J Ijhydene 2018 08 218

international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
ScienceDirect
journal homepage: www.elsevier.com/locate/he
Catalytic performances of Ni-based catalysts on

supercritical water gasification of phenol solution
and coal-gasification wastewater
Yuzhen Wang a,b,*, Yitong Zhu a, Zhuan Liu a, Laibin Wang c,

Donghai Xu b, Changqing Fang a, Shuzhong Wang b,**
a
Xi'an University of Technology, NO.5 South Jinhua Road, Xi'an, Shaanxi, 710048, PR China
b
Key Laboratory of Thermo-Fluid Science and Engineering of MOE, Xi'an Jiaotong University, No.28, Xianning West
Road, Xi'an, Shaanxi, 710049, PR China
c
Jinneng Group Co., Ltd., No.82 Kaihuasi Street, Taiyuan, Shanxi, 030002, PR China
article info abstract
Article history: Activity and stability of the supported Ni-based catalysts for the gasification performances
Received 7 May 2018 of phenol solution and coal-gasification wastewater in supercritical water were studied in a
Received in revised form continuous reactor at 480 C, 25 MPa and oxygen ratio of 0.2 for 50 h operation. The in-
27 August 2018 fluences of the supports (g-Al2O3, active carbon (AC) and carbon nanotube (CNT)) on gas
Accepted 30 August 2018 yields, gasification efficiencies for phenol solution were investigated, and the loading
Available online xxx amount of Ni were optimized. Results showed that the catalytic activity and the stability of
the catalysts followed the order of Ni/CNT > Ni/AC > Ni/g-Al2O3. The activity of Ni/AC and
Keywords: Ni/g-Al2O3 decreased after 30 h continuous operation, and there occurred significant
Catalyst leaching of Ni2þ. For Ni/CNT catalyst, H2 yield increased obviously when the loading
Ni amount of Ni lower than 15 wt%, while increased little at higher loading amount. Then,
Supercritical water gasification 15 wt% Ni/CNT with a thickness of 1.5 mm was coated on 316 L stainless steel (SS316L, an
Coal-gasification wastewater economic material usually used as the reactor material), which can act as a "catalytic tube
Phenol wall" in reactor. The catalytic activity and corrosion resistance of Ni/CNT/SS316L for the
gasification of real coal-gasification wastewater were studied. Results showed that Ni/CNT/
SS316L gave a great positive effect on H2 production. H2 yield increased from 25.36 mmol/g
(total organic carbon) without catalyst to 75.12 mmol/g (total organic carbon) with Ni/CNT/
SS316L after operated for 20 h, respectively. However, obvious pealing of the coating was
found after 50 h operation. Further study is necessary for the improvement of the coating
preparation method.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author. Xi'an University of Technology, NO.5 South Jinhua Road, Xi'an, Shaanxi, 710048, PR China.
** Corresponding author.
E-mail address: yzwang@xaut.edu.cn (Y. Wang).
https://doi.org/10.1016/j.ijhydene.2018.08.218
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Wang Y et al., Catalytic performances of Ni-based catalysts on supercritical water gasification of phenol
solution and coal-gasification wastewater, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.08.218
2 international journal of hydrogen energy xxx (xxxx) xxx
respectively, at 560 C, 25 MPa and oxygen of 0.2. Zhen's study

Introduction on the gasification of real coal-gasification wastewater
showed that the gasification efficiency of hydrogen could
Coal-gasification wastewater is a kind of wastewater with reach 135% at 550 C, 25 MPa [15]. Shu et al. [16] also reported
high concentration of phenol, ammonia, and certain concen- that H2 yield was as high as 10 mol/(kg wastewater) at 600 C,
tration of sulphide and heterocyclic nitrogenous organic 36 MPa. Guan et al. [17] studied the hydrogen production
compounds [1]. The main treatment process mainly focuses performances of phenol and real coal-gasification wastewater
on the harmlessization disposal, usually with the combined in SCW. Results showed that phenol was difficult to be gasified
technology of “ammonia distillation and dephenolization - below 480 C. However, H2 yield was as high as 33.7 mol/(m3
biochemical - chemical technology” [2]. However, this com- wastewater) with the catalysis of Na2CO3 at 450 C, 24 MPa, the
bined process is complicated and easy to generate secondary ratio of oxygen to carbon (O/C) 1.1, and the total organic car-
pollution, such as the chemical and biochemical sludge, bon (TOC) and chroma removal efficiencies and was 96% and
which would further exacerbate the environmental burden of 85%, respectively, which were more higher than that treated
the gasification station. From the resource utilization consid- by biochemical and “biochemical þ activated carbon adsorp-
erations, appropriate technology can be used to convert the tion” method. Results showed that SCWPO not only has the
high concentrated organic matters into hydrogen-rich gas. By advantages over the conventional ways in coal-gasification
this way, the harmlessization and resourcelization of waste- wastewater treatment, but also provides a great potential
water can be achieved simultaneously. way for energy utilization.
Supercritical water partial oxidation (SCWPO) is an efficient However, there are still some problems on the SCWPO of
gasification technology that using supercritical water (SCW) coal-gasification wastewater. Firstly, the aromatic com-
(T > 374.15 C, P > 22.12 MPa) as reaction media to covert the pounds in wastewater are difficulty to be degraded at the
organic matters into hydrogen and other fuel gases at the temperatures below 500 C [12]. Higher operation temperature
presence of trace oxygen [3]. During this process, the organic would aggravate the corrosion of reactor material and in-
compounds, oxygen and water can be soluble with each other crease the investment in equipment and operation risk.
at any proportion because of the unique physical and chemical Adding appropriate catalyst is a common way to reduce the
properties of SCW, which make the reactions more quickly and reaction temperature by changing the reaction paths. Noble
efficiently without interfacial resistance. Compared with metal catalysts such as Ru, Pt, and Pd exhibit considerably
traditional gasification technology, SCWPO technology has the high activity. However, the high cost limit their extensive
following advantages: (1) higher gasification efficiency (>98%); application. Recently, the researchers are focused on the
(2) able to treat wet biomass with water content higher than catalytic properties of the transition metals in group ⅥB and
90% and organic liquids (landfill leachate, petrochemical Ⅷ [18e20]. Among them, Ni has attracted much attention for
wastewater, oily wastewater, phenolic wastewater) [4e7]; (3) its high catalytic activity and low cost [21e23]. Resende et al.
the reaction rate is faster and more thoroughly as the free [24] reported that both Ni and Cu could promote the yields of
radical reactions are dominated; (4) the SCW can supply H2, CO2, CH4, and the activity of Ni is higher than Cu for the
hydrogen atoms as a reactant for the hydrogen product through gasification of lignin in SCW. Elliott's study on SCWG of
the steam reforming and water-gas shift reactions [8,9]. More- glucose by adding Ni and Cr also showed that Ni had an
over, different from the supercritical water gasification (SCWG) excellent catalytic activity, especially for the production of H2
technology that without oxygen presence, the exothermic and CH4, whereas Cr showed little activity [25]. As the Ni2þ in
oxidation reactions during SCWPO process would help to solution and unsupported Ni and NiO were less active in SCW,
maintain the reaction temperature constant [10], and the oxy- the researchers began seeking appropriate supports for Ni
gen in SCWPO could also accelerate the cleavage of carbon- [21]. Common supports included g-Al2O3, ZrO2, TiO2, activated
carbon (CeC) bonds and ring-opening reactions of aromatic carbon (AC), and carbon nanotube (CNT) [21,26,27]. In this
hydrocarbon. In addition, the application of SCWPO technology paper, we selected g-Al2O3, AC and CNT as supports, firstly
on coal-gasification wastewater has the unique advantages, their influences on the activity of Ni for SCWPO of phenol were
that the heat water from SCWPO reactor can serve as the studied. Here, we selected phenol as the model compound of
gasification medium of the gasifier directly [11]. coal-gasification wastewater mainly because that phenolic
Recent years, gasification of coal-gasification wastewater compounds are the main components in coal-gasification
and its model compounds in SCW have been reported. Yong wastewater, which occupy nearly 71% of the total compo-
et al. [12] and Huelsman et al. [13] gasified phenol at 25 MPa, nents [28]. And phenol is the most simple and typical phe-
370e450 C and 500e700 C, respectively. Results showed that nolics. Then, the loading amount of Ni was optimized. Finally,
phenol can be directly gasified at temperatures higher than we prepared the optimized supported catalyst on 316 L
600 C. However, the acid compounds, benzene naphthalene stainless steel (SS316L, usually selected as the reactor mate-
and other refractory intermediates would be generated at rial) to form a “catalytic tube wall”. By this way, the tube wall
temperatures lower than 600 C. In our previous researches, of the reactor can not only play a catalytic role during the
phenol, acetic acid and naphthalene were selected as the reaction process, but also is expected to enhance the corrosion
model compounds of phenolics, acid and polycyclic aromatic resistance of the reactor material. And in this part, the real
hydrocarbons in wastewater, and the gasification perfor- coal-gasification wastewater was selected as the reactant, and
mances and kinetics of the mixture were studied thoroughly the catalytic effect and corrosion resistance of the coated
[11,14]. Results showed that the gasification efficiency of SS316L was studied. This study intends to provide new ideas
hydrogen and carbon could reach 240.25% and 80.58%, for the design of catalysts during SCWPO process.
international journal of hydrogen energy xxx (xxxx) xxx 3
Ltd., Shanghai, China), packed with insulation course outside

Experimental the wall. And the heating rate of the electric heater was about
20 C/min (average value). The temperature inside the reactor
Materials was controlled by a temperature indicator and controller (TIC)
(ZWK-Ⅰ, Wujiang Jiahe Electric Appliance Co., Ltd., Suzhou,
Activated carbon (AC, 20e1000 A) and carbon nanotubes (CNT, China) using Pt (100) as the temperature sensor. After reaction,
30e50 nm) were purchased from Beijing Cnano Technology the products were cooled by a cooler and depressurized by a
Limited. Nickel chloride (NiCl2, analytical grade), aluminum back-pressure regulator (RC 200, Badger Meter Inc., USA) to
oxide (g-Al2O3, >92%), phenol (C6H6O, analytical grade), acetic normal temperature and pressure. A gas-liquid separator was
acid (CH3COOH, analytical grade), naphthalene (C10H8, used for separating the gaseous and liquid products. The
analytical grade), ammonia (NH3H2O, 25e28 wt% purity), volumetric flow rate of gaseous product was measured by a
hydrogen peroxide (H2O2, 30 wt% purity), methanol (CH3OH, wet type gas meter (LML-1, Jinhu Hongcheng Automation In-
chromatographically pure), cetyl trimethyl ammonium bro- strument Co., Ltd. Jinhu, China), and the gas sample was
mide (CTAB, analytical grade) and sodium hydroxide (NaOH, collected by a gas bag. The liquid sampling point was set at the
analytical grade) were purchased from China National Medi- pipeline that between the back end of back pressure valve and
cines Co., Ltd. the front end of gas-liquid separator. To reduce the error of the
In Section Activity and stability of the supported Ni- data, the gas and liquid samples were picked for three times
catalyst and Influences of the Ni loading amount on the ac- (1 min interval) since the operation time was reached. Each
tivity and stability of Ni/CNT, the feed was phenol solution sample was tested for three times, and the data present in this
with mass concentration of 1 wt%. And in Section Catalytic paper was the average value of the three samples.
activity and stability of Ni/CNT/SS316L, we used real coal- For all the experiments, the volumetric flow rate of the
gasification wastewater as feed. The initial chemical oxygen system was 1 L/h. The operation temperature and pressure
demand (COD) and TOC of the wastewater were about were 480 C, 25 MPa, with the corresponding reaction time of
14000 mg/L and 5000 mg/L, respectively. The coal-gasification 2min (the detailed calculation method is shown in Section
wastewater was picked from a coal-gasification station in Data interpretation). The adding amount of the catalysts were
Henan province in China. The main organic components 5 g in Section Activity and stability of the supported Ni-
analyzed by gas chromatograph-mass spectrometer (GC-MS) catalyst and influences of the Ni loading amount on the ac-
(6890-5793N, Agilent, California, USA) are shown in Table 1. tivity and stability of Ni/CNT.
Apparatus and procedures Preparation of the catalysts
The experiments were performed in a continuous flow The supported catalysts of Ni/AC, Ni/g-Al2O3 and Ni/CNT were
reactor, as shown in Fig. 1. The solution from feed and H2O2 prepared by electroless plating method. The AC, g-Al2O3 and
tank were pumped by two high-pressure metering pumps (DJ- CNT were firstly immersed in appropriate amounts of aqueous
Z500/0.5, Qingdao Gigantic Pump Mechanical Engineering Co., solution of NiCl2, respectively. Then 4 ml of the CTAB solution
Ltd., Qingdao, China) to the pre-heater, respectively. Then the (15 mmol/L) was added before ultrasonic dispersed for 20 min.
solutions were mixed in the mixer, and finally to the reactor. And 100 ml of hydrazine hydrate solution (85 wt%) was added
The reactor with a volume of 0.2 L was made of Hastelloy C276 after regulating the pH to 9 ± 0.05. The mixture was then heated
alloy which was designed to withstand a maximum temper- to 85 C and stirred for 60 min. The solid catalysts were obtained
ature and pressure up to 650 C and 30 MPa. The pre-heater through washing, filtering, vacuum drying at 80 C for 5 h, and
and reactor was heated with an electric heater with a power then calcined at 500 C in N2 atmosphere in the tube furnace.
of 5.5 kW (Cr20Ni80, Shanghai Feng Shan Alloy Material Co., The Ni/CNT/SS316L was prepared by electroless plating
method [29]. The base material of SS316L
(14.2 mm 1.8 mm 14 mm) was firstly burnished by the
Table 1 e Organic components in coal-gasification sand paper #2000, and ultrasonic cleaned for 10min. Then the
wastewater analyzed by GC-MS. base material of SS316L was plated in the thermostatic water
Organic compounds Species Proportion (%) bath (85 C) for 2 h using the electroless plating solution, as
shown in Table 2. And then the samples were calcined at
Phenolics 33 71.65
Phenol 1 1.18 500 C in N2 atmosphere for 2 h in the tube furnace. The sur-
Cresol 2 7.54 face and the cross-sectional morphologies and the elemental
Xylenol 5 27.94 distributions of the Ni/CNT/SS316L were shown in Fig. 2. The
Isomers of isopropyl-phenol 7 17.83 thickness of the Ni/CNT coating was about 1.5 mm.
Naphthol 5 5.97
Others 13 11.19
Analytical methods
Pyridines 5 6.97
Benzenes 8 6.29
Ketones 6 3.47 The gas composition was determined using a gas chromato-
Indanols 4 2.26 graph (SP-3420, Beifen-Ruili, Beijing, China) equipped with a
Thiophenes 3 3.27 thermal conductivity detector (TCD) and a 3 m 3 mm TDX-01
Others 2 6.09 packed column. The concentration of phenol in the liquid
Total 61 100 samples was determined by a liquid chromatography (LC)
Fig. 1 e Schematic diagram of the apparatus. 1- feed tank, 2-high-pressure pump, 3- pin valve, 4-pre-heater, 5-hydrogen
peroxide tank, 6- mixer, 7-Reactor, 8- electric heating furnace, 9-catalyst, 10-temperature indicator and controller, 11-cooler,
12- back pressure valve, 13-liquid product collector, 14-gas-liquid separator, 15-wet type gas meter, 16-gas collector.
Table 2 e Components of the electroless plating solution.

Solutes NiSO4$6H2O CrCl3$6H2O NaH2PO2$H2O C6H7O8 C3H6O3 CH3COONa
Concentration (g/L) 13 10.7 42.4 34 18 20
Fig. 2 e Surface and cross-sectional morphologies and the element distributions of Ni/CNT/SS316L ((a) SEM of Surface, (b)
EDS of surface), (c) SEM of cross-section, (d) EDS of cross-section).
Fig. 3 e Gas yields variations with supported Ni catalysts (480 C, 25 MPa, oxygen ratio of 0.2, Ni loading of 15 wt%).
equipped with a C-18 column (4.6 150 mm) and a UV de-

tector (LC-20A, Shimadzu, Japan). The total organic carbon ½O2 0
OR ¼ (2)
(TOC) and total carbon (TC) in the effluent was evaluated using ½COD0
a total organic carbon analyzer (ET1020A, Euro Tech, Hong
where [O2]0 is the concentration of O2 fed into the reactor,
Kong, China). Ni2þ ions in effluents were determined by
calculated by Eq. (3), mg/L. And [COD]0 is the initial COD of the
atomic absorption spectrophotometry (AAS) (TAS-996, Pur-
phenol solution or coal-gasification wastewater, mg/L.
kinje General, Beijing, China).
The morphologies of the catalysts were obtained by a 2H2 O2 /2H2 O þ O2 [ (3)
scanning electron microscopy (SEM) (JSM-6390A, Jeol, Tokyo,
Japan) equipped with X-ray energy dispersion spectroscopy Gas yield (Yi) was defined as Eq. (3):
(EDS). The element distributions on the surface of the cata- Mole yield of gas; mmol
lysts were analyzed by EDS. Surface areas of catalysts were Yi ¼ (4)
Mass of the reactant; g
measured using a surface and porosity analyzer (ASAP-2020,
Micromeritics, U.S.A) based on the BET method. where the subscript “i” represented H2, CO, CH4, and CO2,
respectively. The “reactants” represented phenol in Section
Data interpretation Activity and stability of the supported Ni-catalyst and In-
fluences of the Ni loading amount on the activity and stability
The reaction time (t) of the feed in reactor was calculated from of Ni/CNT, and that of “TOC” in Section Catalytic activity and
Eq. (1) stability of Ni/CNT/SS316L.
Gasification efficiencies (GE) of hydrogen (GEH) and carbon

Vr V0 (GEC) were defined as Eqs. (5) and (6), respectively:
t¼ (1)
Q0 V
Hydrogen atom amount in gas products
where Vr is the reactor volume (0.2 L), Q0 (1 L/h) and V0 (about GEH ¼ 100% (5)
Hydrogen amount in reactants
0.001 m3 kg1) are the volumetric flow rate and specific vol-
ume of liquid effluent under room temperature and atmo-
Carbon atom amount in gas products
spheric pressure conditions, respectively. V (about GEC ¼ 100% (6)
Carbon amount in reactants
0.001 m3 kg1) is the specific volume of feed solution under
The removal efficiencies (RT) of TOC were defined as Eq. (7):
reaction conditions, which is calculated using the physics
property software of water at 480 C, 25 MPa. As the mass Cin;T Cre;T
concentration of organic matter in feed was very low, the RT ¼ 100% (7)
Cin;T
properties of feed were assumed to be similar to those of
where Cin,T was the initial TOC concentration in the feed, mg/
water.
L. Cre,T represented the remained TOC concentration after
The oxygen ratio (OR) is defined as Eq. (2).
treated in the liquid effluent, mg/L.
Fig. 4 e Gasification efficiency and TOC removal efficiency variations with supported Ni catalysts (480 C, 25 MPa, oxygen
ratio of 0.2, Ni loading of 15 wt%).
In order to determine whether solid carbon was produced, the continuous operation process for 50 h. For example, the H2
the carbon balance was analyzed. The carbon balance coeffi- yield with Ni was 45.59 mmol/g (phenol) after operated for
cient (R), which is defined as the ratio of TC in the products to 20 h, and decreased to 35.59 mmol/g (phenol) after 50 h. While
the TC in the reactants, can be expressed as Eq. (8): with Ni/CNT catalyst, H2 yield was maintained at ~59.6 mmol/
g (phenol). Results indicated that the CNT support greatly
TCo;g þ TCo;liq
R¼ 100% (8) promoted the activity of Ni and increased the stability of Ni.
TCin
This may have some account with the BET of the catalyst. And
where TCin is the TC in the reactants, mg/L. TCo,g is the TC in the BET of the Ni/g-Al2O3, Ni/AC and Ni/CNT were 90, 150 and
the gas products, mg/L. TCo,liq is the TC in the liquid products, 275 m2/g, respectively. Li et al. [21] studied the catalytic ac-
mg/L. The value of (1-R) can be a indicator for solid residue tivity of Ni/CNT and Ni/a-Al2O3 on gasification of glycerol in
(such as char and coke) formation. supercritical water, and reported that the BET of Ni/CNT with
a Ni loading of 15 wt% was 290 m2/g, and the used Ni/CNT
catalyst had nearly the same BET 287.3 m2/g as the fresh
Results and discussion sample. The results also showed that Ni/CNT achieved stable
GEC during the 48 h operation, however, Ni/a-Al2O3 exhibited
Activity and stability of the supported Ni catalyst modest GEC decreasing with increasing time. The findings
were consistent with our results. Yin's study on SCWG of
Figs. 3 and 4 displayed the variations of gas yields, gasification glucose also found that the supports can enhance the activity
efficiencies and TOC removal efficiencies with different sup- of Ni [30]. And they found that the supports can prevent the
ported catalysts at 480 C, 25 MPa and oxygen ratio of 0.2, char formation on catalysts. However, the effects were
respectively. In this part, the Ni loading amount of the sup- different with different supports. Kang et al. [31] found that
ported catalysts was 15 wt%, and the adding amount of these the activity of Ni-based catalysts for SCWG of lignin was in the
catalysts were 5 g. And for the experiment points that with Ni
catalyst, the adding amount of Ni was 0.75 g. Results showed
that the yields of H2, CO, CH4, CO2, GEH, GEC and phenol
removal efficiencies decreased after operated for 20 h at the Table 3 e R variations with Ni-based catalysts (480 C,
presence of Ni, Ni/AC and Ni/g-Al2O3, which indicating that 25 MPa, oxygen ratio of 0.2, Ni loading of 15 wt%).
the activity of the catalysts decreased. The catalytic activity of Operation time/h R
Ni decreased more greatly than that of Ni/AC and Ni/g-Al2O3 none Ni Ni/g-Al2O3 Ni/AC Ni/CNT
were modest. Results showed that the AC, g-Al2O3 and CNT
1 82.81 86.01 91.58 93.89 98.51
supports can not only enhance the activity of Ni, but also had
10 82.81 85.80 91.76 93.71 98.51
some positive effects on the stability of Ni. And for Ni/CNT, the 20 83.05 86.04 91.32 93.26 98.98
gas yields, gasification efficiencies and the TOC removal effi- 30 83.05 84.37 89.15 93.70 98.33
ciency were obviously higher than that with Ni catalyst, and 40 82.62 83.18 86.31 92.60 98.05
significant decreasing of these values were not found during 50 82.66 77.89 83.86 90.91 97.91
catalysts was favourable for alleviating the solid residue for-

mation. This mainly because that the Ni-based catalysts used
here prevented the polymerization of phenol or its inter-
mediated. Minowa et al. [32] gasified cellulose (13.51 wt%)
from 200 C to 400 C and found that Ni can promote the seam
reforming reaction of the liquid products and the methana-
tion reaction of the gaseous products. Yin et al. gasified 10 wt%
[30] glucose in SCW with supported Ni catalysts, and found
that the supports of MgO, ZnO, Al2O3 and TiO2 can all reduce
the char formation. They attributed the reason to the inhibi-
tion effect on the generation of furfural or the acceleration
effect on the decomposition of furfural, which was supposed
to polymerize with the other intermediate products to form
the tar and char.
A few previous researches showed that the leaching of Ni2þ
Fig. 5 e Concentration of Ni2þ in the liquid effluent (480 C, may a major factor that influencing the activity of the catalyst
25 MPa, oxygen ratio of 0.2, Ni loading of 15 wt%). [21,33,34]. Thus, we detected the concentration of Ni2þ in the
liquid effluent, as shown in Fig. 5. Results showed that the
concentration of Ni2þ in liquid effluent was ~25.6 mg/L for Ni
catalyst at operation time of 1 h, and decreased sharply to
1.25 mg/L at 50 h. The concentration variations of Ni2þ for Ni/
g-Al2O3 and Ni/AC were similar, which were 16.5 mg/L and
10.21 mg/L at 1 h, respectively, and then decreased greatly and
finally stabilized at ~0.98 and ~0.46 mg/L after 30 h operation,
respectively. Whereas the Ni2þ concentration in effluent for
Ni/CNT kept stable at ~0.3 mg/L within the operation time.
Obviously, the activity and stability of the supported catalysts
was in the order of Ni/CNT > Ni/AC > Ni/g-Al2O3. Li’ [21] study
on SCWG of glycerol at 425 C, 25.2 MPa showed that Ni2þ
leaching from the Ni/a-Al2O3 (Ni loading 15 wt%) catalyst bed
was as high as 280 mg/L after operated for 1 h, and 102 mg/L at
3 h, but decreased to 11.6 mg/L at 23 h. However, the leached
concentration of Ni2þ for Ni/CNT were kept at ~9.0 mg/L from
Fig. 6 e Influences of Ni loading of Ni/CNT on gas yields, the beginning of the operation. The higher leaching concen-
gasification efficiencies, TOC removal efficiencies and R tration of Ni2þ in their research may due to the more filling
(480 C, 25 MPa, oxygen ratio of 0.2). amount of the catalysts. At the end of a 48 h experiment, Ni/a-
Al2O3 and Ni/CNT had lost 21.4% and 2.5% of the loaded Ni
amount, respectively. Behnia et al. [34] investigated the sta-
order of Al2O3 > TiO2 > ZrO2 > MgO. High surface area and bility of 20 wt% Ni/g-Al2O3 for SCWG of glucose at 500 C, and
other properties of the catalyst such as Ni dispersion, Ni found that the catalyst lost 76.9% Ni and 41.7% Al after 6 h of
crystalline phase as well as metal-support interaction have operation. In this work, the loss efficiency of Ni2þ for Ni/g-
significant effect. Al2O3 and Ni/CNT would be 27.51% and 1.94%, respectively,
Table 3 showed that the R values increased when the Ni- after 50 h operation. The results were consistent with Li's [21].
based catalysts were added, which indicating that the
Fig. 7 e -Surface morphology and element distributions of fresh Ni/CNT ((a)SEM of 15 wt% Ni/CNT, (b) SEM of 30 wt% Ni/CNT,
(c)EDS of agglomerates).
Fig. 8 e Influences of Ni/CNT/SS316L on gas yields (480 C, 25 MPa, oxygen ratio of 0.2).
amount of 30 wt%. The results inferred that too high Ni loading

would induce to the formation of solid char or carbon, which
would then decreased the activity of the catalysts.
We also detected the influences of Ni loading amount on the
BET of Ni/CNT. Results showed that when the loading capacity
of Ni was 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% and 30 wt%,
the corresponding BET were 356 m2/g, 315 m2/g, 275 m2/g,
265 m2/g, 250 m2/g and 245 m2/g, respectively. Results indicated
that the BET decreased with the increasing loading amount of
Ni when lower than 15 wt%, while changed little at the higher
loading amount. This mainly because that the loaded Ni
blocked some pores on the supports, which induce to the
reduction of BET. From the results we can conclude that the
unfavourable effect of the decreasing BET was lower than the
positive effect of the increasing active metal of Ni for Ni/CNT.
Fig. 9 e Influences of Ni/CNT/SS316L on GEC and R (480 C,
Kang et al. [31] also reported that the effects of Ni dispersion, Ni
25 MPa, oxygen ratio of 0.2).
crystalline phase were more significant than that of BET. Yan
et al. [35] reported that 15 wt% Ni/ZrO2 catalyst gave the highest
Influences of the Ni loading amount on the activity and activity and H2 yields for SCWG of polyethylene glycol. And Sato
stability of Ni/CNT et al. [36] found that the highest total gas yield was obtained
with 20 wt% Ni/MgO catalyst for hydrogen production of lignin
The influences of Ni loading amount for Ni/CNT on gas yields, in SCW. However, they did not study the influences of higher
gasification efficiencies, TOC removal efficiencies and R values nickel loading amount on the catalytic activity. Pairojpiriyakul
were shown in Fig. 6 (480 C, 25 MPa, oxygen ratio of 0.2). It could [37] studied the catalytic activity of Co/yttria-stabilized zirconia
be seen that the yields of H2, CO, CH4, CO2 increased obviously (YSZ) on SCWG of glycerol, and found that 10 wt% Co loading on
with the increasing of Ni loading amount when lower than 15 wt YSZ support was an optimum amount to enhance the reaction.
%, and then kept stable when the loading amount higher than They also found that the BET decreased with the increasing
20 wt%. The variation of GEH, GEC and TOC removal efficiencies loading amount when Co < 15 wt%, and changed little at the
were similar. And the R value increased form 89.77%e98.73%, higher loading amount. Therefore, there existed an optimal
when the Ni loading amount increased from 5 wt% to 10 wt%, value for the Ni loading. Excessive loading amount of the active
and then stabilized at about 98.5 wt% when at the range of 10 wt metal was easy to agglomerate, which was unfavourable to the
%~20 wt%. Considering the experimental inaccuracy, we spec- increasing of the activity. The surface morphologies and
ulated there was little solid residue generated when R >98.5%. element distribution of the fresh Ni/CNT with 15 wt% and 30 wt
However, the R decreased greatly to 90.4% at the Ni loading % were shown in Fig. 7. Results showed clearly that Ni loaded
Fig. 10 e Surface morphologies and the elements distributions of 316 L and Ni/CNT/SS316L after 50 h operation (480 C,
25 MPa, oxygen ratio of 0.2) ((a)SEM of SS316L, (b)EDS of SS316L, (c)SEM of Ni/CNT/SS316L, (d) EDS of Ni/CNT/SS316L).
on the inside of the CNT evenly when the loading amount of Ni Fig. 10 showed that the morphology of SS316L presented
was 15 wt%, while a large amount of spherical crystal was pitting corrosion, and the main elements on the surface were
found at the outside of CNT when loading 30 wt% Ni. These detected as Ni, Cr, Fe O. The Ni, Cr and Fe are the main com-
agglomerates were detected as NieP by EDS. As the agglomer- ponents of SS316L [40]. The existence of O was mainly because
ated NieP was not loaded on CNT, there was little effect on the that oxygen added in the SCWPO process reacted with the
BET of Ni/CNT. This could explain the reason for the little metal element, which formed metal oxides on the surface of
changed BET of Ni/CNT at higher Ni loading amount (>15 wt%). SS316L. The morphology of the cross-section showed a clear
corrosion layer that with a thickness of 5.55 mm, and the layer
Catalytic activity and stability of Ni/CNT/SS316L was rich in O, Cr and Fe. Gao et al. [41] studied the charac-
teristics of oxide films grown on SS316L exposed to H2O2-
In this part, we prepared the 15 wt% Ni/CNT on SS316L, and containing supercritical water (500 C, 24 MPa), and found that
studied the catalytic activity and stability of Ni/CNT/SS316L on the oxide films formed in the outer layer was rich in Fe, while
the gasification of coal-gasification wastewater in SCW. The the inner layer was rich in Cr and Fe, which agreed well with
variation of gas yields, GEC and R with 15 wt%Ni/CNT/316 L, our results. Guo et al. [40] also found that the oxide film
SS316L and without catalyst were shown in Figs. 8 and 9, formed on SS316L in 500 C and 600 C mainly consisted of two
respectively. Results showed that the influence of 316 L layers. The outer layer was rich in Fe and O, and the inner
stainless gave slightly catalytic effect on gas yields and GEC. layer was rich in Cr. And pores were observed in outer layer of
This was mainly because that 10.0e14.0 wt% Ni was present in the oxide scale. The surface morphology of Ni/CNT/SS316L in
SS316L, which played a catalytic effect on the gasification re- Fig. 11 showed that there distributed large amount of loosed
actions [38,39]. And Ni/CNT/SS316L showed great catalytic particles. The EDS analysis showed that the main elements on
effect on the gas yields and GEC within 20 h operation. For the surface were Cr and O. The content of Ni decreased greatly
example, H2 yield and GEC increased from 25.36 mmol/g (TOC) compared with the fresh Ni/CNT/SS316L (Fig. 2). This indi-
and 35.88% without catalyst to 75.12 mmol/g (TOC) and 96.04% cated that part of Ni/CNT coating had been peeled off from the
with Ni/CNT/SS316L after operated for 20 h, respectively. base material of SS316L. The cross-section morphology and
However, the gas yields and GEC started to decrease at 20 h, EDS showed clearly that the coating was stripped from the
which indicated that the catalytic activity was lower. And the base material, and formed a clear crack. The increasing oxy-
variation of R was similar with that of GEC. Therefore, we gen on the surface of base material indicated that the oxygen
detected the surface and cross-section morphologies of in the reaction medium had permeated into the base material
SS316L and Ni/CNT/SS316L after 50 h operation, as shown in through the cracked coating and then caused further corro-
Figs. 10 and 11, respectively. sion. The above results showed that the bond strength
Fig. 11 e Cross-sectional morphologies and the elements distributions of 316 L and Ni/CNT/SS316L after 50 h operation
(480 C, 25 MPa, oxygen ratio of 0.2) ((a)SEM of 316 L, (b)EDS of 316 L, (c)SEM of Ni/CNT/316 L, (d) EDS of Ni/CNT/316 L).
between the Ni/CNT coating and base material of SS316L Ni/CNT/SS316L. However catalytic activity began to
prepared by electroless plating method was poor, and the decrease after operated for 20 h. And obvious peeling of
preparation methods are still need further improvement. the coating was occurred after 50 h operation.
Results indicated that Ni/CNT/SS316L can give an excellent

Conclusions activity for the gasification of coal-gasification water. How-
ever, further study is necessary for improving the preparation
In this work, the supports of Ni catalysts, and loading amount method of coating.
of Ni for Ni/CNT during SCWPO of phenol were optimized at
480 C, 25 MPa, oxygen ratio of 0.2 in a continuous reactor. The
optimized Ni/CNT as a coating was prepared on the base
Acknowledgements
material of SS316L by electroless plating method to act as a
“tube wall” catalyst. The activity and stability of Ni/CNT/
This study was supported by the Projects from National Nat-
SS316L was investigated. And the main results are as follows:
ural Science Foundation of China (21576219), Natural Science
Foundation of Shaanxi Provincial Department of Education
(1) During the long operation time of 50 h, the activity and
(17JK0566) and Shaanxi Colleges Association of Science and
stability of the catalysts were in the order of Ni/
Technology for Young Talent Lifts (20160115), Natural Science
CNT > Ni/AC > Ni/g-Al2O3, which were main influenced
Foundation of Shaanxi Province of China (2018JQ2032).
by their BET value. And The activity of Ni/AC and Ni/g-
Al2O3 decreased after 30 h continuous operation, which
mainly due to the leaching of Ni2þ. references
(2) For the Ni/CNT catalyst, best activity was gain with the Ni
loading amount of 15 wt%. The BET decreased with the
increasing loading of Ni when lower than 15 wt%, and [1] Wang YZ, Wang SZ, Guo Y, Xu DH, Gong YM, Tang XY,
changed little at higher loading amount. Excessive Ni was Ma HH. Oxidative degradation of Lurgi coal-gasification
agglomerated outside of CNT at higher loading amount, wastewater with Mn2O3, Co2O3, and CuO catalysts in
supercritical water. Int J Hydrogen Energy
which was unfavourable to enhance the activity.
2011;51(51):16573e9.
(3) The Ni/CNT/SS316L showed well catalytic activity on
[2] Cui PZ, Mai ZH, Yang SY, Qian Y. Integrated treatment processes
SCWPO of the real coal-gasification wastewater. GEC for coal-gasification wastewater with high concentration of
increased from 35.88% without catalyst to 96.04% with phenol and ammonia. J Clean Prod 2017;142:2218e26.
[3] Guan QQ, Wei CH, Chai XS. Pathways and kinetics of partial [23] Hossain MZ, Chowdhury MBI, Jhawar AK, Charpentier PA.
oxidation of phenol in supercritical water. Chem Eng J Supercritical water gasification of glucose using bimetallic
2011;175:201e6. aerogel Ru-Ni-Al2O3 catalyst for H2 production. Biomass
[4] Zhao LX, Lu YJ. Hydrogen production by biomass gasification Bioenergy 2017;107:39e51.
in a supercritical water fluidized bed reactor: a CFD-DEM [24] Resende FLP, Savage PE. Effect of metals on supercritical
study. J Supercrit Fluids 2018;131:26e36. water gasification of cellulose and lignin. Ind Eng Chem Res
[5] Wang CY, Zhu W, Gong M, Su Y, Fan YJ. Influence of H2O2 2010;49(6):2694e700.
and Ni catalysts on hydrogen production and PAHs [25] Elliott DC. Catalytic hydrothermal gasification of biomass.
inhibition from the supercritical water gasification of Biofuel Bioprod Bior 2008;2(3):254e65.
dewatered sewage sludge. J Supercrit Fluids 2017;130:183e8. [26] Yu JD, Lu XY, Shi YJ, Chen QL, Guan QQ, Ning P, Tian SL, Gu JJ.
[6] Molino A, Migliori M, Blasi A, Davoli M, Marino T, Chianese S, Catalytic gasification of lignite in supercritical water with Ru/
Catizzone E, Giordano G. Municipal waste leachate CeO2-ZrO2. Int J Hydrogen Energy 2016;41(8):4579e91.
conversion via catalytic supercritical water gasification [27] Reddy SN, Nanda S, Dalai AK, Kozinski JA. Supercritical
process. Fuel 2017;206:155e61. water gasification of biomass for hydrogen production. Int J
[7] Xie RC, Liu Y, Bu T, Yao Y, Deng K, Yang ZB. Supercritical Hydrogen Energy 2014;39(13):6912e26.
water gasification of petrochemical wastewater for hydrogen [28] Wang YZ, Wang SZ, Guo Y, Xu DH, Gong YM, Tang XY,
production. Environ Prog Sustain 2016;35(2):428e32. Zhang J. Oxidative degradation of Lurgi coal gasification
[8] Elif D, Nezihe A. Hydrogen production by supercritical water wastewater: optimization using response surface
gasification of fruit pulp in the presence of Ru/C. Int J methodology. Environ Prog Sustain 2014;33(4):1258e65.
Hydrogen Energy 2016;41(19):8073e83. [29] Ding XY. Study on the corrosion resistance and property of coke
[9] Sheikhdavoodi MJ, Almassi M, Ebrahimi-Nik M, Kruse A, formation inhibition of the electroless coating [D]. Shanghai,
Bahrami H. Gasification of sugarcane bagasse in supercritical China: East China University of Science and Technology; 2013.
water; evaluation of alkali catalysts for maximum hydrogen [30] Yin JR, Cheng ZN, Guo LJ, Li S, Jin H. Products distribution and
production. J Energy Inst 2015;88(4):450e8. influence of nickel catalyst on glucose hydrothermal
[10] Guan QQ, Wei CH, Shi HS, Wu CF, Chai XS. Partial oxidative decomposition. Int J Hydrogen Energy 2017;42(7):4642e50.
gasification of phenol for hydrogen in supercritical water. [31] Kang K, Azargohar R, Dalai AK, Wang H. Systematic
Appl Energy 2011;88(8):2612e6. screening and modification of Ni based catalysts for
[11] Wang YZ, Wang SZ, Zhao GY, Guo YF, Guo Y. Hydrogen hydrogen generation from supercritical water gasification of
production by partial oxidation gasification of a phenol, lignin. Chem Eng J 2016;283:1019e32.
naphthalene, and acetic acid mixture in supercritical water. [32] Minowa T, Ogi T. Hydrogen production from cellulose using a
Int J Hydrogen Energy 2016;41(4):2238e46. reduced nickel catalyst. Catal Today 1998;45:411e6.
[12] Yong TL, Matsumura Y. Kinetics analysis of phenol and [33] Pairojpiriyakul T, Croiset E, Kiatkittipong K, Kiatkittipong W,
benzene decomposition in supercritical water. J Supercrit Arpornwichanop A, Assabumrungrat S. Catalytic reforming
Fluids 2014;87:73e82. of glycerol in supercritical water with nickel-based catalysts.
[13] Huelsman CM, Savage PE. Reaction pathways and kinetic Int J Hydrogen Energy 2014;39(27):14739e50.
modeling for phenol gasification in supercritical water. J [34] Behnia I, Yuan ZS, Charpentier P, Xu CB. Production of methane
Supercrit Fluids 2018;81:200e9. and hydrogen via supercritical water gasification of renewable
[14] Wang YZ, Gao F, Yang JQ, Guo Y, Zhu YT, Zhao GY, Fang CQ, glucose at a relatively low temperature: effects of metal
Guo YF, Wang SZ, Guo N. Partial oxidation kinetics of the catalysts and supports. Fuel Process Technol 2016;143:27e34.
mixture of acetic acid, phenol and naphthalene in [35] Yan Bo, Wu JZ, Xie C, He FM, Wei CH. Supercritical water
supercritical water for hydrogen production. Int J Hydrogen gasification with Ni/ZrO2 catalyst for hydrogen production
Energy 2017;42(31):19843e50. from model wastewater of polyethylene glycol. J Supercrit
[15] Zhen SC. Supercritical water gasification (SCWG) of coking Fluids 2009;50(2):155e61.
wastewater. Oxid Commun 2015;38(3):1464e9. [36] Sato T, Takeshi F, Yasuyoshi I, Hirokazu G, Yasutomo M,
[16] Shu ZZ. Study on gasification of phenol wastewater. Oxid Masahide S, Noboru S, Naotsugu I. Effect of water density on
Commun 2016;39(3A):2630e4. the gasification of lignin with magnesium oxide supported
[17] Guan QQ, Wei CH, Shi HS, Wu CF, Chai XS. Partial oxidative nickel catalysts in supercritical water. Ind Eng Chem Res
gasification of phenol for hydrogen in supercritical water. 2006;45(2):615e22.
Appl Energy 2011;88(8):2612e6. [37] Pairojpiriyakul T, Croisetb E, Kiatkittipong W,
[18] Jia LJ, Yu JD, Chen Y, Ning P, Guan QQ, Gu JJ, Miao RR, Kiatkittipong K, Arpornwichanop A, Assabumrungrat S.
Chen QL. Noble-metal-free bimetallic alloy nanoparticle- Hydrogen production from catalytic supercritical water
catalytic gasification of phenol in supercritical water. J reforming of glycerol with cobalt-based catalysts. Int J
Supercrit Fluids 2017;126:79e88. Hydrogen Energy 2013;38(11):4368e79.
[19] Guan QQ, Huang XD, Liu J, Gu JJ, Miao RR, Chen QL, Niang P. [38] Dileo GJ, Neff ME, Savage PE. Gasification of guaiacol and
Supercritical water gasification of phenol using a Ru/CeO2 phenol in supercritical water. Energy Fuel 2007;21(4):2340e5.
catalyst. Chem Eng J 2016;283:358e65. [39] Zhang LH, Champagne P, Xu CB. Screening of supported
[20] Liu X, Liu J, Wei CH, Guan QQ, Ning P, Gu JJ. Effect of the nature of transition metal catalysts for hydrogen production from
Ru-based catalysts' supports on supercritical water gasification glucose via catalytic supercritical water gasification. Int J
of phenol. Fresenius Environ Bull 2015;24(10):3229e34. Hydrogen Energy 2011;36(16):9591e601.
[21] Li S, Savage PE, Guo LJ. Stability and activity maintenance of [40] Guo XL, Chen K, Gao WH, Shen Z, Lai P, Zhang LF. A research on
Al2O3 and carbon nanotube-supported Ni catalysts during the corrosion and stress corrosion cracking susceptibility of
continuous gasification of glycerol in supercritical water. J 316L stainless steel exposed to supercritical water. Corros Sci
Supercrit Fluids 2018;135:188e97. 2017;127:157e67.
[22] Kang K, Azargohar R, Dalai AK, Wang H. Hydrogen [41] Gao X, Wu XQ, Zhang ZE, Guan H, Han EH. Characterization of
generation via supercritical water gasification of lignin using oxide films grown on 316l stainless steel exposed to H2O2
Ni-Co/Mg-Al catalysts. Int J Hydrogen Energy containing supercritical water. J Supercrit Fluids
2017;41(13):1835e46. 2007;42(1):157e63.

J Ijhydene 2018 08 218

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

J Ijhydene 2018 08 218

Uploaded by

Copyright:

Available Formats

international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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

Catalytic performances of Ni-based catalysts on

Yuzhen Wang a,b,*, Yitong Zhu a, Zhuan Liu a, Laibin Wang c,

article info abstract

respectively, at 560 C, 25 MPa and oxygen of 0.2. Zhen's study

Ltd., Shanghai, China), packed with insulation course outside

Apparatus and procedures Preparation of the catalysts

Table 2 e Components of the electroless plating solution.

equipped with a C-18 column (4.6 150 mm) and a UV de-

catalysts was favourable for alleviating the solid residue for-

amount of 30 wt%. The results inferred that too high Ni loading

Results indicated that Ni/CNT/SS316L can give an excellent

You might also like