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

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

Experimental apparatus and procedure (1) During the experiment, the output of the solid residual
char was obtained by the direct weighing method. The
The experimental apparatus and procedure has been tar and the gasification water in the liquid product were
described in the previous paper [8,9]. The BF slag was taken as extracted and separated by CH2Cl2. The mass output of
heat carrier in the rotary apparatus. A screw feeder fed sludge the gaseous products is calculated from the volume
(the feeding rate was set at 500 g/min) into the rotary reactor. output and density of the gas, and the gas density is
Intense mixing promotes the heat transfer between particles, calculated through the gas composition.
which was helpful to the heating of sludge during gasification. (2) The ash content in the dust collection device is little.
Purified nitrogen was used as the carrier gas to provide an Therefore, the sensible heat of the ash collected in the
inert atmosphere for pyrolysis and to remove any gaseous and cyclone cleaner can be neglected.
condensable products that evolved. After reactions, the cool- (3) The water in the liquid product includes the water and
ing BF slag and the sludge residues were discharged together the vapors produced by the reaction of hydrogen and
from the reactor and weighted, respectively. The sludge resi- oxygen in the gasification material, which contains a
dues was separated from BF slag by vibrating screen. The small amount of water-soluble organic compounds, so
gaseous product was discharged after dust removal, conden- the chemical heat can be ignored when the energy is
sation, purification and measurement. calculated.
(4) In the calculation process, the whole gasification sys-
tem is used as the research object, so the input water is
Results and discussion calculated in the form of liquid (25  C), and the output
water is calculated in the form of steam (880  C). The
Table 2 shows the gas composition obtained by different flue gas temperature is calculated by the temperature
gasification temperature. The gas compositions were measured at the outlet of the gasification reactor.
analyzed by a gas chromatograph. The results show that the (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.
product of the residual char output and the heat value.
Under the optimized conditions, the energy balance rela-
tionship of the gasification system is as follow:
Q5 ¼ m6  qc (6)
Q1 þ Q2 ¼ Q3 þ Q4 þ Q5 þ Q6 þ Q7 þ Q8 þ Q9 þ Q10 þ Q11 (1)
The chemical heat of the residual char calculated by
formula (6) is 255332 kJ.
Energy input of the gasification system
(4) The sensible heat of residual char (Q6), the measured
(1) The chemical heat (Q1) of gasification raw materials, temperature at the outlet of the gasification chamber is
which is equal to the product of raw material feed and 988  C, and then cooled to 25  C at room temperature, so
sludge calorific value: 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.


5174 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

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