-grade ZnO. According to the results from TG-DSC analysis of zinc ash,
Materials 2022, 15, 5246 5 of 10
a roasting chloride-removal duration of 60 min is set. The influences on zinc ash dechlo-
rination by different roasting temperatures (600 °C, 700 °C, 800 °C, 900 °C, and 1000 °C)
are investigated, as shown in Figure 4. In addition, the corresponding XRD results are
presented
are in Figure
presented 5. It can5.beItseen
in Figure can that no other
be seen thatimpurities
no other are observedare
impurities in the zinc oxide
observed in the zinc
products obtained at different temperatures, which is due to the low content
oxide products obtained at different temperatures, which is due to the low content of chloride.of chloride.

2.0

1.6

Chlorine content/%
1.2

0.8

0.4

0.0
600 700 800 900 1000
Materials 2022, 15, x FOR PEER REVIEW Roasting temperature/℃ 6 of 11

Figure 4.4.Effect
Figure Effectofof
roasting temperature
roasting on chlorine
temperature content
on chlorine of zincof
content ash.
zinc ash.

Figure 5.
Figure 5.XRD
XRDpattern
patternof of
zinc ashash
zinc after dechlorination
after at different
dechlorination roasting
at different temperatures.
roasting temperatures.

As
As we
weknow,
know,Cl Clcontent
contentininzinc ash
zinc is incredibly
ash is incredibly reduced, thanks
reduced, to thetodecomposi-
thanks the decomposition
tion
of Znof5 (OH)
Zn5(OH) Cl 8Cl2H2O in zinc ash at high temperature and the breakdown of Zn(OH) 2
H O in zinc ash at high temperature and the breakdown of Zn(OH)2 to
8 2 2
to ZnO
ZnO [18–22].ItIt can
[18–22]. can be
be seen
seenfromfrom Figure
Figure4 that the Cl
4 that thecontent in zincinash
Cl content zincis 1.69%
ash isafter
1.69% after
being dechlorinated at 600 °C,◦which is mainly attributed to the low volatile temperature.
being dechlorinated at 600 C, which is mainly attributed to the low volatile temperature.
When the temperature goes up to 700 °C, the Cl content is 0.74%, and the partial ZnCl2 is
When the temperature goes up to 700 ◦ C, the Cl content is 0.74%, and the partial ZnCl2
not fully volatilized, since its boiling point is at 732 °C. When the temperature rises to 800
is
°C,not
the fully volatilized,
Cl content since
in zinc ash its boiling
is lowered point
to 0.35%, andisthe 732 ◦ C. When
atdechlorination ratethe temperature
is 90%. When rises
to 800 ◦ C, the Cl content in zinc ash is lowered to 0.35%, and the dechlorination rate is
the temperature is increased to 900 °C, the Cl content decreases to 0.16 wt.%. Although
90%. ◦ C, the Cl content decreases to 0.16 wt.%.
the ClWhen
contentthe hastemperature is increased
decreased significantly, theto 900products
ZnO are still not qualified. When
Although the Clgrows
the temperature content has decreased
to 1000 significantly,
°C, the Cl content in zincthe
ashZnO products
is 0.021 wt.% with are astill not qualified.
dechlo-
When
rinationtheratetemperature
of 99.5%, which grows to 1000
completely ◦ C, ZnO
meets the Cl content in
production, zinc ash
as shown is 0.021
in Table wt.% with
3. The
removed chlorine exists in the form of ZnCl in the flue gas. ZnCl
a dechlorination rate of 99.5%, which completely meets ZnO production, as shown in
2 2 can be dissolved into
the aqueous
Table 3. Thesolution,
removed by washing
chlorinethe flue gas
exists to further
in the form of prepare
ZnClZnCl
2 in the2 products.
flue gas. As listed
ZnCl2 can be
in the chemical analysis of zinc ash, after chloride removal,
dissolved into the aqueous solution, by washing the flue gas to further prepare ZnO content ascends to ZnCl
2
95.05%. The optimal conditions for dechlorination are determined as a
products. As listed in the chemical analysis of zinc ash, after chloride removal, ZnO content roasting tempera-
ture of 1000 °C and a roasting time of 60 min.
ascends to 95.05%. The optimal conditions for dechlorination are determined as a roasting
temperature of 1000 ◦ C and a roasting time of 60 min.
Table 3. Chemical analyses of zinc ash after dechlorination, wt.%.

Table 3. Chemical
Component ZnOanalyses of
Cl zinc ash
Feafter
2O3 dechlorination,
SiO2 wt.%.
CaO MgO Al2O3
Content 95.05 0.021 0.35 1.68 0.63 0.42 0.73
Component ZnO Cl Fe2 O3 SiO2 CaO MgO Al2 O3
Content
3.2. Effect 95.05on Reduction
of Temperature 0.021 Rate0.35
of Zinc Oxide1.68 0.63 0.42 0.73
Reduction temperature affects not only the reduction rate of Zn in carbon-containing
pellets but also the heating mode and energy consumption for smelting. The effects on the
ZnO-reduction rate in carbon-containing zinc ash pellets are studied at different reduction
temperatures (1100 °C, 1150 °C, 1200 °C, and 1250 °C) under the conditions of a 22% re-
duction agent dosage and a 40 min reduction duration, with the test results diagrammed
in Figure 6.
Materials 2022, 15, 5246 6 of 10

3.2. Effect of Temperature on Reduction Rate of Zinc Oxide

Reduction temperature affects not only the reduction rate of Zn in carbon-containing
pellets but also the heating mode and energy consumption for smelting. The effects
on the ZnO-reduction rate in carbon-containing zinc ash pellets are studied at different
reduction temperatures (1100 ◦ C, 1150 ◦ C, 1200 ◦ C, and 1250 ◦ C) under the conditions
Materials 2022, 15, x FOR PEER REVIEW 7 of of
11
a 22% reduction agent dosage and a 40 min reduction duration, with the test results
diagrammed in Figure 6.
100
Zinc ash reduction rate/%

95

90

85

80

75

70
1100 1125 1150 1175 1200 1225 1250
Temperature/℃
Figure 6. Effect
Figure 6. Effect of
of temperature
temperature on
on reduction
reduction rate
rateof
ofzinc
zincoxide.
oxide.

As
As shown
shown in in Figure
Figure 6,6, reduction
reduction in
in carbon-containing
carbon-containing zinc zinc ash pellets increases
ash pellets increases grad-
grad-
ually
ually with
with the
the rising
rising reduction
reduction temperature,
temperature, soso the
the higher
higher the
the reduction
reduction temperature
temperature is,is,
the ◦ C, the re-
the greater
greater thethe Zn-reduction
Zn-reductionrate.rate.When
Whenthe the reduction
reduction temperature
temperature is 1100
is 1100 °C, the reduc-
duction
tion raterate
of Zn of Zn is only
is only 74.23%.
74.23%. A layer
A layer of white
of white zinczinc oxide
oxide powder
powder waswas observed
observed on
on the
the surface of the reduced pellet, and the low reduction rate and zinc oxide
surface of the reduced pellet, and the low reduction rate and zinc oxide evaporation rate evaporation
rate
werewere mainly
mainly attributed
attributed to low
to the the low reduction
reduction temperature
temperature andand vapor
vapor pressure.
pressure. When
When the
the reduction temperature increases up to 1150 ◦ C, the reduction rate of Zn increases to
reduction temperature increases up to 1150 °C, the reduction rate of Zn increases to
86.95%,
86.95%, which
which meansmeans that
that the
the increased
increased reduction
reduction temperature
temperature can
can greatly
greatly enhance
enhance the
the
reduction
reduction of zinc ash and the volatilization rate of zinc vapor. When the temperature
of zinc ash and the volatilization rate of zinc vapor. When the temperature rises rises to
1200 ◦ C, reduction rate of Zn increases to 92.58%, only a small amount of zinc oxide powder
to 1200 °C, reduction rate of Zn increases to 92.58%, only a small amount of zinc oxide
covers the surface of the reduced pellets. When the reduction temperature increases up to
powder covers the surface of the reduced pellets. When the reduction temperature in-
1250 ◦ C, reduction rate of Zn increases to 97.75%, only minimal ZnO residues are observed,
creases up to 1250 °C, reduction rate of Zn increases to 97.75%, only minimal ZnO residues
and a small amount of the liquid phase turning into sintered blocks is also observed, which
are observed, and a small amount of the liquid phase turning into sintered blocks is also
demonstrates that the rapid reduction of carbon-containing zinc ash pellets contributes
observed, which demonstrates that the rapid reduction of carbon-containing zinc ash pel-
to the fast evaporation of the reduced zinc vapor, instead of oxidization on the surface
lets contributes to the fast evaporation of the reduced zinc vapor, instead of oxidization
of the pellets. Therefore, the optimal reduction temperature should be controlled below
on the surface of the pellets. Therefore, the optimal reduction temperature should be con-
1250 ◦ C, to avoid the formation of a large amount of the liquid phase and to obtain a higher
trolled below 1250 °C, to avoid the formation of a large amount of the liquid phase and to
reduction rate.
obtain a higher reduction rate.
3.3. Effect of Time on Reduction Rate of Zinc Oxide
Reduction time affects not only the reduction rate of Zn in carbon-containing pellets
but also the smelting efficiency and energy consumption [12,15,23–27]. The relation of the
ZnO reduction rate of zinc ash pellets and the different reduction times (30 min, 40 min,
50 min, and 60 min) are investigated, as shown in Figure 7. It can be seen that the reduction
time exhibits great influence on the reduction rate of the zinc ash pellets, so the longer the
reduction time is, the higher the Zn-reduction rate. When the reduction temperature is
1200 ◦ C, the growth rate of the zinc-reduction rate is about 1.6%, with the increase in
reduction time. When the reduction temperature is 1200 ◦ C, the growth rate of the zinc-
reduction rate is about 1.42%. When the reduction time is 30 min, reduction temperatures
are 1200 ◦ C and 1250 ◦ C, and the reduction rates of Zn are 88.94% and 93.56%, respectively.
When the reduction time increases to 50 min, the reduction rates of Zn increase up to 93.87%
 time exhibits great influence on the reduction rate of the zinc ash pellets, so the longer the
reduction time is, the higher the Zn-reduction rate. When the reduction temperature is
1200 °C, the growth rate of the zinc-reduction rate is about 1.6%, with the increase in re-
duction time. When the reduction temperature is 1200 °C, the growth rate of the zinc-
reduction rate is about 1.42%. When the reduction time is 30 min, reduction temperatures
Materials 2022, 15, 5246 7 of 10
are 1200 °C and 1250 °C, and the reduction rates of Zn are 88.94% and 93.56%, respectively.
When the reduction time increases to 50 min, the reduction rates of Zn increase up to
93.87% and 98.23%, respectively. When the reduction time increases to 50 min, the reduc-
and
tion 98.23%,
rates ofrespectively.
Zn increase When
up to the reduction
95.34% time increases
and 99.25%. to 50increasing
Therefore, min, the reduction rates
the reduction
of Zn increase up to 95.34% and 99.25%. Therefore, increasing the reduction temperature
temperature and time can significantly improve the reduction rate of zinc. Based on the
and time can
test results significantly
from improve
the different the times,
reduction reduction rate of zinc.
the reduced Based
pellets on the test
are covered withresults
white
from the different reduction times, the reduced pellets are covered with white ZnO powder
ZnO powder after reduction at 1200 °C, which is caused by the oxidization of zinc vapor.
after reduction at 1200 ◦ C, which is caused by the oxidization of zinc vapor. However, no
However, no ZnO residue is found on the surface of reduced pellets after reduction at
ZnO residue is found on the surface of reduced pellets after reduction at 1250 ◦ C, which
1250 °C, which indicates that the higher reduction temperature increases the vapor pres-
indicates that the higher reduction temperature increases the vapor pressure of zinc and
sure of zinc and accelerates the evaporation of zinc. On the basis of the Zn-reduction rate
accelerates the evaporation of zinc. On the basis of the Zn-reduction rate and industrial
and industrial application feasibility, the optimal reduction temperature and time of zinc
application feasibility, the optimal reduction temperature and time of zinc ash pellets are
ash pellets are finally specified as 1250 °C and 60 min.
finally specified as 1250 ◦ C and 60 min.
100.0

97.5
Zinc ash reduction rate/%

95.0

92.5
1200℃
90.0 1250℃

87.5

85.0
30 35 40 45 50 55 60
Reduction time/min
Figure 7. Effect of time on reduction
reduction rate
rate of
of zinc
zinc ash.
ash.

3.4.
3.4. Effect
Effect of
of Reducing
Reducing Agent
Agent Dosage
Dosage on
on Reduction
Reduction Rate
Rate of
of Zinc
Zinc Oxide
Oxide
As a reducing agent, coal powder
As a reducing agent, coal powder is
is used in carbon-containing zinc
used in carbon-containing zinc ash
ash pellets.
pellets. When
When
the reduction temperature is 1200 ◦ C, and the reduction time is 60 min, the effects of
the reduction temperature is 1200 °C, and the reduction time is 60 min, the effects of dif-
different
ferent coalcoal content
content (18(18 wt.%,2020wt.%,
wt.%, wt.%,2222wt.%,
wt.%,and
and2424wt.%)
wt.%)on
onthe
the reduction
reduction rate
rate of
of zinc
zinc
oxide were studied. Figure 8 shows the effect of coal additive amount on reduction rate of
oxide were studied. Figure 8 shows the effect of coal additive amount on reduction rate
zinc ash. It can be seen that with the increase in pulverized coal content, the reduction
Materials 2022, 15, x FOR PEER REVIEW rate
9 of 11
of zinc ash. It can be seen that with the increase in pulverized coal content, the reduction
of zinc oxide increases significantly, and excessive coal dosage wastes energy and consumes
rate of zinc oxide increases significantly, and excessive coal dosage wastes energy and
more heat. Therefore, it is necessary to find the premium coal content.
consumes more heat. Therefore, it is necessary to find the premium coal content.
100.0
Zinc ash reduction rate/%

97.5

95.0

92.5

90.0

87.5

85.0
18 19 20 21 22 23 24
Pulverized coal additive amount/%
Figure 8. Effect of coal additive amount on reduction
reduction rate
rate of
of zinc
zinc ash.
ash.

As
As presented
presented in in Figure
Figure 8,
8, as
as the
the coal additive increases,
coal additive increases, Zn
Zn reduction
reduction inin zinc
zinc ash
ash rises
rises
gradually
gradually and becomes stable with a dosage of up to 22%. At 18% dosage, an 86.34% Zn
and becomes stable with a dosage of up to 22%. At 18% dosage, an 86.34% Zn
reduction
reduction isis tested. According to
tested. According to the
the calculation
calculation of
of aa 1:1
1:1 mole
mole ratio
ratio of
of oxygen
oxygen inin ZnO
ZnO and
and
FeO
FeO and
and fixed
fixedcarbon
carbonininthe
thecoal
coalpowder,
powder, coal additive
coal additiveamounts
amounts to about 18%,
to about theoretically,
18%, theoreti-
although
cally, although it is up to the demand for coal addition in theory, as the loss of (LOI)
it is up to the demand for coal addition in theory, as the loss of ignition of
ignition
(LOI) of carbon-containing pellets in high-temperature heating causes inadequate carbon
addition and low Zn reduction. As the coal is added to 20 wt.%, Zn reduction grows to
94.35%, about 8% more, which means that the increased coal addition can greatly enhance
Zn reduction. When the coal addition increases up to 22%–24 wt.%, the reduction rate of
 Figure 8. Effect of coal additive amount on reduction rate of zinc ash.

As presented in Figure 8, as the coal additive increases, Zn reduction in zinc ash rises
gradually and becomes stable with a dosage of up to 22%. At 18% dosage, an 86.34% Zn
Materials 2022, 15, 5246
reduction is tested. According to the calculation of a 1:1 mole ratio of oxygen in ZnO8 of and
10
FeO and fixed carbon in the coal powder, coal additive amounts to about 18%, theoreti-
cally, although it is up to the demand for coal addition in theory, as the loss of ignition
(LOI) of carbon-containing pellets in high-temperature heating causes inadequate carbon
carbon-containing pellets in high-temperature heating causes inadequate carbon addition
addition and low Zn reduction. As the coal is added to 20 wt.%, Zn reduction grows to
and low Zn reduction. As the coal is added to 20 wt.%, Zn reduction grows to 94.35%,
94.35%, about 8% more, which means that the increased coal addition can greatly enhance
about 8% more, which means that the increased coal addition can greatly enhance Zn
Zn reduction. When the coal addition increases up to 22%–24 wt.%, the reduction rate of
reduction. When the coal addition increases up to 22%–24 wt.%, the reduction rate of
zinc oxide reached 99.25% to 99.42%, which indicates that when the amount of pulverized
zinc oxide reached 99.25% to 99.42%, which indicates that when the amount of pulverized
coal is 22 wt.%, the carbon amount in pellets is already enough to meet ZnO reduction in
coal is 22 wt.%, the carbon amount in pellets is already enough to meet ZnO reduction in
zinc ash, and more coal addition makes little difference to Zn-reduction enlargement. On
zinc ash, and more coal addition makes little difference to Zn-reduction enlargement. On
the contrary, excessive pulverized coal will only increase coal consumption and reduce
the contrary, excessive pulverized coal will only increase coal consumption and reduce
energy efficiency.
energy efficiency.
Under the optimal process conditions, a ZnO product with a purity of 99.5% is ob-
Under the optimal process conditions, a ZnO product with a purity of 99.5% is ob-
tained. Figure 9 presents the XRD pattern of the ZnO product, and the SEM images of the
tained. Figure 9 presents the XRD pattern of the ZnO product, and the SEM images of the
ZnO product
ZnO product isis shown
shown inin Figure
Figure 10.
10. Due
Due to
to the
the extremely
extremely high
high purity
purity of
of the
the zinc
zinc oxide
oxide
products, no other material phases are observed in the XRD pattern. SEM image
products, no other material phases are observed in the XRD pattern. SEM image shows that shows
thatzinc
the the oxide
zinc oxide
productproduct has a needle-like
has a needle-like crystal structure
crystal structure with of
with a length a 10
length
µm. of 10 μm.
Therefore,
Therefore,
the the high-purity
high-purity zinc oxide
zinc oxide obtained obtained
by direct by direct
reduction reduction
can replace the can
zincreplace the zinc
oxide produced
oxide produced by the indirect process and can be used as a rubber vulcanizing
by the indirect process and can be used as a rubber vulcanizing agent, zinc oxide arrester, agent,
zinc oxide arrester, manganese zinc soft
manganese zinc soft magnetic material, etc. magnetic material, etc.

50000
◆
40000 ◆ ZnO
◆
Intensity

30000

20000
◆
◆ ◆
10000
◆ ◆
◆
◆ ◆◆ ◆ ◆
0
10 20 30 40 50 60 70 80 90
Materials 2022, 15, x FOR PEER REVIEW Position(°2Theta) 10 of 11

9. XRD pattern of ZnO

Figure 9.
Figure ZnO product.
product.

Figure10.
Figure 10.SEM
SEMimages
imagesof
ofZnO
ZnOproduct.
product.

4. Conclusions
(1) Zn in zinc ash mainly exists in the form of zinc oxide (ZnO), basic zinc chloride
(Zn5(OH)8Cl2H2O), and metallic zinc (Zn). The optimal conditions for zinc ash dechlorin-
ation are determined as a roasting temperature of 1000 °C and a roasting time of 60 min.
After roasting, Cl content in zinc ash is only 0.021 wt.%, and the removal rate of the Cl
Materials 2022, 15, 5246 9 of 10

4. Conclusions
(1) Zn in zinc ash mainly exists in the form of zinc oxide (ZnO), basic zinc chloride
(Zn5 (OH)8 Cl2 H2 O), and metallic zinc (Zn). The optimal conditions for zinc ash dechlori-
nation are determined as a roasting temperature of 1000 ◦ C and a roasting time of 60 min.
After roasting, Cl content in zinc ash is only 0.021 wt.%, and the removal rate of the Cl
element reached 99.5%.
(2) The reduction test of carbon-containing zinc ash pellets shows that the reduction
temperature has the most influence on the reduction rate of zinc oxide. The optimal process
parameters are a reduction temperature of 1250 ◦ C, a reduction time of 60 min, and a coal
powder content of 22 wt.%. Under the optimal process conditions, the reduction rate of
Zn in zinc ash reaches 99.25%, and the ZnO content increases up to 99.5 wt.%. The ZnO
content of the product is close to that of indirect zinc oxide.
(3) Due to the extremely high purity of the zinc oxide products, no other material
phases are observed in the XRD pattern. SEM image shows that the zinc oxide product has
a needle-like crystal structure with a length of 10 µm. The high-purity zinc oxide obtained
by direct reduction can replace the zinc oxide produced by the indirect process and can
be used as a rubber vulcanizing agent, zinc oxide arrester, manganese zinc soft magnetic
material, etc.

Author Contributions: The manuscript was written through the contributions of all authors. Y.Z.:
conceptualization, investigation, and supervision. J.G. and H.W.: writing original draft and image
processing. J.G., J.W. and F.W.: validation, resources, investigation, writing—review and editing. J.G.,
S.Y. and S.L.: visualization, writing—review and editing. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was supported by the National Key R&D Program of China (No. 2018YFC1900601)
and the Anhui Province Science Foundation for Excellent Young Scholars (No. 2108085Y19).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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