catalysts
Article
Acid Gas and Tar Removal from Syngas of Refuse Gasification
by Catalytic Reforming
Guoan Yuan 1,2 , Wei Zhou 3 , Rui Yang 3 , Yuru Liu 3 , Jingyu Zhu 3 , Ke Yin 3, * and Dezhen Chen 1, *
Citation: Yuan, G.; Zhou, W.; Yang,
R.; Liu, Y.; Zhu, J.; Yin, K.; Chen, D.
Acid Gas and Tar Removal from
Syngas of Refuse Gasification by
Catalytic Reforming. Catalysts 2022,
12, 1519. https://doi.org/10.3390/
catal12121519
Academic Editors: Jingbo Jia and
Haiming Wang
Received: 31 October 2022
Accepted: 21 November 2022
Published: 25 November 2022
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Catalysts 2022, 12, 1519. https://doi.org/10.3390/catal12121519
1 Thermal and Environmental Engineering Institute, Tongji University, 1239 Siping Road,
Shanghai 200092, China
2 Shanghai Institute for Design & Research on Environmental Engineering Co., Ltd., 345 Shilong Rd,
Shanghai 200232, China
3 School of Biology and the Environment, Nanjing Forestry University, 159 Longpan Road,
Nanjing 210037, China
* Correspondence: yinke@njfu.edu.cn (K.Y.); chendezhen@tongji.edu.cn (D.C.)
Abstract: The existence of acid gas and tar in syngas of municipal solid waste gasification limits its
downstream utilization as a clean energy source. Here, we investigated the catalytic removal of HCl
and tar. The key parameters affecting the catalytic reaction, including space velocity, temperature, the
amounts of active metals in the catalyst and the carrier material, were studied, targeting optimized
operating conditions for enhanced syngas purification. The morphology, mineral phases, surface
area and pore size before and after the reaction were investigated to understand the mechanism to
dominate the reaction. The results showed that the removal rate of CaO adsorbent and HCl reached
96% at 400 ◦ C. When the space velocity ratio was 1.0 and the temperature was 400 ◦ C, HCl removal
(97%) by NaAlO2 was even better. Nevertheless, clogging was observed for NaAlO2 via the BET
test after reaction to jeopardize its durability. A level of 25% Ni doping on Zr1-x (Cex )O2 support
provides high stability for tar removal. This is because the Zr1-x (Cex )O2 carrier has higher carbon
deposition resistivity than the Al2 O3 carrier. The EDX results confirmed that a large amount of C
(79.3%) was accumulated on the commercial catalyst surface supported by Al2 O3 (25% Ni-based). As
for the temperature, a temperature higher than 800 ◦ C could not enhance the efficiency of tar removal,
likely due to catalyst deactivation. Carbon deposition and agglomeration are the two main causes
of catalyst deactivation. At 800 ◦ C, 25% Ni-based synthetic catalyst can convert 48.5 ± 19.4% tar
to low molecular weight organic compounds. By contrast, such a conversion rate under the same
temperature only accounted for 5.0 ± 6.8% based on a commercial catalyst. These insights point to
the important role of catalyst support materials.
Keywords: municipal solid waste; syngas purification; pyrolysis; HCl; tar
1. Introduction
Incineration and pyrolytic gasification are the current mainstream methods of thermal
treatment of municipal solid waste (MSW). Incineration refers to the vigorous oxidative
combustion reaction of MSW mixed with excess air to generate water, carbon dioxide and
ash. Although a volume reduction of MSW can be achieved, pollutants such as dioxins,
heavy metals, nitrogen oxides, sulfur oxides and acid gases generated during the incinera-
tion process endanger the ecological environment and human health. Pyrolytic gasification
refers to the thermal treatment technology of incomplete combustion of MSW under the
condition of insufficient oxygen (excess air coefficient α < 1) to produce syngas, coke, and
tar. Compared with traditional incineration technology, the advantages of pyrolytic gasifi-
cation technology mainly include low pollutant emission levels, high power generation
efficiency, and diversified products (combustible gas, coke, and other products) [1,2].
However, syngas also contains impurities such as tar, particulate matter, and acid
gas [3]. In syngas, the acid gases contained are mainly HCl, which may cause corrosion
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Catalysts 2022, 12, 1519 2 of 17

of metal equipment and environmental problems, and can harm human health when
exposed to acid gases. In the gas phase, acid gases are likely to form new pollutants with
other substances, resulting in pollutant deposition and blockage [4]. Therefore, in the
whole purification process, the removal of acid gases should be given priority to avoid the
deactivation of catalysts caused by them in the subsequent high-temperature gasification
process. In addition, alkali metal oxide catalysts can be effectively retained in the solid
phase by means of physical adsorption and chemical adsorption in the gasification process,
which is a relatively effective catalyst to eliminate acid gases [5,6]. Transition metal catalysts
are also widely used to remove pollutants from syngas because of their stable performance
and anti-carbon deposition ability [7].
Compared with particulate matter and acid gas, the concentration of tar in syngas is
higher, usually around 1–100 g Nm−3 [8]. Tar is an inevitable by-product in the gasification
process, and generally refers to all products with a molecular weight greater than benzene.
The existence of organic pollutants and tar will seriously restrict the application of syngas,
such as causing corrosion to gas turbines, internal combustion engines and downstream
pipelines. Tar is carried by the syngas flow, and gradually condenses in the pipelines
and related equipment in the process of transporting syngas, forming a viscous liquid
substance. The production of tar reduces gasification efficiency. The energy of the tar
product in gasification can account for 5–15% of the calorific value of the raw material [9],
and this part of the energy is difficult to be utilized together with the combustible gas at low
temperature. Some polycyclic aromatic hydrocarbon (PAH) substances with high content
in tar components are toxic, which poses a threat to people who may come into contact
with the gasification system.
According to the principle of pollutant removal, it can be generally divided into
physical and chemical methods. The physical method uses physical means (such as water
washing, filtration, cyclone separation, electrostatic decoking, etc.) to transfer pollutants
from the gas phase to the condensed phase, so as to achieve the purpose of removing
them [10]. Although the physical method is simple and less costly, it cannot fundamentally
remove specific contaminant such as tar, which will also cause certain pollution to soil and
water resources. Chemical removal is a method in which pollutants are converted into
harmless matter by chemical reaction by changing the gasification temperature and adding
a gasification agent or catalyst [11].
For tar removal, catalytic cracking is an ideal way. Compared with thermal cracking, it
can achieve high-efficiency removal of tar at a lower temperature. Taking steam reforming
as an example, the catalytic reforming mechanism of tar is as follows. First, the compound
molecules in the tar are adsorbed onto the metal active sites of the catalyst surface which
undergoes a dehydrogenation reaction to generate intermediate products and hydrogen
radicals [12]. At the same time, the water vapor adsorbed on the catalyst is dissociated into
hydroxyl radicals and hydrogen radicals, and the hydroxyl radicals will then hydroxylate
the catalyst surface. At an appropriate reaction temperature, hydroxyl radicals gradually
migrate to the center of the metal active site, oxidizing hydrocarbon intermediates and
surface carbon to carbon monoxide and hydrogen [13].
Among the gas cleaning systems currently known for gas production, the hot gas
cleaning system is considered superior to the condensation technology because it helps to
solve the heat loss problem associated with condensation [14]. This approach promises
higher cooling efficiency but also reduces harmful by-products and wastewater treatment
problems [3]. As a result, hot gas cleaning systems have attracted the most attention in the
last decade, especially for removing tar, particulate matter and chlorine, etc. However, the
main limitation of the hot gas purification is the rapid inactivation of the catalysts during
reaction [15].
The key to adopting the hot gas purification method for domestic waste pollutants
is to select a catalyst suitable for the reaction and with high catalytic activity. At present,
the catalysts commonly used in the reforming process mainly include the following three
types: natural ore catalysts, alkali metal catalysts and transition metal catalysts [16].
Catalysts 2022, 12, 1519 3 of 17

Catalysts where the active component is Ni, Zn, Cu, Fe have gradually become a
promising alternative for catalysts made of precious metals due to their wide sources,
low cost, easy preparation and good catalytic activity. Common carriers of Ni-based
catalysts include metal oxides, natural ores, molecular sieves, biochar etc. The carrier can
effectively control the metal particle size and improve the uniformity of its dispersion,
thereby enhancing the catalytic activity [17]. Metal oxides are the most used supports. The
metal compound supports that can be used as transition metal catalysts usually include
Al2 O3 , ZrO2 , MgO, and CaCO3 , and common additives include CeO2 [18]. Among them,
Al2 O3 can provide more active sites for the catalyst due to its higher specific surface
area. The addition of CeO2 may improve the performance of catalysts through a redox
mechanism. Low-valence Ce may adsorb water and dissociate it to generate oxygen radicals
(·O) or hydroxyl (·OH), which react with carbon on the catalyst surface to generate CO,
CO2 , and H2 . Zhang et al. [19] studied the effect of CeO2 -doped Ni/olivine catalysts on
tar in the steam reforming process and found that CeO2 -doped CeO2 had special effects in
both catalytic activity and coking resistance.
The aim of this study is to investigate the performance of HCl and tar removal us-
ing hot gas cleaning process on the basis of different catalysts, explore the best process
parameters, and confirm whether it can meet the standard of syngas use.

2. Results and Discussion

2.1. HCl
2.1.1. CaO Adsorbent
This experiment is mainly to study the effect of gasification temperature on the re-
moval of hydrogen chloride in domestic waste (Figure 1). Under the condition that the
airspeed ratio is determined, the optimum temperature of hydrogen chloride removal
can be determined by changing the temperature of hydrogen chloride gasification. Mura
and Lallai [20,21] studied the reaction between calcium oxide and hydrogen chloride and
determined that the activation energy of the reaction was 45 kJ·mol−1 . Weinell and Jensen
analyzed the reaction of HCl with lime and limestone at 60–1000 ◦ C. They showed that lime
and limestone are able to capture most of the HCl at 500–600 ◦ C and then, beyond 500 ◦ C,
the chemical balance between gas and solid reduces the adsorption capacity. Therefore,
we set the gasification temperature of 300 ◦ C, 400 ◦ C and 500 ◦ C, to determine the best
temperature for HCl purification of Shanghai municipal solid waste.

Figure 1. Effect of different temperatures on (a) HCl removal rate (%) and (b) HCl adsorption (mg/L).

By analyzing the change in HCl concentration over time, we can see that the removal
efficiency of HCl at different temperatures finally stabilized above 90%. This shows that the
reaction between CaO and hydrogen chloride is particularly intense at medium and high
temperatures, and the adsorption effect is excellent. When the gasification temperature
is at 500 ◦ C for the first 30 min, the removal efficiency obviously increases. Through the
experiments of removing hydrogen chloride with CaO at different gasification temperatures,
it can be found that the removal efficiency of HCl with CaO at 400 ◦ C is the highest, which
Catalysts 2022, 12, 1519 4 of 17

is up to 95.62%, conforming with the results of Weinell et al. [22]. At 300 ◦ C, the efficiency
of hydrogen chloride removal decreases slightly with the increase in temperature. This may
be due to the increase in temperature, surface morphology and structure of CaO adsorbent
changing before and after the reaction, resulting in reduced HCl removal efficiency.

2.1.2. NaAlO2 Adsorbent

This experiment is mainly aimed at the optimal temperature for the removal of HCl by
CaO, to study the influence of airspeed ratio on the removal of hydrogen chloride (Figure 2).
The effect of space velocity ratios on catalytic efficiency is often discussed in gas–solid
reactions. Reaction space velocity refers to the amount of gas treated by adsorbent/catalyst
per unit volume of catalyst per unit time under specified conditions. In the calculation, it
can be considered as the ratio of the carrier gas flow rate and the catalyst stack volume.
Generally, the airspeed ratio should be less than 5 s−1 . When the carrier gas flow rate is
unchanged, the more adsorbent/catalyst added, the greater the airspeed ratio, and the
higher the pollutant removal rate.

Figure 2. Effect of different space velocity ratios on (a) HCl removal rate (%) and (b) HCl
adsorption (mg/L).

To obtain the best space velocity ratio of adsorbent, the same catalytic temperature
(400 ◦ C) and the same catalyst (NaAlO2 ) were set. The flow rate of N2 was 148 mL/min,
and the removal efficiency of HCl was studied by changing the amount of adsorbent (0.5 g,
0.9 g and 1.8 g).
Within 3 h of the experiment, the removal rate and HCl adsorption of 0.5 g adsorbent
was relatively low. Both 0.9 g and 1.8 g NaAlO2 could absorb more than 95% of HCl. In
the whole reaction process, the cumulative adsorption rate of 1.8 g adsorbent for HCl was
higher than that of 0.9 g. However, the adsorption efficiency of 1.8 g adsorbent decreased
when the reaction was carried out for 60 min. The reason may be that HCl did not fully
contact and react with the adsorbent below after fully reacting with NaAlO2 on the surface.
Therefore, there was a process of decline. As time went on, the reaction between HCl and
NaAlO2 became more sufficient, and the removal efficiency increased again. At 180 min,
the conversion rate of 1.8 g was slightly lower than 0.9 g, which may have led to the
change in chemical bonds in the adsorbent due to the long running time, thus affecting
the adsorption efficiency. In general, in the two experiments with changed space velocity
ratios, the removal rate of 1.8 g adsorbent was slightly better than that of 0.9 g adsorbent.

2.1.3. Characterization of NaAlO2 before and after the Experiment

BET
The type III isotherm indicates that the material interaction between adsorbent molecules is
strong, and it is difficult to adsorb the adsorbent at the initial stage. With the progress of the
adsorption process, the adsorption appears as a self-accelerating phenomenon (Figure 3).
In this section, BET representation of NaAlO2 before and after the reaction was made, as
shown in Table 1. Among them, the specific surface area and pore size of the fresh adsorbent
are both low, and the specific surface area of the adsorbent after the reaction increases
Catalysts 2022, 12, 1519 5 of 17

from 0.8188 m2 /g to 0.9314 m2 /g, which may be due to the collapse of its structure during
the reaction, resulting in the appearance of new micropores on the surface of the sample,
so it has a larger specific surface area than before the reaction. After the HCl removal
experiment, the mesoporous volume of the adsorbent was reduced from 0.0067 cm3 /g
to 0.00458 cm3 /g. This may be because during the experiment, the metal oxides inside
the adsorbent void reacted with HCl gas, and the resulting products plugged the void of
the adsorbent.

Figure 3. The nitrogen adsorption–desorption isotherms of NaAlO2 before (a) and after (b) the
catalytic reforming process.

Table 1. BET characterization of NaAlO2 before and after reaction.

NaAlO2 Before Reaction After Reaction

BET surface area (m2 /g) 0.8188 0.9314
Pore volume (cm3 /g) 6.77 × 10−3 4.58 × 10−3
Average diameter (nm) 44.61 26.09

SEM
Figure 4 represents SEM photos before and after the adsorbent reaction. As can be seen
from the figure, the surface of the sample presents a loose and porous morphology, and
has a certain degree of agglomeration phenomenon, forming a large aggregate structure.
Compared with the adsorbent before the reaction, the structure of NaAlO2 after the reaction
showed obvious shrinkage and collapse, the agglomeration phenomenon was more serious,
and some voids were blocked.

XRD
In this section, the XRD analysis of the crystal phase of NaAlO2 before and after
the reaction was carried out. The results are shown in Figure 5. For fresh adsorbents,
Na2 ZnSiO4 can be clearly identified. By comparing the adsorbents after reaction, only
Na2 CO3 and NaClO3 can be observed, indicating that most of the substances in sodium
metalate reacted with HCl and were reduced. In general, the XRD characterization results
of NaAlO2 before and after the reaction very reliably show that NaAlO2 can effectively
absorb HCl.

2.2. Tar
2.2.1. Determination of the Flux of Naphthalene
Naphthalene was used as a model tar compound, so it was necessary to ensure a stable
naphthalene vapor flow rate for each experiment. The vapor flow rate of naphthalene
during the experiment was required to stabilize at 4.2 ± 0.4 mg/L, which is the typical
concentration of tar in wet biomass and MSW syngas (based on the mean standard deviation
of 4 measurements). The actual flow rate of naphthalene vapor was measured in blank
operation state (no catalyst added), and the reducing environment was maintained during
Catalysts 2022, 12, 1519 6 of 17

the reforming process (the N2 flow rate was controlled at 200 mL/min). Test the vapor flow
of naphthalene at different temperatures, and determine the evaporator temperature when
the vapor flow of naphthalene is close to 4.2 mg/L. The results are shown in Figure 6.

Figure 4. SEM of NaAlO2 (a,c) before reaction, (b,d) after reaction (* is only used as a magnification
mark, no special significance).

Figure 5. XRD of NaAlO2 before and after the reaction.

Catalysts 2022, 12, 1519 7 of 17

Figure 6. Naphthalene vapor fluxes under various heating temperatures.

Vapor flow of naphthalene was tested at four temperatures, 57 ◦ C, 62 ◦ C, 69 ◦ C, and

74 ◦ C,respectively. The corresponding vapor flow of naphthalene increased with the rise
in temperature, indicating that high temperature promotes the melting of naphthalene and
then into a gaseous state into the reactor. When the temperature is 62 ◦ C, the vapor flow
rate of naphthalene is stable at 4.3 mg/L (the average value of four parallel experiments),
which is closest to the targeting value. Therefore, evaporating temperature was set to 62 ◦ C.

2.2.2. The Effects of Space Velocity on Tar Catalytic Reforming

Reaction space velocity refers to the amount of gas processed per unit volume of
catalyst per unit time under specified conditions. In the process of gas–solid catalytic
reaction, the effect of space velocity ratio on catalytic efficiency is often discussed. When
calculating, it can be considered as the ratio of the flow rate of the carrier gas to the volume
of the catalyst stack. In a typical syngas scrubbing process, the space velocity ratio is
often less than 5 s−1 [11,23]. When the flow rate of the carrier gas remains unchanged, the
more catalyst added, the larger the space velocity ratio, and the higher removal rate of
naphthalene. In the study, to obtain the best space velocity ratio of the catalyst, the same
catalyst temperature (750 ◦ C) and the same catalyst (25% Ni-based synthetic catalyst) were
compared. Since the carrier gas flow rate was controlled at 200 mL/min, by varying the
amount of catalyst (0.5 g and 1.0 g), the effect of the space velocity ratio (3.78 and 1.89 s−1 ,
respectively) on the gas components (CO, CO2 and CH4 ) was obtained (Figure 7).

Figure 7. The Naphthalene conversion (a) rate (%) and (b) amount (mg) with different space velocity
ratios on tar catalytic reforming in 2 h.
Catalysts 2022, 12, 1519 8 of 17

For the application of 0.5 g of catalyst (reaction time = 2 h), the removal rate of naph-
thalene highly fluctuated in the range of 80.1–97.5% (the lowest was 80.1% at 80 min, and
the highest was 97.5% at 40 min), which would be unfavorable for sustainable naphtha-
lene cracking. We postulate that as the operation time extended, carbon deposition more
likely occurred under the low space velocity ratio resulting in deteriorating tar-cracking
performance. For the application of 1.0 g of catalyst, the removal rate of naphthalene fell
within the lower range of 77–87%. It yields the cumulative conversion of naphthalene
corresponding to 0.5 g catalyst was higher than that of 1.0 g during the whole reaction
process. However, it should be noted that the conversion rate demonstrated a rising trend
with time when more catalyst was present in the reaction system, suggesting that there
could be a longer adaptation period before the reaction reaches full-scale speed. In addition,
studies [24] have shown that increasing the catalyst loading can provide a larger reaction
area for the catalytic reforming of naphthalene. More nickel surface active sites can greatly
reduce the activation energy required for naphthalene cleavage, thereby reducing the re-
action time. At the same time, increasing the loading height can prolong the contact time
between naphthalene and the catalyst, thereby improving the reforming efficiency of naph-
thalene. In this regard, 1.0 g catalyst was selected in the following experiments. It is also
worth noting that excessive Ni leads to the sintering and agglomeration of NiO particles,
which reduces the specific surface area of the catalyst and inhibits the catalytic activity.

2.2.3. The Effects of Temperature on Tar Catalytic Reforming

The effects of reaction temperature on the catalytic reforming of naphthalene were
investigated, and 1.0 g of 25% synthetic catalyst was introduced, with reaction temperatures
set at 750 ◦ C, 800 ◦ C, 850 ◦ C and 900 ◦ C, respectively. The results are shown in Figure 8.

Figure 8. The Naphthalene conversion (a) rate (%) and (b) amount (mg) with different temperatures
on tar catalytic reforming in 2 h.

Under 750 ◦ C, the removal rate of naphthalene was stable in the range of 77.3–86.1%
(the lowest was 77.3% in 20 min, and the highest was 86.1% in 120 min), which was similar
to the rate under 900 ◦ C (76–84%). The conversion of naphthalene was maintained at a low
level. Under the working condition of 800 ◦ C, the removal rate of naphthalene fluctuated
greatly, reaching 110.8% in 20 min. This compared with removal rates of 77.3%, 107.8%,
and 80.7% in 20 min at 750 ◦ C, 850 ◦ C, and 900 ◦ C, amounting to an increase of 33.6%, 3.0%,
and 30.2%, respectively. At all other reaction times, the catalytic reforming efficiency of
naphthalene and the cumulative amount at 800 ◦ C were the highest (except in 100 min at
850 ◦ C). When the reaction temperature rose moderately (up to 800 ◦ C), the active sites on
the catalyst surface were activated, and the π electron cloud of the polyaromatic ring of the
tar precursor was adsorbed on the active sites to be readily destroyed. C-C and C-H bonds
are prone to be broken first, and the activation energy required for naphthalene reforming
was reduced, thereby increasing the conversion rate of naphthalene. When temperature
rose further up to 850–900 ◦ C, however, catalytic efficiency started to decrease. The reason
may be ascribed to carbon deposition, resulting in the reduction of reduced catalyst activity
Catalysts 2022, 12, 1519 9 of 17

and even deactivation. This suggests that 800 ◦ C is the optimal temperature for catalytic
reforming of naphthalene.

2.2.4. The Effects of Different Catalysts and Associated Loading Rates on Tar Removal
The catalytic effect of 25%-Ni synthetic catalyst is better than that of 15%-Ni synthetic
catalyst. It shows that higher nickel loading provides more nickel surface active sites for
promoted catalytic reforming and simultaneously reduces the activation energy required
for naphthalene cracking. Compared to commercial catalysts (25% Ni), the naphthalene
conversion was comparable (87–110% and 89–102%, respectively). However, in terms of
the total conversion of naphthalene, the synthetic one is slightly better. It can be seen from
the SEM-EDX characterization (Figure 9) that the carbon content of the 25%-Ni commercial
catalyst after the reaction increased by 59.2% compared with the fresh counterpart, and
significant coking was observed in the SEM image, which indicates that the commercial
catalyst is easier to deposit carbon, which leads to the reduction in its catalytic activity. In
fact, the structure of alumina support in the commercial catalyst tends to collapse (to form
agglomerates) under high temperature [25]. Therefore, 25% Ni-based synthetic catalyst is
an ideal catalyst with higher durability and thermal resistance.

Figure 9. The Naphthalene conversion (a) rate (%) and (b) amount (mg) with different catalysts and
associated loading rates on tar catalytic reforming in 2 h.

2.2.5. Gas Chromatography Analysis of Tar-Reforming End Products

For commercial catalysts (25% NiO), the content of C10 group and those greater than
C10 (referring to higher C-containing compounds than naphthalene (C = 10) after catalytic
reforming) in the liquid phase at 750 ◦ C is the highest (Figure 10a). Since the reaction
temperature is not optimized, as noted earlier, only a small amount of naphthalene (12.2%)
is broken down into smaller molecular organics (designed as <C10 group). As the tem-
perature increased from 800 ◦ C to 900 ◦ C, only 6.7–14.8% of naphthalene residue was
collected (Figure 6). More naphthalene was either cracked (48.5–60.2%) or polymerized into
high-molecular organic matter (25.7–44.7%). However, the phenomenon of polymerization
was less pronounced with increased temperature. In another words, cracking activities
became significantly facilitated with the incremental rise in temperature. Under 900 ◦ C, the
content of these three groups of compounds in the liquid phase leveled off, indicating the
achievement of an equilibrium state in which raising the temperature posed limited effects
on the promotion of decomposition or polymerization. Multiple factors are responsible
for this, including the space velocity ratio, the available surface-active sites of the catalyst,
and the coking effect. For self-made catalysts (25% NiO), temperature played a significant
role in the formation of <C10 and C10 groups, while the influence towards >C10 groups
was comparable among different temperatures. With the increase in temperature, a greater
amount of tar tended to be cracked. The cracking effect likely peaks (at around 60% of
<C10 groups) after 850 ◦ C, corresponding to an optimized catalyst performance. Compara-
Catalysts 2022, 12, 1519 10 of 17

tively, self-made catalysts perform better than commercial ones in respects of tar-cracking
ability, as shown in Figure 10c.

Figure 10. Distribution of various reforming compounds under different reaction temperature for
(a) commercial catalysts, (b) self-made catalysts, and (c) distribution of various reforming compounds
between self-made and commercial catalysts.

2.2.6. Characterization of Various Catalysts before and after Tar Reforming for
Mechanism Investigation
XRD Characterization
For the freshly synthetic catalyst, the characteristic peaks of NiO, ZrO2 and CeO2
were clearly identified (Figure 11). Surprisingly, the crystal phase of Ni was not observed.
All Ni appeared in its oxide format, which indicated that the catalyst was manufactured
successfully. In contrast, for the catalyst after the reaction, only elemental nickel can be
observed (no characteristic peaks of nickel oxide), indicating that most of the nickel oxides
had been reduced to elemental nickel during the catalytic reforming process. Nevertheless,
a small amount of nickel oxide could not be ruled out. The XRD characterization results of
the catalysts before and after the reaction were very reliable to illustrate the fact that the
nickel oxide was reduced in the catalytic reforming.

SEM Characterization
Figure 12 shows the SEM-EDX scanning results of the 25%-Ni commercial catalyst
and 25%-Ni synthetic catalyst, before and after the tar reforming process. For the synthetic
catalyst, the distribution between nickel and the carrier is loose and largely uniform. As the
precipitated nickel particles have much smaller volume compared to the carrier particles,
the SEM image shows a scattered distribution of Ni. For the commercial catalyst, due to
its larger particle size, its special preparation process makes its appearance flatter, and
the pores are not as obvious as those of the synthetic catalyst. For both commercial and
synthetic catalysts, the semi-quantitative results of EDX elements after the reaction show
fewer oxygen elements than before the reaction, which is attributed to the consumption of
oxygen in the nickel oxide during the catalytic reforming reaction to form CO, CO2 , etc. It
is further echoed by the EDX mapping results (according to the different density of oxygen
elements presented before and after reaction), and a small amount of oxygen elements
remaining after the reaction may originate from the carrier part.
Catalysts 2022, 12, 1519 11 of 17

Figure 11. XRD characterization of synthetic catalysts before and after catalytic reforming process.

Figure 12. SEM characterization of 25%-Ni commercial catalyst and 25%-Ni synthetic catalyst
catalysts before catalytic reforming process (a,b) and the commercial catalyst after the process (c).
Catalysts 2022, 12, 1519 12 of 17

For the EDX results, obvious peaks (Ni, Zr and Al) can be seen for both catalysts in
the spectrum, and the Ce peak is not easily observed due to its small content. It is worth
noting that a large amount of C (79.3%) was observed on the surface of the commercial
catalyst after reaction, while no significant carbon content was noticed in the fresh one.
With surface carbon precipitation, it blocks pores of catalyst and prevents naphthalene from
diffusing into the interior part of the catalyst during the high-temperature reaction, thus
resulting in incomplete tar removal. This phenomenon also suggests the weaker durability
of the commercial catalysts.

BET Characterization
The type IV isotherm with an H1 hysteresis loop at higher relative pressure demon-
strated that the synthetic catalyst is a mesoporous material (Figure 13a) [18]. Among them,
the fresh one had a higher specific surface area (3.03 m2 /g) and a lower pore size, which
was due to the surface area provided by zirconia for the dispersion of the catalyst and
the smaller pore size of the impregnated catalyst (Table 2). After catalytic reforming, the
specific surface area, pore volume and average pore size of the catalyst became larger,
which was attributed to the consumption of oxygen element. As a result, the catalysts
became macro-porous solid materials and no longer had adsorption characteristics, which
was supported by the III type isotherm in Figure 3b.

Figure 13. The nitrogen adsorption–desorption isotherms of the 25% Ni-based synthetic catalysts
(a) before and (b) after catalytic reforming process.

Table 2. BET characterization of synthetic catalysts before and after catalytic reforming process.

25% Ni-Based Synthetic Catalyst Before Reaction After Reaction

BET surface area (m2 /g) 3.03 4.84
Pore volume (cm3 /g) 2.74 × 10−2 4.82 × 10−2
Average diameter (nm) 36.90 39.80

3. Materials and Methods

3.1. Catalyst Preparation
The commercial catalyst was a Ni-based spherical particle with Al2 O3 as a carrier,
purchased from a chemical engineering company in Shanghai, China. The Ni-based catalyst
particle had a loading of 25% Ni by weight, with the particle diameter at 0.5–1 mm. Ni-
based synthetic catalysts were synthesized using ceria-stabilized zirconia as a support. The
carrier was purchased from a company in Beijing, China, and the addition of cerium oxide
was 8% to enhance the stability of the carrier at high temperature [19]. Ni-based synthetic
catalysts with Ni loadings of 15% and 25% were prepared. The carrier was added to a
deionized aqueous solution containing Ni(NO3 )2 ·6H2 O and mixed. The solvent water was
evaporated using a rotary evaporator at 82 ◦ C. The material was then dried in an oven at
105 ◦ C for 12 h, and finally placed in a muffle furnace for 2 h air roasting at 500 ◦ C (with a
Catalysts 2022, 12, 1519 13 of 17

heating rate of 2 ◦ C/min). The calcined samples were ground and sieved, and the powder
with a particle size of 0.053–0.1 mm was collected and stored in a sealed container before
the experiments began.
A series of characterizations were performed on the prepared catalysts. An X-ray
fluorescence spectrometer (XRF) was used to determine the type and content of oxides in
the catalyst. An X-ray diffractometer (XRD) was used with Cu Kα radiation (40 kV, 35 mA),
where the θ ranges from 10◦ to 80◦ with a step size of 0.02◦ to analyze the crystal structure
of the catalyst. The morphology and surface elements were determined by environmental
scanning electron microscopy (SEM). The specific surface area, total pore volume and pore
size of the oxygen carrier were analyzed by nitrogen adsorption–desorption isotherm at
−196 ◦ C using an automatic specific surface area and pore size distribution analyzer (BET).

3.2. Experimental Setup

In this experiment, the catalysts and the effect of additives in the tube furnace on
syngas absorption, which was pyrolytically gasified by domestic waste, were studied by
using a fixed-bed pyrolysis reaction device in a vertical tube furnace. The experimental
device, shown in Figure 14, was mainly composed of three parts: (1) Gas supply: it mainly
includes the gas source of the high-pressure gas cylinder, the gas flow controller needed
to maintain the reaction atmosphere in the gasification process, and the device needed
to simulate pollutants; (2) Main element: including heating temperature control device,
vertical tube furnace and quartz tube; (3) Sample collection: mainly air bag collection and
condensation collection. The main part of the quartz tube diameter was 15 mm, the outer
diameter was 20 mm, the length was 65 cm; 32 cm away from the lower end we placed a
sand core plate aperture of 50–90 µm. Contaminants were exposed to the sample on the
core board through a quartz tube and then removed.

Figure 14. Simulation diagram of synthetic gas purification experiment for municipal solid waste.

In the HCl experiment, we first put the adsorbent in the quartz reactor, wrapped the
heating belt on the pipes, and opened the standpipe furnace and heating belt to heat it to
a preset temperature. When the temperature was stable, the hydrochloric acid solution
was injected with a syringe pump with the injection rate at 0.042 mL/min to ensure that
the hydrochloric acid solution could be vaporized at a stable rate. The whole experiment
was carried out with nitrogen as the carrier gas at a flow rate of 148 mL/min. Hydrogen
chloride was exposed to an adsorbent placed on a quartz tube sand core plate, and then the
chlorine was adsorbed and removed. To prevent condensation of hydrogen chloride in the
pipeline during the experiment, heating bands were wrapped on the tubes before and after
the reactor, and the heating band temperature was controlled at 120–130 ◦ C. After heating
the heating belt to the evaporation temperature and stabilizing for 30 min, we started the
Catalysts 2022, 12, 1519 14 of 17

timing. Hydrogen chloride gas was captured in 0.1 mol/L NaOH glass washing bottles
for tail collection, and chloride ions collected in tail washing bottles were detected by ion
chromatography (IC). Reaction samples were collected every 30 min and glass bottles were
replaced every half an hour. All experiments were repeated twice, and the results were
expressed as the average of the two experiments.
The experiment for catalytic tar reforming used naphthalene as a model tar compound [26].
Naphthalene vapor was produced by vaporizing naphthalene followed by N2 purging. A
certain temperature was set to ensure that the naphthalene was evaporated at a constant
flux in the evaporator, and brought into the catalytic reforming device through N2 as a
carrier gas. Naphthalene contacted the catalyst pre-placed on the sand core plate through
the quartz tube, and then catalytic reforming occurred. It generated small molecular carbon-
based compounds and synthesis gas (H2 , CO and a small amount of CH4 and CO2 ). To
avoid condensation of naphthalene vapor from the pipeline, the tetrafluoride pipelines at
the front and rear ends of the reactor were constantly heated (at 85–95 ◦ C), the naphthalene
vapor was captured by an isopropanol trap in the end, and the isopropanol solution was
analyzed by GC-MS, while the tailing gas was collected with a PTFE gas bag and passed
through a GC-Thermal Conductivity Detector (TCD)/Flame Ionization Detector (FID) The
carbon-containing gas content was measured to calculate the catalytic efficiency. In a typical
operation, the catalyst was first loaded into the quartz reactor, and the entire experiment
was fluidized with 200 mL/min of N2 gas. After the experiment began, the reactor was
heated to a preset temperature with a vertical tube furnace. We then turned on the heating
belts at the front and rear ends of the naphthalene evaporator and the reactor, allowing the
naphthalene evaporator to heat up to the designated temperature and stabilizing for 30 min.
The gas was passed through two isopropanol solutions to capture the residual naphthalene
vapor, and was then passed through anhydrous sodium sulfate to remove moisture. The gas
samples were collected every 20 min, lasting 5 min at a time. Naphthalene collection bottles
were replaced every half hour, and the exhausting gas was analyzed by GC-FID/TCD. All
experiments were triplicated, and the average value was reported.

3.3. Calculations and Characterization

3.3.1. Data Analysis
HCl conversion rate (%) can be calculated as follows:

n0HCl − n HCl
HCl conversion rate (%) = × 100% (1)
n HCl

where n0HCl (mg/L) refers to the concentration of HCl after reaction, and n HCl refers to the
inlet concentration.
Naphthalene conversion rate was calculated as follows:

nCO2 + nCO + nCH4

Naphthalene conversion rate (%) = × 100% (2)
nnap × 10

where nCO2 , nCO and nCH4 refer to the molar concentration of CO2 , CO and CH4 generated
during naphthalene reforming (mol/min), respectively. nnap (mol/min) refers to the
concentration of naphthalene.
Reaction space velocity was calculated as follows:

Q Nap
GHSV = (3)
V
where GHSV (/h) stands for gas hourly space velocity, Q Nap refers to the volumetirc flow
rate of naphthalene (L/h), and V refers to the volume of catalyst (L).
Catalysts 2022, 12, 1519 15 of 17

3.3.2. Characterization
Nickel in fresh catalysts is usually in an oxidized state. The contents of oxides in the
catalysts were tested by XRF, and the characterization results of catalysts are shown in
Table 3.

Table 3. XRF characterization results of Ni-based catalysts.

Metal Oxides (%) Commercial (25%) Self-Made (15%) Self-Made (25%)

Al2 O3 71.896 0 0
ZrO2 0 71.05 63.21
CeO2 0 - -
NiO 24.252 17.43 27.83
SO3 1.157 0.79 0.69
SiO2 2.219 0 0
P2 O5 0 0 0
CaO 0.228 0 0
Ta2 O5 0.089 0 0
Fe2 O3 0.092 0 0
Cr2 O3 0.021 0 0
K2 O 0.027 0 0
HfO2 0 1.45 1.23
MoO3 0 0.62 0.62
Nb2 O3 0 0.31 0.16
Na2 O 0 0 0.13

The nickel content of the commercial catalysts was close to the corresponding theo-
retical values, whereas that of the self-made catalysts (17.43% and 27.83%) was slightly
higher than the theoretical values (15% and 25%). It is noteworthy that cerium could not be
detected in the XRF spectrum, likely due to its low sensitivity for detection. In addition to
active component and support components, several types of trace metal oxides were also
detected. Commercial catalysts tend to be mixed with more SO3 , CaO, Fe2 O3 etc., which
may be the admixture of impurities in the preparation process. Self-made catalysts, on
the other hand, exhibit doping with trace amounts of noble metal oxides because of the
impurities inherent from the support.

4. Conclusions
With the improvement in living standards, the disposal of municipal solid waste has
become a serious challenge. Due to the advantages of incineration in the aspects of “Recycle,
Reuse and Reduce”, the proportion of these three disposal methods is increasing. Therefore,
in the context of sustainable energy, this research successfully developed a household-
waste synthetic-gas purification system for toxic and harmful substances in modern urban
household waste. The removal efficiency and conversion amount of hydrogen chloride and
tar in syngas were measured. The results of this study are summarized as follows:
(1) CaO adsorbent shows high efficiency of combining with HCl. At 400 ◦ C, the removal
rate of CaO adsorbent with HCl reaches 95.62%, and the adsorption capacity of the
adsorbent may decrease when the temperature exceeds 500 ◦ C. The reaction between
NaAlO2 adsorbent and HCl is more intense, but with the increase in the amount of
adsorbent, HCl cannot easily enter the interior of the adsorbent and react with it.
Therefore, for NaAlO2 , the removal efficiency of HCl is the highest when the reaction
space velocity ratio is 1.0.
(2) Experiments show that both the prepared nickel-based industrial catalysts for tar
catalytic reforming and the synthesized catalysts can provide more than 80% tar
removal. When the space velocity ratio is 1.89, a larger reaction area can be provided
for naphthalene catalytic reforming. At 800 ◦ C, 25% Ni-based synthetic catalyst can
convert tar to low-molecular-weight organic compounds (compounds with a carbon
number greater than 10). While commercial catalysts may have similar tar removal
Catalysts 2022, 12, 1519 16 of 17

effects, the greater carbon precipitation potential hinders the sustainability of their
long-term applications.
(3) For tar catalytic reforming experiments, no matter whether for commercial or home-
made catalysts, the oxygen of nickel oxide in the catalyst is consumed in the catalytic
reforming process to form CO, CO2 , etc., which indicates that a small amount of
oxygen left after the reaction may come from the carrier. Naphthalene has difficulty
reaching the catalyst in the process of high temperature reaction, thus forming an
incomplete reaction to yield fixed carbon, covering the reactor and the surface with
catalyst particles, thus preventing further catalytic reaction. Carbon deposition and
coking are the two main causes of catalyst deactivation.
(4) The syngas purification system used in this study has strong potential application
value in removing tar and acid gas produced by gasification. However, the larger scale
of domestic waste purification technology needs to be discussed in future studies, and
more attention should be paid to the possibility of converting tar into small molecular
organic compounds for reuse and the treatment of deactivated catalysts.

Author Contributions: Conceptualization, G.Y. and D.C.; methodology, G.Y., K.Y. and D.C.; valida-
tion, G.Y., W.Z., R.Y., Y.L. and J.Z.; formal analysis, W.Z., R.Y., Y.L. and J.Z.; investigation, G.Y., K.Y.
and D.C.; resources, G.Y.; data curation, W.Z., R.Y., Y.L. and J.Z.; writing—original draft preparation,
G.Y. and K.Y.; writing—review and editing, G.Y., Y.L., J.Z. and K.Y.; visualization, Y.L. and J.Z.;
supervision, K.Y. and D.C.; project administration, D.C.; funding acquisition, G.Y. All authors have
read and agreed to the published version of the manuscript.
Funding: This research was funded by Shanghai Rising-Star Program (22QB1403000) and Shanghai
Sailing Program (19YF1420800).
Data Availability Statement: No data availability.
Acknowledgments: We thank the financial support from Shanghai Rising-Star Program (22QB1403000);
Shanghai Sailing Program (19YF1420800).
Conflicts of Interest: The authors declare no conflict of interest.

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