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The production of hydrogen-rich gas by wet sludge

gasification using waste heat of blast-furnace slag:
Mass and energy balance analysis

Siyi Luo a, Junzhi Wang a, Xianjun Guo b, Zhifei Liu a,*, Wei Sun c
a
School of Environmental and Municipal Engineering, Qingdao Technological University, 11 Fushun Rd., Qingdao,
266033, China
b
School of Environmental and Material Engineering, Yantai University, 30 Qingquan Rd., Yantai, 264005, China
c
Shandong Suo Yuan Environmental Technology Co., Ltd, Linyi 276000, China

article info abstract

Article history: Sludge gasification for the production of hydrogen-rich gas is a promising technology. In
Received 2 September 2018 this paper, a pilot study on the hydrogen-rich gas production by sludge gasification using
Received in revised form waste heat of blast furnace slag was carried out, and the mass and energy balance of
25 September 2018 gasification process using waste heat from blast furnace slag were evaluated. The results
Accepted 8 October 2018 show that the higher the gasification temperature, the higher the hydrogen content in the
Available online 30 October 2018 gas. When the gasification temperature reaches 880
C, the hydrogen content in the gas
reaches the maximum,35.3%. The technology of sludge gasification combined with waste
Keywords: heat recovery of high furnace slag is feasible. Its efficiency of heat recovery can reach up to
Sludge 64.35%, and the gasification efficiency and energy consumption ratio can reach to 42.30%
Gasification and 3.67, respectively.
Hydrogen-rich gas © 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Waste heat
Blast furnace slag

However, due to the lack of reasonable heat source, the sludge

Introduction
The sludge contains a large amount of organic matter and
combustible components, which has high energy develop-
ment and utilization value [1,2]. The sludge gasification tech-
nology can not only recycle, utilize and convert the organic
matter into clean energy, but also can avoid the secondary
pollution problems, compared to the traditional sludge treat-
ment and disposal [3e5], such as incinerate, landfill and
compost. Sludge gasification for the production of hydrogen-
rich gas is a promising hydrogen production technology.
pyrolysis or gasification technology has not achieved large-
scale production.
Blast furnace slag contains a lot of sensible heat, but there
is no better method to recycle [6]. The temperature and heat of
blast furnace slag can meet the requirements of sludge gasi-
fication and provide 'free' energy for it, which can effectively
solve the problem of high cost of sludge gasification [7,8]. In
addition, blast furnace slag has the catalytic activity for the tar
cracking, also can promotes the conversion of low molecular
hydrocarbons into H2 and CO [9e12]. Based on this, the

DOI of original article: https://doi.org/10.1016/j.ijhydene.2018.11.149.

* Corresponding author.
E-mail address: lzf-qd@163.com (Z. Liu).
https://doi.org/10.1016/j.ijhydene.2018.10.044
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
5172 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 5 1 7 1 e5 1 7 5

application of waste heat from blast furnace slag is proposed

Table 2 e The gas composition obtained by different
for the sludge gasification to produce fuel gas. Siyi Luo et al. [6]
temperature.
presents a heat recovery system from the heat of BF slag,
Gasifier temperature (
C) 720 750 768 820 880
which generates hydrogen-rich gas via the endothermic re-
Gas production (Nm3/kg) 1.56 1.71 1.8 2.14 2.20
actions of sludge gasification. While the mass and energy
H2 21.3 25.7 28.1 34.1 35.3
balance of the gasification process has not been discussed, an CO 19.4 24.5 32.2 28.0 30.3
it is necessary to guide the industrial production. In this paper, CO2 33.9 27.7 22.4 25.8 28.2
a pilot study on sludge gasification using waste heat of BF slag CH4 10.2 9.10 8.32 7.99 5.72
was carried out, and the material and energy balance of sludge C2H4 9.72 10.2 10.3 8.25 6.43
gasification were analyzed and calculated, which provided C2H6 3.10 2.02 1.87 1.45 0.91

theoretical basis and data support for the industrial produc-

tion of sludge gasification in conjunction with waste heat re-
covery of BF slag. higher the gasification temperature, the higher the hydrogen
content in the gas. When the gasification temperature reaches
880
C, the hydrogen content in the gas reaches the maximum.
Experiment and methods Thus the pilot scale test was carried out at 880
C.

Materials The mass balance of sludge gasification process

The BF slag was prepared by Iron & Steel plant. The liquid blast
furnace slag is pretreated by centrifugal granulation and
converted into high temperature slag particles. The particles
size was between 5 mm and 10 mm. Sewage sludge was
collected from a waste water treatment plant. The proximate
and ultimate analysis of sludge are shown in Table 1.
For the gasification system, the mass input includes the mass
of BF slag (m1) and the gasification raw materials dry sludge
(m2) and water vapor (m3); while the mass output includes the
gaseous products (m4), solid semi coke (m5), cooling BF slag
(m6), tar (m7) and ash in the gas (m8). Table 2 shows the results
of mass balance of gasification system.

Experimental apparatus and procedure
The experimental apparatus and procedure has been
described in the previous paper [8,9]. The BF slag was taken as
heat carrier in the rotary apparatus. A screw feeder fed sludge
(the feeding rate was set at 500 g/min) into the rotary reactor.
Intense mixing promotes the heat transfer between particles,
which was helpful to the heating of sludge during gasification.
Purified nitrogen was used as the carrier gas to provide an
inert atmosphere for pyrolysis and to remove any gaseous and
condensable products that evolved. After reactions, the cool-
ing BF slag and the sludge residues were discharged together
from the reactor and weighted, respectively. The sludge resi-
dues was separated from BF slag by vibrating screen. The
gaseous product was discharged after dust removal, conden-
sation, purification and measurement.
Results and discussion
Table 2 shows the gas composition obtained by different
gasification temperature. The gas compositions were
analyzed by a gas chromatograph. The results show that the
(1) During the experiment, the output of the solid residual
char was obtained by the direct weighing method. The
tar and the gasification water in the liquid product were
extracted and separated by CH2Cl2. The mass output of
the gaseous products is calculated from the volume
output and density of the gas, and the gas density is
calculated through the gas composition.
(2) The ash content in the dust collection device is little.
Therefore, the sensible heat of the ash collected in the
cyclone cleaner can be neglected.
(3) The water in the liquid product includes the water and
the vapors produced by the reaction of hydrogen and
oxygen in the gasification material, which contains a
small amount of water-soluble organic compounds, so
the chemical heat can be ignored when the energy is
calculated.
(4) In the calculation process, the whole gasification sys-
tem is used as the research object, so the input water is
calculated in the form of liquid (25
C), and the output
water is calculated in the form of steam (880
C). The
flue gas temperature is calculated by the temperature
measured at the outlet of the gasification reactor.
(5) The average value obtained by continuous operation of
the gasification system at 60min is taken as the calcu-
lation result.

Table 1 e Proximate analysis and elemental analysis of From the Table 3, the error of material balance under
sludge. experimental conditions is 4.4%, which indicates that the
Proximate analysis/wd% Ultimate analysis/wd % method of determining the output of each product in the
Higher heating value (kJ/kg) 16875.50 C 45.17 experiment is feasible, and the experiment is carried out in a
Moisture content 6.20 H 3.78 small error range. The error of mass balance may be due to:
Volatile matter 41.33 O 9.63
Fixed carbon 14.47 N 2.87
Ash 33.45 S 18.4
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(2) The waste heat of BF slag (Q2), is equal to the sensible

Table 3 e Material balance calculation.
heat of BF slag feed as an external heat source.
Quality input Quality output (g/min) Mass
(g/min) balance
Raw Gas Tar Semi Water Total
(%) Q2 ¼ m1  qBF (3)
material coke According to formula (3), the chemical heat of biomass as
500 61.7 232.3 162.0 22.0 478.0 95.6 fuel is 1160610 kJ.

Energy output of the gasification system

(1) Tar is not completely separated from condensed water,
and some liquid products adhere to the inner wall of the (1) The chemical heat (Q3) of gas products is equal to the
condensing device; product of gas production and calorific value of gas.
(2) The separation of granulated slag particles and gasifi-
cation residue of sludge is incomplete;
Q3 ¼ Vg  qg (4)
(3) Not all the gas products can be detected. As a result, the
amount of gas production is low [8,9]. According to formula (4), the chemical heat of gas product
can be obtained as 780918 kJ.
The energy balance of sludge gasification process
(2) The sensible heat of gas products (Q4).The measured
The following factors are ignored in the calculation of the
temperature of gas at the outlet of the gasification
energy balance of the sludge gasification system:
chamber is 650
C, which is convenient to calculate at
800
C and then cooled to room temperature 25
C.
(1) Neglecting the microscopic energy transfer of gasifica-
tion process. X
(2) Calculate the energy balance of the gasification system Q4 ¼ Vg ð800Cp;i;800  25Cp;i;25 Þ  Ci (5)
only, ignoring the pyrolysis stage of sludge.
The sensible heat of gas product is 203934 kJ by formula (5).
(3) Only calculate the energy balance of the whole system.

(3) The chemical heat (Q5) of residual char is equal to the

The energy balance of gasification is shown in the Fig. 1.
Under the optimized conditions, the energy balance rela-
tionship of the gasification system is as follow:
Q1 þ Q2 ¼ Q3 þ Q4 þ Q5 þ Q6 þ Q7 þ Q8 þ Q9 þ Q10 þ Q11
Energy input of the gasification system
(1) The chemical heat (Q1) of gasification raw materials,
which is equal to the product of raw material feed and
sludge calorific value:
product of the residual char output and the heat value.
Q5 ¼ m6  qc (6)
(1)
The chemical heat of the residual char calculated by
formula (6) is 255332 kJ.
(4) The sensible heat of residual char (Q6), the measured
temperature at the outlet of the gasification chamber is
988
C, and then cooled to 25
C at room temperature, so
the sensible heat of the residual char is as follows:

Q1 ¼ m3  qb (2) Q6 ¼ m6  Cpc  ð988  25Þ (7)

The chemical heat of gasification material is 497410 kJ by The sensible heat of the residual char calculated by
formula (2). formula (7) is 8621.6 kJ.

Fig. 1 e Energy balance of gasification system.

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(5) The chemical heat (Q7) of tar is equal to the product of is measured by 800
C. Therefore, the sensible heat contained
tar production and heat value of semi coke. in it is as follows:
Q10 ¼ m8  ð800$Cp;800  100$Cp;100 Þ þ m8  DHvap þ m8  Cw
Q7 ¼ m7  qt (8)  ð100  25Þ
(11)
The chemical heat of tar calculated by formula (8) is
30637 kJ. The sensible heat of the residual steam calculated by
formula (11) is 24704.2 kJ.
(6) The sensible heat (Q8) of the tar, the original tar is To sum up, the energy balance of the sludge gasification
released from the gasification chamber in a gas state, system is shown in the Table 4.
and the temperature is 795
C as the furnace tempera-
ture, and then cooled to 25
C at room temperature, so The gasification efficiency, energy recovery rate and energy
the sensible heat of the tar is as follows: consumption ratio

Q8 ¼ m7  ½Cpt  ð795  25Þ þ DHt 
The sensible heat of tar calculated by formula (9) is 1658 kJ.
(7) The sensible heat of flue gas (Q9), the main components
of combustion flue gas include CO2, O2 and N2, while other
gas components are relatively small, so they can be ignored.
The measured temperature at the exit of the flue gas outlet of
the waste heat steam generator is 289
C, which is conve-
nient to calculate at 300
C and then cooled naturally to room
temperature 25
C, so the sensible heat of the flue gas is as
follows:
X technical index, which is defined as follows:
Q4 ¼ Vf ð300Cp;i;300  25Cp;i;25 Þ  Ci
Where, Cp, I, 300 is the average constant pressure spe-
cific heat capacity of the i-th kind of gas at 300
C, per
standard atmospheric pressure, kJ/(m3.
C), Cp, I, 25 is the
average constant pressure specific heat capacity of the
kind of gas at 25
C, per standard atmospheric pressure,
kJ/(m3.
C), Ci is the volume fraction of the kind of gas. The
sensible heat of gas product calculated by formula (10) is
87376.6 kJ.
(8) The sensible heat of residual water vapor (Q10),
The process of steam exothermic discharge from the outlet
of the gasification chamber is, first from 795
C to 100
C, the
gaseous water vapor at 100
C is converted to 100
C liquid
water and then cooled to 25
C at room temperature. In order
to facilitate calculation, the initial temperature of water vapor
(9) The gasification efficiencyh1 is usually used to measure the
performance of the gasification system. It refers to the
chemical energy contained in the gas products to the chemical
energy of the raw material. The Gasification efficiency of the
gasification system is defined as follows:
Eg
h1 ¼ (12)
Ein
where in, Ein is the chemical energy of gas products, being Q3;
Eg is the chemical energy of gasification raw materials.
The energy recovery rate h2 represents a energy balance
(10)
Ep
h2 ¼ (13)
Ein
where in, Ep is the chemical energy contained in all gasifica-
tion products (gas, semi coke and tar), that is Q3þ Q5þ Q7.
The energy consumption ratio of gasified productsxis the
ratio of the chemical energy contained in the gasification
products and the external energy, which is defined as follows:
Ep
x¼ (14)
EBF
In general, the heat recovery system from wastes heat
generated from the steelmaking industry, by utilizing the
endothermic heat of sludge gasification reactions instead of
sensible heat is feasible. The energy evaluation of the gasifi-
cation system is shown in Table 5, its efficiency of heat re-
covery can reach 64.35%, and the gasification efficiency and

Table 4 e Energy balance of the gasification system.

Program Heat（kJ） Ratio（%）
Input Chemical heat of gasification materials (Q1) 497410 30
Sensible heat of BF slag (Q2) 1160610 70
Total 1658000 100
Output Chemical heat of gas product (Q3) 780918 47.1
Sensible heat of gas product (Q4) 203934 12.3
Chemical heat of residual semi coke (Q5) 255332 15.4
Sensible heat of residual semi coke (Q6) 8621.6 0.52
Chemical heat of tar (Q7) 30637 1.85
Sensible heat of tar (Q8) 1658 0.10
Sensible heat of the gas (Q9) 87376.6 5.27
Sensible heat of residual steam（Q10） 24704.2 1.49
Heat loss（Q11） 268098 16.17
Total 1658000 100
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Table 5 e The gasification efficiency, energy recovery rate
and energy consumption ratio of gasification system.
Gasification Energy recovery Energy consumption
efficiency (h1,%) rate (h2,%) ratio (x)
42.30 64.35 3.67
energy consumption ratio can reach to 42.30% and 3.67,
respectively. In actual operation, the chemical energy in
sludge can not be completely converted into gas chemical
energy because of the inevitable loss of energy in the process
of gas condensation and system heat loss.
Conclusion
This paper studies the possibility of a heat recovery system
from wastes heat generated by the steelmaking industry, by
utilizing the endothermic heat of sludge gasification reactions
instead of sensible heat. The results showed that the higher
the gasification temperature, the higher the hydrogen content
in the gas. When the gasification temperature reaches 880
C,
the hydrogen content in the gas reaches the maximum,35.3%.
The energy input of the sludge gasification system using
waste heat of BF slag include the chemical heat of gasification
raw materials and the waste heat of BF slag. The energy
output of the gasification system consist of the chemical heat
of gas product, the sensible heat of gas product, the chemical
heat of residual semi coke, the sensible heat of residual semi
coke, the chemical heat of tar, the sensible heat of tar, the
sensible heat of the flue gas, the sensible heat of residual
vapor and the heat loss. As it concerns the chemical method,
hot slag was served as heat carrier for chemical reactions of
gasification. Its efficiency of heat recovery can reach 64.35%,
and the gasification efficiency and energy consumption ratio
can reach to 42.30% and 3.67, respectively.
Acknowledgments
The authors wish to acknowledge the financial support from a
project of Qingdao Science and Technology Program (17-3-3-
77-nsh), China; the Key research and development plan of
Shandong Province (2018GSF117042), China.
5175
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