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abstract
Article history:
This paper proposes a novel system for continuous hydrogen production from waste
reforming process (SERP). The system was operated in successive processes of several
26 December 2015
sections: (a) gasifying a WP into a raw gas comprising CO, H2, CH4, total hydrocarbons
(THC), and small amount of HCl contaminant, etc.; (b) passing the raw gas to hydrogen
production through two moving-bed reactors by continuous SERP process over Ni-based
catalyst mixed CaO sorbent for in-situ CO2 capture and HCl removal; (c) simultaneously
Keywords:
regenerating CaCO3 formed and catalyst with carbons deposited in other moving-bed
reactor at the regeneration condition selected; and (d) carrying the particles of catalyst
and sorbent to continuous steam reforming and their regeneration between two moving-
(SERP)
bed reactors by riser. Gradually expanding chamber design of FBG reactor suitable for
Hydrogen production
different particles flow to prolong the residence times of gas and solid phases makes high
carbon conversion and the maximum value is up to 83.6% at 880 C during FBG stage. The
combination of FBG and SERP has produced a stream of high-purity hydrogen at some
certain conditions, and about 88.4 vol % of hydrogen (H2O- and N2-free basis) was obtained
at 818 C of FBG temperature with 706e583 C of SERP temperature. Reduced Ni-based
catalyst efficiently converted raw gas from FBG and steam to H2, and CaO sorbent in the
moving-bed reactor are capable of reducing the HCl and CO2 to low levels at all the temperatures tested.
Copyright 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
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 x x x ( 2 0 1 6 ) 1 e8
Introduction
Depletion of fossil fuels is creating opportunities in exploring
alternative sources of energy, and at the same time, hydrogen
is a clean energy carrier for the development of potential high
efficiency power generation alternatives such as fuel cells.
The suitable waste plastic (WP) management strategy for the
manufacture of value added products is very important aspect
of sustainable development in modern society. Economical
hydrogen production from thermal-chemical conversion of
WP as a viable renewable energy source in some ready manners remain a challenge [1,2]. It is very difficult for the design
and operation of conversion systems due to various compositions of WP, and the differences in its thermal degradation
behavior. Some limitations in fluidized-bed gasification (FBG)
of WP still need to be tackled to increase the feeding conversion and decrease the contaminants in the gas products [3]. As
we know, the continuous removal of CO2 by CaO sorbent from
the water-gas shrift (WGS) reaction will incessantly drive the
equilibrium-limited WGS reaction in the forward direction,
which will ensure a high yield and purity of H2 with near
stiochiometric amount of steam needed for the reaction [4,5].
In addition, HCl gas contaminant from WP conversion can
simultaneously be removed by solid sorbents including CaO at
high temperatures [6].
A few papers specifically reported FBG to syngas and energy production [7e9], and the attention should be directed
towards achieving high carbon conversion and obtaining the
desire products. Seven mixtures of coals, plastics and wood
have been fed into a pre-pilot scale fluidized-bed gasifier in
order to investigate the main aspects of the co-gasification of
these materials, and the raw gas consists of CO, H2, CO2, CH4,
CnHm, etc [8]. Ruoppolo et al. reported the results of gasification tests using a catalytic fluidized-bed gasifier to obtain a H2rich stream and only 32 vol% of hydrogen concentration was
produced [9]. It has been indicated that the composition of the
gas products from gasification depends on the inherent nature
of the feeding and the process conditions employed, the
concentration of raw gas components is very difficult to adjust
and control. Tar and heavy hydrocarbons produced during
FBG of WP are undesired and dangerous for typical postprocess applications.
In the past few decades, the extensive studies on novel
systems for low-cost hydrogen production have been carried
out and the sorption-enhanced steam reforming process
(SERP) with in-situ CO2 capture has been considered to change
the normal equilibrium limits of WGS reaction for producing
high-purity hydrogen and reducing the number of processing
steps required for subsequently separating CO2 [10e13].
Recently, we reported a approach on continuous SERP [14,15]
to high-purity hydrogen production and the process was
characterized by a continuous flow concept of catalyst and
sorbent for steam reforming and regeneration using two
moving-bed reactors by the integration of continuous steam
reforming, WGS, CO2 capture, and hydrogen separation in one
single reactor, which can result in improved process efficiency
and reduced capital costs. The operating flexibility of continuous SERP by two moving-bed reactors makes it possible to
utilize different types of gas and liquid feedstock such as raw
gas including CO, H2, CH4, total hydrocarbons (THC), etc. from
FBG of WP. Our previous researches were directly related to
high temperature pyrolysis, and gasification [16,17], and some
reasonable amounts of gas products were produced during the
processes.
To our knowledge, there is hardly any publication in the
literature providing information on the ways of integrating
FBG and continuous SERP for hydrogen production from a
typical WP, which is not very needed to consider the composition of the raw gas produced from FBG. The integrated system indeed consolidates several unit operations including FBG
of WP, steam reforming of raw gas, WGS, in-situ CO2 capture
and HCl removal. Fundamental studies and experimental
works are also developed for high quality energy production
from low-cost fuels as well as the reduction of environmental
impact.
Experimental
Preparation of WP
Samples of WP from industrial plastic plant in China were
prepared in order to obtain fine particles and sieved to
0.5e1.2 mm. The proximate analysis was carried out using the
method described by ASTM D5142. The ultimate analysis was
conducted using an element analyzer (EA1110, CE instrument). Thermogravimetric analysis (TGA) for WP pyrolysis
was carried out using a StantoneRedcroft thermogravimetric
apparatus (STA 780). The calorific value of the sample (LHV)
was calculated by the Dulongs equation:
LHV HHV 600 9H W
O
2500S
where; HHV 8100C 34000 H
8
Characterization of catalyst
The specific surface areas of fresh catalyst and sorbent were
determined using a Micrometric Acusorb 2100E apparatus
Please cite this article in press as: Dou B, et al., Fluidized-bed gasification combined continuous sorption-enhanced steam reforming
system to continuous hydrogen production from waste plastic, International Journal of Hydrogen Energy (2016), http://dx.doi.org/
10.1016/j.ijhydene.2015.12.197
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 x x x ( 2 0 1 6 ) 1 e8
Apparatus
Fig. 1 showed a schematic of the experimental system and
apparatus, which presented combined concept of FBG and
SERP. It primarily consisted of raw gas and H2 production, as
well as CO2 and HCl removal. FBG furnace with 30e60 mm in
ID and 800 mm in length was made of a dense alumina
ceramic tube. A diagram of FBG is also shown in Fig. 2. The
expanding chamber design of FBG reactor, which is very
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 x x x ( 2 0 1 6 ) 1 e8
suitable for different particles flow, is to prolong the residence times of gas and solid phases. Sand particles of
300e500 mm were used as FBG bed materials. The hydrodynamics of fluidization, and chemical reactions in FBG
reactor were studied based on the EulerianeEulerian twofluid approach by laminar finite-rate model in the previous
studies [18,19]. The gas-solids mixture and flow, fluidizedbed expansion and pressure drop were predicted for
different inlet gas velocities, the results indicated the gassolids flow system exhibited a more heterogeneous structure, and the core-annulus structure of gasesolids flow led
to back-mixing and internal circulation behavior. This has
been suggested the expanding chamber can also increase
the mixture of gases and solids. FBG process of WP particles
to raw gas was performed at a constant temperature in an
inert atmosphere of pure nitrogen (500 ml/min at STP) and
steam (500 ml/min at STP). The FBG furnace was heated to a
certain temperature and WP of 10e20 g/hr carried by nitrogen was injected to FBG furnace. The steam is injected at
250 C from a steam generator. A tubular electric furnace
wt, %
Moisture
Volatile matter
Fixed carbon
Ash
Ultimate analysis
C
H
O
N
S
Cl
0.51
62.35
18.05
19.09
wt, %
65.18
15.61
9.15
0.16
0.11
2.98
Please cite this article in press as: Dou B, et al., Fluidized-bed gasification combined continuous sorption-enhanced steam reforming
system to continuous hydrogen production from waste plastic, International Journal of Hydrogen Energy (2016), http://dx.doi.org/
10.1016/j.ijhydene.2015.12.197
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 x x x ( 2 0 1 6 ) 1 e8
The steady state conditions for continuous hydrogen production from FBGSERP system were achieved within 30 min.
After that, the content of each gas component remained
rather stable. The effect of temperature on the raw gas and
hydrogen production from FBGSERP of WP was showed in
Fig. 6. The FBG experiments were carried out at the temperatures of 810, 846 and 880 C. Fig. 6(a), (c), (e) showed the
concentrations of CO, H2, CH4, HCl and THC in raw gas from
FBG at various temperatures. CO, THC and HCl in raw gas
Molecular formula
H2
CO
CO2
CH4
C2H4
C2H6
C3H8
C4H6
C4H10
C5H8
C5H12
C6H12
e
6.9
12.6
6.7
21.1
11.6
6.3
5.9
7.5
5.3
3.9
3.1
0.6
8.5
100
Please cite this article in press as: Dou B, et al., Fluidized-bed gasification combined continuous sorption-enhanced steam reforming
system to continuous hydrogen production from waste plastic, International Journal of Hydrogen Energy (2016), http://dx.doi.org/
10.1016/j.ijhydene.2015.12.197
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 x x x ( 2 0 1 6 ) 1 e8
Fig. 6 e Raw gas, temperature and gaseous products in FBGSERP system: (a), raw gas from FBG stage at 880 C of FBG
temperature; (b), temperature and gaseous products from SERP stage at 880 C of FBG temperature; (c), raw gas from FBG
stage at 846 C of FBG temperature; (d), temperature and gaseous products from SERP stage at 846 C of FBG temperature; (e)
raw gas from FBG stage at 818 C of FBG temperature; (f), temperature and gaseous products from SERP stage at 818 C of FBG
temperature.
should be a key parameter during FBG of WP. At high temperature, the steam gasification and partial decomposition
of the organic compounds from WP could produce the more
H2, CO and other gaseous products. According to
literature reported [21e24], the use of steam in gasification
process allows to foster the chemical reactions promoted by
steam, such as carbon steam gasification and hydrocarbon
steam reforming, in which the ultimate effect should be the
enrichment of gaseous products in its H2 and CO contents.
Such effect was shown clearly in Fig. 6 where a comparison
among the compositions of the product gases is presented
by taking into account the mean value of each permanent
gas component at the steady state, and calculated on dry
and N2-free basis. The slag from FBG showed the aggregate
Please cite this article in press as: Dou B, et al., Fluidized-bed gasification combined continuous sorption-enhanced steam reforming
system to continuous hydrogen production from waste plastic, International Journal of Hydrogen Energy (2016), http://dx.doi.org/
10.1016/j.ijhydene.2015.12.197
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 x x x ( 2 0 1 6 ) 1 e8
formation and a strip structure. During FBG process, pyrolysis and gasification occurred to the volatiles and char,
resulting in the formation of soot particles, which deposited
on the wall of the reactor. A typical slag analyzed consisted
of carbon of 4e6 wt % and ash. The calculation of carbon
element balance during FBG stage showed a loss of 7e10 wt
% carbon, which may be total heavy hydrocarbons (CiHj,
i > 6) and carbon particles in raw gas.
However, a crucial requirement of the process is that raw
gas containing CO, H2, CH4, THC, heavy hydrocarbons and
carbon particles can effectively convert to H2 with in-situ
CO2 capture and HCl removal in SERP stage. In the proposed system on continuous production of hydrogen from
WP by FBGSERP, the mixture of NiO/NiAl2O4 and CaO sorbent was moved continually by the velocity of 9e11 cm/
min between two moving-bed reactors, and the operation
for H2 production was not needed to stop for generation
both sorbent and catalyst. In a typical experiment, the SERP
reactor was preheated to initial temperatures of 500 C. The
heating was turn off when the temperature of SERP reactor
was up to its initial temperature and the reforming reactor
was then heated by high temperature gas from FBG stage. A
mixture of raw gas, N2 and steam were fed into the SERP
reactor and the value of the molar ratio of steam to carbon
in raw gas was 3.0e4.0. Fig. 6(b), (d), and (f) depicted temperatures at the central of SERP reactor and gaseous products distribution at the different temperatures of FBG stage.
The temperatures of SERP reactor for a certain temperature
of FBG were gradually decreased, and it is due to heating
steam and endothermic reactions of steam reforming of
CH4, THC and some compositions also including carbon
particles gasification. The temperatures at SERP reactor for
initial temperature of 500 C showed the endothermic and
exothermic reactions can achieve hydrogen production and
energy requirement in this system, and the SERP reactor
was continuously operated without heating when the value
of S/C is not higher than 3e4, while the temperature is
decreased gradually with steam-on-time and the lowest
temperature in three cases was above 580 C. High steam
Please cite this article in press as: Dou B, et al., Fluidized-bed gasification combined continuous sorption-enhanced steam reforming
system to continuous hydrogen production from waste plastic, International Journal of Hydrogen Energy (2016), http://dx.doi.org/
10.1016/j.ijhydene.2015.12.197
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 x x x ( 2 0 1 6 ) 1 e8
Conclusions
First, the isothermal pyrolysis of WP was carried out by TGA at
the temperature of 700 C and the weight decreased sharply to
23% in 6 min. The effect of temperature on raw syngas and H2
production from FBGSERP of WP was determined. The carbon
conversation in FBG stage was increased with temperature
increasing and the maximum value is 83.6% at 880 C. The
value of CO/H2 in the range of 1.15e1.77 was increased with
increasing gasification temperature. The H2 concentration
was related to the temperature of moving-bed SWGS reactor,
at the temperature of above 700 C, H2 concentration was very
low due to CO2 produced is not removed. High-purity H2 was
produced in low reaction temperature due to favor SERP reaction with in-situ CO2 removal. CaO sorbent in the movingbed reactor was capable of reducing the HCl from raw syngas to very low levels. Continuous moving, reaction and
regeneration did not lead to great decay in the activity of
catalyst and sorbent. The novel approach on FBGSERP system
for H2 production from WP with long time is feasible.
Acknowledgment
This work is supported by the Natural Science Foundation of
China (Project Nos. 91434129, 51476022, 51276032, and
51522605).
This work was also supported by International Science and
Technology Cooperation Program of China under grant
No.2014DFA60600, and the Fundamental Research Funds for
the Central Universities (DUT15JJ(G)02).
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Please cite this article in press as: Dou B, et al., Fluidized-bed gasification combined continuous sorption-enhanced steam reforming
system to continuous hydrogen production from waste plastic, International Journal of Hydrogen Energy (2016), http://dx.doi.org/
10.1016/j.ijhydene.2015.12.197