Energy Conversion and Management 153 (2017) 473–481

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Co-gasification of municipal solid waste with high alkali coal char in a three- T
stage gasifier
⁎
Binhang Hua, Qunxing Huanga, , Alfons Buekensa,b, Yong Chia, Jianhua Yana
a
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, People's Republic of China
b
Chemical Engineering Department, Vrije Universiteit Brussel, Brussels, Belgium

A R T I C L E I N F O A B S T R A C T

Keywords: The commercial scale up of municipal solid waste (MSW) gasification system is restricted by the low quality of
Three-stage the syngas, especially due to the low heating value and high contents of tar and HCl. In this study, an innovative
Co-gasification three-stage system for co-gasification of MSW with high alkali coal char was developed. The modeled MSW was
Coal pyrolyzed in the first stage and the raw syngas was partially oxidized in the second stage and then reduced with
Syngas
high alkali coal char in the final stage to produce high quality syngas. The effects of temperatures and
HCl
equivalence ratios (ER) have been evaluated experimentally and the concentration of condensable tar species
Tar
and HCl was examined carefully. In general, the two key pollutants in produced gas could be controlled as low as
11.3 mg/Nm3 (tar content) and 17.6 mg/Nm3 (HCl content). Meanwhile, the level of H2, CO, CH4 in synthesis
gas reach a stable high level of 41.9 vol%, 29.3 vol% and 7.49 vol%, respectively, while the lower heating value
(LHV) attains 12.2 MJ/Nm3, meeting the intake-gas conditions for internal combustion engines. The experi-
mental results confirm that the highest pyrolysis temperature leads to the maximum gas yield from oxidation
stage (i.e., 0.913 Nm3/kg at 650 °C), to be compared with 0.898 Nm3/kg (550 °C) and 0.747 Nm3/kg (450 °C).
The lowest gasification temperature (800 °C) is indicated as most favorable for HCl removal from syngas, linked
with the advancement of reversible reactions between HCl and Ca-based compounds. H2, tar and LHV all de-
crease with rising equivalence ratio. In summary, the high-quality syngas can be produced at a steady yield rate
of 1.57 Nm3/kg from three-stage gasifier, due to dichlorination and catalytic tar cracking action of high alkali
coal char at a low cost.

1. Introduction
The amounts of municipal solid wastes (MSW) are endlessly in-
creasing with economy growth, raising the sustainable management
solutions issues [1–10]. Gasification is another thermochemical process
involving a partial oxidation of organic compounds between 500 and
1800 °C to realize high-quality and clean utilization of MSW, producing
a syngas which can be used as a fuel for efficiently yielding heat and
power, or as a feedstock for the production of organic chemicals and
ammonia after some reforming reactions [11–13]. Various studies have
also pointed out the gasification possesses better performance in higher
electrical and overall energy efficiency, lower emissions and lower in-
vestment costs than direct combustion [14–19].
As a consequence, lots of studies have focused on the performance
of MSW gasification, as well as co-gasification process. A compact de-
sign of “UNIQUE” gasification concept integrating gasification, gas
cleaning and conditioning in one single reactor unit was developed
after collaborative R & D efforts [20]. The activity of catalysts and
sorbents sited in the gasifier is improved through the integral layout,
while keeping the thermal efficiency high [21]. A specially designed
three-stage gasification process of “FLETGAS” was proposed by Nilsson
et al. [22], which was consist of a first, fluidized bed devolatilization
(700–750 °C), a subsequent steam reforming of fresh tar at 1200 °C and
a final moving bed downdraft gasifier [23]. Nevertheless, the actual
industrial implementation of gasification processes of MSW faces sev-
eral challenges when brought to the market. In particular, the gas
produced contains a high level of condensable organic compounds
(usually referred to as tars) which cause blockage and corrosion in
gasifiers and also reduces overall efficiency [24–27]. Secondly, MSW
typically contains significant amounts of chlorine, mainly associated
with the food waste stream and plastic waste, forming acid gas (HCl)
during gasification and causing severe corrosion of down-stream
equipment, as well as poisoning the catalysts used for tar cracking
[28–30].
These two obstacles result in a lower calorific value of syngas, with
impurities that impose restrictions on a wider market penetration of

⁎
Corresponding author.
E-mail address: hqx@zju.edu.cn (Q. Huang).

http://dx.doi.org/10.1016/j.enconman.2017.10.026
Received 17 July 2017; Received in revised form 7 October 2017; Accepted 9 October 2017
Available online 16 October 2017
0196-8904/ © 2017 Elsevier Ltd. All rights reserved.
B. Hu et al.
commercial advanced gasification technologies. The inferior coal at a
low-cost contains significant amounts of alkali metals which are im-
portant catalysts for tar cracking, and it can be co-gasified with MSW to
improve the syngas quality. Co-gasification of waste with coal is very
promising method to convert the solid waste into syngas which can be
burned or used as chemical feedstock. It has received intensive interests
in the past few years. Pinto et al. [31] tested the co-gasification of coal
mixed with waste and compared tar cracking catalysts. Five mixtures of
coals, plastics and wood have been pelletized and fed into a bubbling
fluidized bed gasifier by Zaccariello et al. [32] to compare the overall
performance efficiency of the co-gasification process. Filomena et al.
[33] performed the co-gasification experiment of different grade coals
mixed with different types of biomass waste. Whereas, some problems
exist in these direct blending co-gasification as: (1) the waste must be
dried and shredded to achieve well blending and the syngas contains
high concentration of particulate matters; (2) the syngas contains high
content of tar due to the lack of reduction stage; (3) the HCl problem
during the gasification of waste with high chlorine content is ignored
[31–37]. In this study, an innovate three-stage system was developed
for co-gasification of MSW and coal char. The innovation points lie in
the usage of high alkali coal char as catalyst for tar cracking, absorbent
for HCl removal and gasification reactant, and the two feedstocks are
separated into two reactors in the integrated gasification system. The
findings of this paper are expected to provide a deeper understanding
on the characteristic of the multi-stage co-gasification process and
suggest a feasible gasification way for the disposal of municipal solid
waste with high chlorine content, which can be driven to the market.
2. Materials and experimental methods
2.1. Materials
The major raw materials adopted were wood chips from Shanghai
Yourui Wood Industry Co., Ltd, simulating a first key component (wood
waste) of MSW [1]. The wood material was sieved to a size between 0.1
and 0.84 mm (average: 0.4 mm) [38]. The chlorine content of the feed
was less than 0.01% by weight; no polymer resin or glue was present.
Polyvinyl chloride (PVC) powder was purchased from Sigma-Aldrich
Co. (USA) and used as an additive, simulating a second key component
(plastic waste) of MSW [1], the particle size of which was less than
0.125 mm. A mixture of wood chips and PVC powder (chlorine content
1%) was employed as simulated waste feedstock. The proximate and
ultimate analysis of raw materials was shown in Table. 1. The “Zhun-
dong” coal char added during the third stage serves as reactant and
catalyst for tar cracking. It derives from the giant Eastern Junggar
coalfield (Sinkiang Uygur Autonomous Region, China) and is rich in
both alkali and alkaline-earth metals. Table. 2 shows its ash composi-
tion; the Na2O and K2O content attains 4.7% and 0.5%, respectively,
and the CaO and MgO content 35.1% and 12.5%, respectively.
2.2. Experimental set-up
A schematic representation of the three-stage laboratory-scale co-
gasification of MSW and coal char apparatus is shown in Fig. 1. The
apparatus mainly consists of a reverse L tubular reactor made of steel
(length: 1150 mm, height: 650 mm, outer diameter: 30 mm, inner
Table 1
Proximate and ultimate analysis of raw materials.
Sample Proximate analysis/% Ultimate analysis/%
Mad Aad Vad FCad Cad
Wood 11.9 ± 0.3 9.2 ± 0.3 59.8 ± 1.2 19.1 ± 0.5 48.0 ± 0.6
PVC 1.4 ± 0.0 0.0 ± 0.0 93.6 ± 2.1 5.0 ± 0.1 39.1 ± 0.3
Coal char 0.9 ± 0.0 8.9 ± 1.7 6.9 ± 0.2 83.3 ± 1.1 78.2 ± 1.5
474
Energy Conversion and Management 153 (2017) 473–481
diameter: 20 mm). The reactor is subdivided into three stages, sig-
nifying pyrolysis, oxidation and reduction. The three process stages are
heated by three electric furnaces (SKF-2-13 Hangzhou blue sky Instru-
ment Co., ltd, China) and temperature is controlled for pyrolysis at 450,
550, and 650 °C, for oxidation at 800 °C, and for reduction at 800, 900,
and 1000 °C.
The first treatment stage is a pyrolysis process [16]. Simulated MSW
feedstocks are delivered at 1.33 g/min by a screw feeder compactly
installed in a steel tube to seal the entrance. Initial trials demonstrated
that the 1.33 g/min of the screw feeder could reach the complete re-
actions. The second stage is oxidation of pyrolysis tar and gas with a
mix of nitrogen and oxygen. Two mass flowmeters (D08-1F, Beijing
seven-star Huachuang Electronics Co., Ltd, China) are used to set the
gas flow of N2 and O2, at three different equivalence ratios (ER), to
define an appropriate amount of oxidizing agent. The third stage is an
up-draft fixed bed gasifier with coal char of high alkali contents placed
above an air distributor using oxidation gas from the burning chamber
as a reacting agent. A stack of 250 mm high alkali coal char provides
enough residence time (about 3 s) to complete the Boudouard, water-
gas reaction and methanation reaction [39]. Since the last chemical
reaction is strongly endothermic and the upward flue gas could transfer
a portion of heat to downward feed in up-draft gasification furnace, the
synthetic gas cools down to below 300 °C. Therefore, this “chemical
quenching” enhances the calorific value.
Gas is sampled at the entrance and exit of this third stage, with two
flowmeters to measure the gas yield rates, respectively. The gas bubbles
through two 50 ml scrubbing bottles containing 30 ml of 0.1 mol/L
sodium hydroxide solutions for capturing HCl gas before and after the
third stage in the flue gas, respectively. The chloride ion concentration
in the mixed solutions, which accounts for the HCl gas concentration
can be directly detected through high-pressure ion chromatography
(Integrion Thermo scientific, USA) with maximum operating pressure
up to 6000 psi. When detecting the tar content in the gas, the sodium
hydroxide solution in the scrubbing bottles is replaced by aqueous so-
lutions and the tar in the tar trap is collected by washing with about
50 mL of dichloromethane for three times. The mixture of water and
organic solvent (mixture of tar and dichloromethane) was separated by
a tap funnel. Then, the tar was separated from the mixed organic sol-
vent by a rotary evaporator [40]. Eventually, the gas lines are con-
nected to gas sampling bags and gas is collected for 6 min for every bag.
The entire experimental procedure lasts for 60 min. Thus, 20 gas sam-
pling bags (2 L for each one) in each experiment are analyzed by gas
chromatography and the key components of the produced gas (H2, CO,
CH4, C2H4, C2H2, C2H6, CO2, O2) are analyzed using an Agilent
490 micro GC (type of chromatographic columns, MS5A 10 m BF and
PPU 10 m BF; and temperature of the columns, 80 °C, Agilent Tech-
nologies Inc., USA). After the co-gasification experiments, the coal char
after reaction in Run 2 was analyzed with an Empyrean 200895 X-ray
diffractometer system with Cu Kα as radiation source (λ = 1.5406 Å)
made by Panalytical, Netherlands to characterize the crystalline phases.
All detail experimental conditions were displayed in Table. 3. Each run
was performed for three times, ensuring the experimental repeatability.
3. Results and discussion
The experimental results featuring three-stage co-gasification
Qnet,ad (kJ/kg)
Had Nad St,ad Oad Clad
4.9 ± 0.1 0.2 ± 0.0 0.9 ± 0.1 24.9 ± 0.4 0.0 ± 0.0 15980.2 ± 33.6
5.0 ± 0.1 0.4 ± 0.0 1.2 ± 0.1 0.0 ± 0.0 52.9 ± 0.2 20710.3 ± 42.7
1.1 ± 0.1 1.1 ± 0.0 0.4 ± 0.0 9.4 ± 0.6 0.0 ± 0.0 31210.9 ± 53.1
B. Hu et al. Energy Conversion and Management 153 (2017) 473–481

Table 2
Ash composition of “Zhundong” coal sample.

Coal char Ash composition / wt.%

SiO2 Al2O3 CaO MgO Fe2O3 Na2O K2O SO3
Zhundong 31.6 ± 0.5 5.4 ± 0.1 35.1 ± 0.8 12.5 ± 0.4 5.3 ± 0.2 4.7 ± 0.5 0.5 ± 0.0 4.8 ± 0.5

include: gas yield rate, syngas composition and LHV, gasification effi- Table 3
ciency, and impurities in the gas produced. They are presented in Table. Experimental conditions.
4 (The Y(gas)oxidation refers to the yield gas from the second oxidation
Experimental Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7
stage, and the Y(gas)reduction refers to the yield gas from the third re- conditions
duction stage). Each mass balance is established on a basis of total
input. The cold gas efficiency (CGE) and the carbon conversion effi- Pyrolysis temperature 450 550 650 550 550 550 550
ciency (CCE) which can estimate the effectiveness of three-stage co- (°C)
Oxidation temperature 800 800 800 800 800 800 800
gasification process are defined as [41]: (°C)
CV of syngas × total syngas output Reduction temperature 800 800 800 900 1000 800 800
CGE(%) = × 100 (°C)
CV of waste feedstock × total waste input ER 0.35 0.35 0.35 0.35 0.35 0.25 0.45
+ CV of coal char × total consumption Waste feed rate (g/ 1.33 1.33 1.33 1.33 1.33 1.33 1.33
(1)
min)
Stack height of coal 2.49 2.50 2.51 2.49 2.52 2.51 2.51
Total carbon (c1−c2) in syngas
CCE(%) = char (cm)
Total carbon in waste feedstock + Total carbon in coal char Co-gasification time 60.0 60.0 60.0 60.0 60.0 60.0 60.0
× 100 (2) (min)

where CV in formula (1) represents the calorific value, the total syngas
output, waste input and coal char consumption in formula (1) refer to total
amounts during 60 min of co-gasification reaction time. The C1-C2 in
formula (2) refers to carbon contents of CO2, CO, CH4, C2H2, C2H4, and
C2H6 in syngas. Both CGE and CCE produce an estimate of the co-ga-
sification efficiency. In these experiments, the LHV of the produced gas
is in the range of 10.6–12.2 MJ/Nm3. Their impurity content depends
on the process variables, as explained in more detail in the following
sections.
3.1. Gas analysis
The yield rate of gas emitted from the second and third stage (oxi-
dation and reduction stage), and the ratio of coal char consumption and
waste feedstock are presented in Fig. 2. In general, the syngas yield rate
is in the range of 0.972 – 1.57 Nm3/kg, with the ratio of coal char
consumption and waste feedstock from 0.195 to 0.238 during the total
60 min of co-gasification reaction time. The highest syngas yield rate at
1.57 Nm3/kg in Run 2 also leads to the optimal cold gas efficiency
(97.4%) and carbon conversion efficiency (90.4%).
Fig. 3 shows the volumetric composition of the gaseous products,
evolving from the second and third stage of the three-stage co-gasifi-
cation apparatus during Run 2. A steady-state was achieved after
24 min of gasification. Prior to that, the pyrolysis gas from the first
pyrolysis stage was gradually discharged and sufficient oxidizing agent
was furnished into the second oxidation stage, consequently, resulting
in an escalated growth of CO2. Some H2 and CO might result from
catalytic tar cracking accomplished by an abundant content of alkali
and alkaline earth metals in coal char in the third reduction stage in

Fig. 1. Schematic representation of experimental apparatus.

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B. Hu et al. Energy Conversion and Management 153 (2017) 473–481

Table 4
Experimental results.

Experimental results Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7

Composition (vol%)
N2 22.3 17.2 18.1 19.8 23.0 27.8 20.8
CO2 4.45 3.90 3.61 6.31 8.14 2.26 10.7
H2 39.3 41.9 41.4 39.0 36.8 37.9 33.2
CO 27.1 29.3 28.6 27.6 25.3 24.7 28.8
CH4 6.64 7.49 8.11 7.11 6.57 7.18 6.29
C2H2 1.04 × 10−1 9.92 × 10−2 6.43 × 10−2 8.44 × 10−2 1.03 × 10−1 1.36 × 10−1 1.60 × 10−1
C2H4 5.31 × 10−2 1.25 × 10−1 5.31 × 10−2 9.02 × 10−2 7.83 × 10−2 7.71 × 10−2 9.93 × 10−2
C2H6 5.23 × 10−3 3.29 × 10−3 1.43 × 10−3 2.21 × 10−3 1.43 × 10−3 1.25 × 10−3 3.48 × 10−3
LHV (MJ/Nm3) 11.8 12.2 11.6 11.4 10.6 10.9 10.5

Gas yield rate (Nm3/kg)

Y(gas)oxidation 0.747 0.898 0.913 0.863 0.791 0.752 0.926
Y(gas)reduction 1.21 1.57 1.49 1.37 1.17 0.972 1.30
H2O(gas)oxidation (g/Nm3) 15.7 17.8 18.5 17.1 18.2 14.6 18.1
H2O(gas)reduction (g/Nm3) 4.41 3.62 4.68 5.36 6.74 5.12 7.33
Coal char consumption /waste feedstock 0.195 0.228 0.215 0.197 0.171 0.148 0.238
Boudouard reaction /Water-gas reaction 0.761 0.831 0.922 0.998 0.963 0.956 0.775
Total tar (mg/Nm3) 106 124 215 116 120 236 53.0
Total HCl (mg/Nm3) 255 256 256 259 258 259 260

Process efficiency (%)

Cold Gas Efficiency 72.5 97.4 88.1 79.2 63.4 54.1 69.6
Carbon Conversion Efficiency 65.1 90.3 84.4 78.8 66.0 46.8 83.8
Tar removal efficiency 83.1 90.9 89.5 84.6 86.3 89.1 82.0
HCl removal efficiency 93.2 93.1 93.1 83.7 72.9 93.0 93.2

Impurity in produced gas (mg/Nm3)

Tar 17.9 11.3 22.6 17.9 16.5 25.7 9.56
HCl 17.4 17.6 17.7 42.1 69.9 18.1 17.5

contained H2, CO and CH4, with H2 possessing the highest yield, fol-
lowed by CO and CH4. In detail, the H2 and CO accounting for the
syngas could reach a stable high level of 41.9% vol.% and 29.3% vol.%,
respectively. The fluctuation portion after 24 min could be ascribed to
the deactivated catalyst of coal char during the co-gasification of MSW
and coal char [42]. The low heating value (LHV) of syngas could be
calculated by the following formula [18]:
LHVsyngas = SUM (LHVn Vol%). (3)

where the LHVsyngas refers to the low heating value of total syngas,
while the LHVn represented the specific calorific value of a gas com-
ponent specie, and the SUM signified a summation operation. The ty-
pical gas specie of 12.6 MJ/Nm3 for CO, 39.8 MJ/Nm3 for CH4,
12.7 MJ/Nm3 for H2 and 0 MJ/Nm3 for CO2 were referenced here. By
weighted calculation, the calorific value of syngas produced from the
three-stage co-gasification system could run up to 12.2 MJ/Nm3 which
met the intake-gas requirement for internal combustion engine.
Fig. 2. The yield rate of gas from the oxidation and reduction stage, and the ratio of coal
char consumption and waste feedstock.
3.2. Effect of pyrolysis temperature

addition to the portion converted from the oxidation process. The re-
duction zone between the two gas sampled positions contains hetero-
geneous reactions of CO2 and carbon to produce CO. The consumption
of CO2 occurred through the gasification stage in accordance with the
comparison of CO2 gas component in Fig. 3(b), and the small peak
appeared at about 54 min was due to the Boudouard reaction. This
reaction worked well at high temperatures that were required for the
endothermic reaction. Therefore, the molar fraction of CO increased
gradually to a stable level with the reaction time. Another endothermic
and heterogeneous reaction also occurred between water vapor and
carbon in the reduction zone, wherein water participated in producing
CO and H2. The production of methane derived from numerous com-
plicated chemical reactions, mainly by decomposition of volatiles from
feedstocks and exothermic reaction of carbon, CO or CO2 with H2.
These reactions collectively increased the calorific value of the pro-
duced gas as its products are combustible. The combustible gases
The pyrolysis process is an essential preliminary step in this three-
stage gasifier, described by a general reaction formula [18]:
heat
Cn Hm Op (Waste ) ⎯⎯⎯→ ∑ Cx Hy Oz + ∑ Ca Hb Oc + H2 O + Char
Liquid Gas (4)
Encinar et al. [43] investigated the effect of temperature
(300–900 °C) on the char, gases and liquids from olive and grape ba-
gasse pyrolysis, and found the higher pyrolysis temperature resulted in
greater amount of gas yield while low temperatures resulted in less.
Such trends could also be confirmed in this study through the contrast
of gas yield from the second oxidation stage in Run 1-3, which was set
at three different pyrolysis temperatures (450 °C, 550 °C and 650 °C). It
can be clearly observed from Fig. 2 that the highest pyrolysis tem-
perature leaded to the maximum gas yield from oxidation stage (i.e.,
0.913 Nm3/kg at 650 °C), associated with further devolatilization of the
solid fraction, to be compared with 0.898 Nm3/kg (550 °C) and

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B. Hu et al. Energy Conversion and Management 153 (2017) 473–481

0.747 Nm3/kg (450 °C). The volume percentages of main syngas com-
ponents at three pyrolysis temperatures are shown in Fig. 4. Both pri-
mary syngas composition of H2 and CO showed a maximum value at
550 °C, reaching 41.9% vol.% and 29.3% vol.%, respectively. As we
know, a higher pyrolysis temperature would favor the decomposition of
hydrocarbon compounds into smaller hydrocarbons which will be ea-
sily oxidized to form more water and carbon dioxide molecules.
Therefore, the water concentration in gases from the oxidation stage
increased gradually from 15.7 to 18.5 g/Nm3 with the rising pyrolysis
temperature. Besides, the decomposition of hydrocarbon compounds
had been revealed from some light hydrocarbons (CH4, C2H2, C2H4 and
C2H6) in the produced gas. For instance, CH4 accounts for 6.64 vol%,
7.49 vol% and 8.11 vol% in produced gas, with increasing pyrolysis
temperature from 450 °C, 550 °C to 650 °C, respectively. Similar trends
could be observed for the other three micromolecular hydrocarbons.
Besides, the tar content in the gas yielded from the second stage was
strongly dependent on pyrolysis temperature. A significant rise of tar
concentration from 106 to 215 mg/Nm3 was seen from 450 °C to 650 °C
(Run 1 and 3), due to more gaseous products yielded from the higher
pyrolysis temperature could not be oxidized completely with the con-
stant amount of oxygen.
Fig. 5 shows the process efficiency and syngas LHV of all seven
experiment conditions. The contrast of Run 1, 2 and 3 revealed the
highest cold gas efficiency (97.4%), carbon conversion efficiency
(90.3%) and LHV (12.2 MJ/Nm3) attain at 550 °C of pyrolysis tem-
perature. It demonstrated that the pyrolysis gas yielded from the first
stage at 550 °C could be oxidized completely, thus achieving high
conversion efficiency of chemical energy.

3.3. Effect of reduction temperature

Comparing Runs 2, 4 and 5 reveals the effect of reduction tem-

Fig. 3. The produced gas composition in the second (a) and third stage (b) of the three-
stage co-gasification process in Run 2.
perature on gas composition, amount of pollutants and co-gasification
efficiency (Table. 3), and Fig. 6 exhibits the main syngas components at
three reduction temperatures. The CO2 content augmented from 3.90 to
8.14 vol% with temperature ascending from 800 °C to 1000 °C, while H2
and CO declined from 41.9 to 36.8 vol% and from 29.3 to 25.3 vol%,
respectively. It might be associated with the melting of some metal
chlorides such as CaCl2 and MgCl2 formed from the metallic oxide in
coal char incorporating HCl in high reduction temperature conditions,
resulting in slagging phenomenon, which would seriously reduce the
activity of coal char as both gasification reactant and catalysts for tar
cracking. Hence, the tar removal efficiency is greatly related to the
reduction temperature, which will be explained particularly in Section
3.5.
The combustible gas decrease of CO and H2 also directly leads to a

Fig. 4. The volume percentages of main syngas components at three pyrolysis tempera-
tures.

Fig. 5. The process efficiency and syngas LHV of all seven experiment conditions.

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B. Hu et al.
Fig. 6. The volume percentages of main syngas components at three reduction tem-
peratures.
lower LHV at high reduction temperature. For instance, the LHV de-
clined to 10.6 MJ/Nm3 at the reduction temperature of 1000 °C com-
pared with a high LHV value of 12.2 MJ/Nm3 at the gasification tem-
perature of 800 °C. As for co-gasification process efficiency shown in
Fig. 5, the cold gas efficiency, carbon conversion efficiency and LHV of
syngas all decrease progressively with ascending reduction tempera-
ture, as low as 63.4%, 66.0% and 10.6 MJ/Nm3 at 1000 °C, respec-
tively.
The Boudouard reaction and water-gas reaction were considered as
two primary gasification reactions in the third reduction stage. While
leaving out the other chemical reactions in the reduction stage, the
intensity of Boudouard reaction could be estimated by the decrement of
carbon dioxide during the reduction stage on the basis of gas yield rate
and volume fraction of CO2 in Table. 4. On the other hand, the intensity
of water-gas reaction could be estimated by the decrement of water
concentrations during the reduction stage according to the water con-
centrations from the oxidation and reduction stage. In general, the
decreased volume ratio of carbon dioxide and water vapor (consump-
tion of CO2 reduction stage/consumption of H2Oreduction stage) could be used
to indicate which reaction is dominating, Boudouard reaction or water-
gas reaction. As shown in Table. 4, the intensity ratio of Boudouard
reaction and water-gas reaction was lower than one for each run, which
indicated that water-gas reaction played dominating role during the
reduction stage. Besides, Boudouard reaction occupied an increasingly
greater part compared with water-gas reaction with increasing reduc-
tion temperature, because Boudouard reaction and water-gas reaction
tend to benefit syngas yield at a higher temperature while the water-gas
reaction was weakened with the increasing reduction temperature. It
might be caused by the slagging and blocking of chlorides in the coal
char placed on the reduction stage at a high reduction temperature
[28].
3.4. Effect of equivalence ratio
The effect of ER on the co-gasification parameters of the three-stage
experimental apparatus is derived from Run 2, 6 and 7, and Fig. 7 re-
veals the main syngas components at three equivalence ratios. A higher
ER value indicates a higher oxygen supply in the second oxidation
stage, enhancing oxidation reactions and abundantly producing CO2
and H2O before entering into the third-stage. Thus, the water contents
in gases emitted from the oxidation stage reached 18.1 g/Nm3 at ER of
0.45, compared with 14.6 g/Nm3 at ER of 0.25. H2, tar and LHV all
decrease with rising ER. When ER amplifies from 0.25 to 0.45, the H2
content reduced from 37.9 to 33.2 vol%, while CO and CO2 augment
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Energy Conversion and Management 153 (2017) 473–481
Fig. 7. The volume percentages of main syngas components at three equivalence ratios.
from 24.7 vol% to 28.8 vol% and 2.26 vol% to 10.7 vol%, respectively.
Furthermore, a significant tar reduction could be seen, from 236 (ER
0.25) to 53.0 mg/Nm3 (ER 0.45).
The HCl formed from the first-stage pyrolysis reaches 259 mg/Nm3,
256 and 260 mg/Nm3 in the gas yielded from the second stage, for ER-
values of 0.25, 0.35 and 0.45, respectively. It is quite stable during high
temperature oxidation. A maximum LHV of 12.2 MJ/Nm3 is attained at
an ER of 0.35, to be compared with 10.9 MJ/Nm3 (ER 0.25) and
10.5 MJ/Nm3 (ER 0.45), since the lack of oxygen supply resulted in less
gasification reactants of CO2 and H2O, and the excessive oxygen supply
caused the existence of a mass of CO2 in the produced gas (10.7 vol%)
which strongly lowered the LHV of produced gas. As for yield rate of
produced gas, the gas yielded from the second oxidation stage sig-
nificantly possessed a higher production rate at a higher ER value, from
0.752 Nm3/kg (ER 0.25) to 0.926 Nm3/kg (ER 0.45), seen in Table. 3.
Since the higher ER promotes the oxidation of hydrocarbons including
tar micromolecular hydrocarbons, which appears to result in the in-
creased production of produced gas. In addition, the variation of ER
also has a great influence on the cold gas efficiency and carbon con-
version efficiency. Both two parameters revealing the gasification per-
formance achieved its maximum at an optimum ER value of 0.35, seen
in Fig. 5. Besides, a relatively high process efficiency was obtained at a
high ER value of 0.45, while attaining a lowest value of LHV (10.5 MJ/
Nm3) due to the dilution effect of excess nitrogen.
3.5. Tar content analysis
The tar concentration in the dry syngas was also a key parameter for
the design of three-stage co-gasification apparatus. The concentrations
of tar produced from the second and third stage of the three-stage ga-
sification apparatus under seven operating conditions of Run 1-7, and
tar removal efficiency through the third gasification process stage were
illustrated in Fig. 8. The tar removal efficiency mentioned here is de-
fined by the following formula [40]:
Tar removal efficiency
tar content in second stage−tar content in third stage
=
tar content in second stage (5)
In general, the tar contents in the flue gas were all significantly
reduced while going through the third gasification stage, which was
particularly obvious at Run 2, resulting in a tremendous decline by
90.863%. The most decrease of tar content could be attributed to the
catalytic cracking effect of alkali and alkaline earth metal which was
abundant in the “Zhundong” coal char also as a reactant of Boudouard
reaction. Deeply, the tar removal efficacy of different catalysts
B. Hu et al. Energy Conversion and Management 153 (2017) 473–481

Fig. 8. The tar contents in the second and third stage of the three-stage co-gasification Fig. 9. The HCl gas content in the second and third stage of the three-stage gasification
apparatus, and the tar removal efficiency through the third stage. apparatus, and the HCl removal efficiency through the third stage.

compared by a large amount of studies had revealed that the oxide and that HCl could be significantly reduced (up to about 93%) while passing
carbonate compounds of alkali and alkaline earth metals were rather through the “Zhundong” coal char located in the third reduction stage.
efficient catalysts for tar cracking [29,44–45]. The following catalytic Combined with the proximate and ash composition analysis of coal char
reactions might take place during catalytic cracking of tar: (Table. 1 and 2), this coal char has a high content of alkali and alkaline
Catalytic cracking: Cn Hm·C + Cx Hy + H2 earth metal (Table. 1). Ca-, Mg-, Na- and K-based sorbents are quite
effective in removing HCl [47–48]. Their oxide, carbonate and hydro-
Dry reforming : Cn Hm + n CO2 ⇌ 2n CO + 1/2m H2 xide easily reacts with HCl to form the corresponding chloride. Fig. 10
which shows the XRD spectrograms analysis result of the raw coal char
Steam reforming: Cn Hm + n H2 O⇌ n CO + (n + 1/2m)H2 before co-gasification and the coal char after co-gasification at reduc-
tion temperature of 800 C (Run 2), 900 °C (Run 4) and 1000 °C (Run 5),
where CnHm refer to various types of tars (the compounds with its
also confirmed the majority of HCl was assimilated by CaO and MgO to
molecular masses larger than that of benzene), while CxHy represented
form CaCl2 and MgCl2, with melting points of 782 °C, 714 °C, and
hydrocarbon with a smaller carbon number than CnHm.
boiling points of 1600 °C, 1412 °C, respectively. Thus, the operating
As for comparison of different reduction temperatures in Run 2, 4
temperatures (800 °C, 900 °C, 1000 °C) were between the melting and
and 5, the tar removal efficiency presented a more inferior effectiveness
boiling points of CaCl2 and MgCl2, causing the slagging and agglom-
at a higher reduction temperature, which was speculated that the
erate of coal char. Theoretically, the vaporization of these two chlorides
higher reduction temperature leaded to a slagging phenomenon caused
could not occur during the reduction stage. The results of chlorine mass
by melting of some metal chlorides such as CaCl2 and MgCl2 formed
balance were supplemented to evaluate the effects of vaporization of
from the metallic oxide in coal char incorporating HCl. The slagging
other chlorides, as shown in Fig. 11. The recovery percent of chlorine
phenomenon would significantly weaken the tar catalytic cracking of
could reach a high level above 95%, with a chlorine loss less than 5%.
coal char. Although, the reactivity of coal chars related to thermal
Therefore, the slagging of coal char played a primary and increasingly
cracking for tar increased as the gasification temperature was elevated.
destructive effects on the coal char reactivity by the rising reduction
While the increasing extent of the reactivity of coal chars was smaller
temperature. Apparently, the CaO played the main role in HCl removal
and smaller above the ash fusion temperature and even almost un-
changed in the higher temperature range [46]. It could be inferred that
the chlorides slagging played a larger role than increasing reduction
temperature on the coal char reactivity of thermal cracking. For in-
stance, the tar removal efficiency at reduction temperature of 900 °C
decreased to 84.6%, compared with 90.9% (800 °C). Whereas, the tar
removal efficiency increased slightly to 86.3% at reduction temperature
of 1000 °C compared with 900 °C, due to the enhancement of tar
thermal cracking with increasing reduction temperature.

3.6. HCl analysis

The concentration of HCl gas evolving from the second and third
stage is depicted in Fig. 9 for Runs 1-7. The HCl removal efficiency is
defined by the following formula [40]:

HCl removal efficiency

HCl content in second stage−HCl content in third stage
=
HCl content in second stage (6)

After the second stage, the HCl content reaches about 250 mg/Nm3
under all seven operating conditions, due to the release of almost all
chlorine from the PVC in the feedstock as HCl, after the first pyrolysis
stage. The HCl concentration is far less after the third stage, inferring
Fig. 10. XRD spectrograms of the raw coal char before co-gasification and the coal char
after co-gasification at reduction temperature of 800 °C (Run 2), 900 °C (Run 4) and
1000 °C (Run 5).

479
B. Hu et al.
Fig. 11. The results of chlorine mass balance.
Table 5
BET specific surface areas (m2/g) of coal chars after reduction reaction in Run 2, 4 and 5.
Reduction temperature (°C) BET Specific surface area (m2/g)
800 127.6 ± 1.2
900 98.2 ± 0.6
1000 74.9 ± 0.8
during the third reduction zone. However, the temperature higher than
800 C are required for the simultaneous catalytic tar elimination and
the Boudouard reaction for yielding syngas. Then the particles of these
two chlorides melt and agglomerate or glue themselves, causing the
collapse of the bed materials of coal char placed in the reduction zone.
Thus, the adsorbing capacity of coal char weakened significantly with
the increasing reduction temperature from 800 C to 1000 °C [28]. As
confirmed in Fig. 10, the peaks of CaCl2 (at about 25.8° and 32.3°) and
MgCl2 (at about 65.7°) all decreased as reduction temperature raised
from 800 C to 1000 °C. Table. 5 presented the BET specific surface areas
of coal chars after reduction reaction in Run 2, 4 and 5. It could be seen
that the BET specific surface area of coal chars after reduction reaction
decreased from 127.6 to 74.9 m2/g with the increasing reduction
temperature.
HCl removal efficiency (Run 2, 4 and 5) diminished with rising
reduction temperature, indicating that higher temperature is unfavor-
able for de-chlorination by Ca-based compounds as HCl absorbents
[41,42]. A number of studies also pointed that the capacity of Ca-based
additive for capturing HCl gas weakened with increasing temperature
over 750 °C and CaCl2 had poor stability at high temperature. Fur-
thermore, the phenomenon has been explained by a thermogravimetric
analysis of CaCl2 that the CaCl2 had an obvious weight loss at about
750 °C [37], which meant a higher temperature (over 750 °C) would
favor the CaCl2 decomposition reaction, then, promoting the reversible
reactions of Ca-based compound and HCl to the reverse and accordingly
producing more HCl gas.
4. Conclusions
The laboratory-scale three-stage co-gasification of MSW and
“Zhundong” coal char apparatus consists of the first pyrolysis, the
second oxidation and the third reduction process was experimentally
studied. The primary findings are summarized as follows:
(1) The proposed staged-gasification could optimize the MSW gasifi-
cation effectively. With the use of high alkali content coal char, the
480
Energy Conversion and Management 153 (2017) 473–481
syngas quality could be greatly improved, and meanwhile the HCl
concentration could be controlled to a low level.
(2) The syngas could reach a stable level of 41.9 vol% of H2, 29.3 vol%
of CO, 7.49 vol% of CH4 and 3.90 vol% of CO2 with the calculated
low heating value achieving 12.2 MJ/Nm3.
(3) The highest syngas yield rate at 1.57 Nm3/kg was attained in Run 2,
leading to the optimal cold gas efficiency (97.4%) and carbon
conversion efficiency (90.3%).
(4) The tar and HCl contents could be reduced to a minimum value of
9.56 mg/Nm3 and 17.4 mg/Nm3 with the catalytic effect of coal
char.
(5) A higher reduction temperature (over 800 °C) would be unfavorable
for tar catalytic cracking and dichlorination effect of high alkali
coal char, caused by the melting of corresponding metal chlorides.
(6) The XRD analysis confirmed the majority of HCl in syngas was as-
similated by CaO and MgO, and CaO plays the main role in HCl
removal.
Notes
The authors declare no competing financial interest.
Acknowledgments
The authors would like to greatly acknowledge National Natural
Science Foundation of China (Grant No. 51621005), the National Key
Research and Development Program of China (2016YFE0202000),
Science and Technology Plan Project of Zhejiang Province (No.
2016C33005) and the Environmental Protection Special Funds for
Public Welfare (201509013) and the Fundamental Research Funds for
the Central Universities.
References
[1] Zhou H, Meng A, Long Y, Li Q, Zhang Y. An overview of characteristics of municipal
solid waste fuel in China: physical, chemical composition and heating value. Renew
Sustain Energy Rev 2014;36:107–22.
[2] Cheng H, Hu Y. Municipal solid waste (MSW) as a renewable source of energy:
current and future practices in China. Biores Technol 2010;101(11):3816–24.
[3] Zhang DQ, Tan SK, Gersberg RM. Municipal solid waste management in China:
status, problems and challenges. J Environ Manage 2010;91(8):1623–33.
[4] Chen X, Geng Y, Fujita T. An overview of municipal solid waste management in
China. Waste Manage 2010;30(4):716–24.
[5] Tan ST, Ho WS, Hashim H, Lee CT, Taib MR, Ho CS. Energy, economic and en-
vironmental (3E) analysis of waste-to-energy (WTE) strategies for municipal solid
waste (MSW) management in Malaysia. Energy Convers Manage 2015;102:111–20.
[6] Ouda OKM, Raza SA, Nizami AS, Rehan M, Al-Waked R, Korres NE. Waste to energy
potential: a case study of Saudi Arabia. Renew Sustain Energy Rev 2016;61:328–40.
[7] Cucchiella F, D Adamo I, Gastaldi M. Sustainable waste management: waste to
energy plant as an alternative to landfill. Energy Convers Manage 2017;131:18–31.
[8] Luo S, Feng Y. The production of fuel oil and combustible gas by catalytic pyrolysis
of waste tire using waste heat of blast-furnace slag. Energy Convers Manage
2017;136:27–35.
[9] Couto ND, Silva VB, Rouboa A. Assessment on steam gasification of municipal solid
waste against biomass substrates. Energy Convers Manage 2016;124:92–103.
[10] Demirbas A. Waste management, waste resource facilities and waste conversion
processes. Energy Convers Manage 2011;52(2):1280–7.
[11] Bosmans A, Vanderreydt I, Geysen D, Helsen L. The crucial role of Waste-to-Energy
technologies in enhanced landfill mining: a technology review. J Cleaner Prod
2013;55:10–23.
[12] Wei J, Guo Q, He Q, Ding L, Yoshikawa K, Yu G. Co-gasification of bituminous coal
and hydrochar derived from municipal solid waste: reactivity and synergy. Biores
Technol 2017;239:482–9.
[13] Wei J, Guo Q, Gong Y, Ding L, Yu G. Synergistic effect on co-gasification reactivity
of biomass-petroleum coke blended char. Biores Technol 2017;234:33–9.
[14] Marculescu C, Cenuşă V, Alexe F. Analysis of biomass and waste gasification lean
syngases combustion for power generation using spark ignition engines. Waste
Manage 2015;47:133–40.
[15] Arena U. Process and technological aspects of municipal solid waste gasification. A
review. Waste Manage 2012;32(4):625–39.
[16] Nguyen TLT, Hermansen JE, Nielsen RG. Environmental assessment of gasification
technology for biomass conversion to energy in comparison with other alternatives:
the case of wheat straw. J Cleaner Prod 2013;53(16):138–48.
[17] Luz FC, Rocha MH, Lora EES, Venturini OJ, Andrade RV, Leme MMV, et al. Techno-
economic analysis of municipal solid waste gasification for electricity generation in
B. Hu et al.
Brazil. Energy Convers Manage 2015;103:321–37.
[18] Hu M, Guo D, Ma C, Hu Z, Zhang B, Xiao B, et al. Hydrogen-rich gas production by
the gasification of wet MSW (municipal solid waste) coupled with carbon dioxide
capture. Energy 2015;90:857–63.
[19] Wang J, Cheng G, You Y, Xiao B, Liu S, He P, et al. Hydrogen-rich gas production by
steam gasification of municipal solid waste (MSW) using NiO supported on mod-
ified dolomite. Int J Hydrogen Energy 2012;37(8):6503–10.
[20] Heidenreich S, Foscolo PU. New concepts in biomass gasification. Prog Energy
Combust Sci 2015;46:72–95.
[21] Nacken M, Ma L, Heidenreich S, Baron GV. Performance of a catalytically activated
ceramic hot gas filter for catalytic tar removal from biomass gasification gas. Appl
Catal B 2009;88(3–4):292–8.
[22] Nilsson S, Gómez-Barea A, Fuentes-Cano D, Ollero P. Gasification of biomass and
waste in a staged fluidized bed gasifier: modeling and comparison with one-stage
units. Fuel 2012;97:730–40.
[23] Gómez-Barea A, Leckner B, Villanueva Perales A, Nilsson S, Fuentes Cano D.
Improving the performance of fluidized bed biomass/waste gasifiers for distributed
electricity: a new three-stage gasification system. Appl Therm Eng
2013;50(2):1453–62.
[24] Arena U, Zaccariello L, Mastellone ML. Tar removal during the fluidized bed gasi-
fication of plastic waste. Waste Manage 2009;29(2):783–91.
[25] Shen Y, Yoshikawa K. Recent progresses in catalytic tar elimination during biomass
gasification or pyrolysis—a review. Renew Sustain Energy Rev 2013;21:371–92.
[26] Aravind PV, de Jong W. Evaluation of high temperature gas cleaning options for
biomass gasification product gas for solid oxide fuel cells. Prog Energy Combust Sci
2012;38(6):737–64.
[27] de Sales CAVB, Maya DMY, Lora EES, Jaén RL, Reyes AMM, González AM, et al.
Experimental study on biomass (eucalyptus spp.) gasification in a two-stage
downdraft reactor by using mixtures of air, saturated steam and oxygen as gasifying
agents. Energy Convers Manage 2017;145:314–23.
[28] Cho M, Choi Y, Kim J. Air gasification of PVC (polyvinyl chloride)-containing
plastic waste in a two-stage gasifier using Ca-based additives and Ni-loaded acti-
vated carbon for the production of clean and hydrogen-rich producer gas. Energy
2015;87:586–93.
[29] Wu C, Williams PT. Pyrolysis–gasification of plastics, mixed plastics and real-world
plastic waste with and without Ni–Mg–Al catalyst. Fuel 2010;89(10):3022–32.
[30] Fang S, Yu Z, Ma X, Lin Y, Lin Y, Chen L, et al. Co-pyrolysis characters between
combustible solid waste and paper mill sludge by TG-FTIR and Py-GC/MS. Energy
Convers Manage 2017;144:114–22.
[31] Pinto F, Lopes H, André RN, Gulyurtlu I, Cabrita I. Effect of catalysts in the quality
of syngas and by-products obtained by co-gasification of coal and wastes. 1. Tars
and nitrogen compounds abatement. Fuel 2007;86(14):2052–63.
[32] Zaccariello L, Mastellone M. Fluidized-bed gasification of plastic waste, wood, and
their blends with coal. Energies 2015;8(8):8052–68.
[33] Pinto F, Andr RN, Carolino C, Miranda M. Hot treatment and upgrading of syngas
481
Energy Conversion and Management 153 (2017) 473–481
obtained by co-gasification of coal and wastes. Fuel Process Technol
2014;126:19–29.
[34] Ahmed II, Nipattummakul N, Gupta AK. Characteristics of syngas from co-gasifi-
cation of polyethylene and woodchips. Appl Energy 2011;88(1):165–74.
[35] Tursun Y, Xu S, Wang C, Xiao Y, Wang G. Steam co-gasification of biomass and coal
in decoupled reactors. Fuel Process Technol 2016;141:61–7.
[36] Li H, Chen Z, Huo C, Hu M, Guo D, Xiao B. Effect of bioleaching on hydrogen-rich
gas production by steam gasification of sewage sludge. Energy Convers Manage
2015;106:1212–8.
[37] Kai X, Li R, Yang T, Shen S, Ji Q, Zhang T. Study on the co-pyrolysis of rice straw
and high density polyethylene blends using TG-FTIR-MS. Energy Convers Manage
2017;146:20–33.
[38] Hu B, Huang Q, Bourtsalas ACT, Ali M, Chi Y, Yan J. Effect of chlorine on the
structure and reactivity of char derived from solid waste. Energy Fuels
2017;31(7):7606–16.
[39] Lahijani P, Zainal ZA, Mohamed AR, Mohammadi M. CO2 gasification reactivity of
biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.
Biores Technol 2013;144(3):288–95.
[40] Baldinelli A, Cinti G, Desideri U, Fantozzi F. Biomass integrated gasifier-fuel cells:
Experimental investigation on wood syngas tars impact on NiYSZ-anode Solid Oxide
Fuel Cells. Energy Convers Manage 2016;128:361–70.
[41] Choi Y, Ko J, Kim J. A new type three-stage gasification of dried sewage sludge:
Effects of equivalence ratio, weight ratio of activated carbon to feed, and feed rate
on gas composition and tar, NH3, and H2S removal and results of approximately 5 h
gasification. Energy 2017;118:139–46.
[42] Kim K, Jeon S, Hasolli N, Lee K, Lee J, Han J, et al. HCl removal characteristics of
calcium hydroxide at the dry-type sorbent reaction accelerator using municipal
waste incinerator flue gas at a real site. Korean J Chem Eng 2017:1–10.
[43] Encinar JM, Beltrán FJ, Bernalte A, Ramiro A, Gonzalez JF. Pyrolysis of two agri-
cultural residues: olive and grape bagasse. Influence of particle size and tempera-
ture. Biomass Bioenerg 1996;11(5):397–409.
[44] Di Felice L, Courson C, Foscolo PU, Kiennemann A. Iron and nickel doped alkaline-
earth catalysts for biomass gasification with simultaneous tar reformation and CO2
capture. Int J Hydrogen Energy 2011;36(9):5296–310.
[45] Han J, Kim H. The reduction and control technology of tar during biomass gasifi-
cation/pyrolysis: An overview. Renew Sustain Energy Rev 2008;12(2):397–416.
[46] Wu S, Gu J, Zhang X, Wu Y, Gao J. Variation of carbon crystalline structures and
CO2 gasification reactivity of shenfu coal chars at elevated temperatures. Energy
Fuels 2008;22(1):199–206.
[47] Corella J, Toledo JM, Molina G. Performance of CaO and MgO for the hot gas clean
up in gasification of a chlorine-containing (RDF) feedstock. Biores Technol
2008;99(16):7539–44.
[48] Dou B, Wang C, Chen H, Song Y, Xie B, Xu Y, et al. Research progress of hot gas
filtration, desulphurization and HCl removal in coal-derived fuel gas: a review.
Chem Eng Res Des 2012;90(11):1901–17.