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Hydrogen production via steam reforming of bio-oilHydrogen production via steam reforming of bio oil model compounds over NixMgyO solid solution
11th European Conference on Coal Research and its ApplicationsUniversity of Sheffield, UK
Presenter: Xiang Luo
S i P f T W P f Ed LSupervisor: Prof. Tao Wu, Prof. Ed Lester
Sep 2016
Content
1. Introduction
2. Catalytic synthesis
3 Steam reforming of Methanol3. Steam reforming of Methanol
4. Catalyst characterization
5. Catalyst promotion
6. Steam reforming of ethanol
7. Steam reforming of Acetic acid
8 St f i f Ph l8. Steam reforming of Phenol
9. Steam reforming of model bio-oil
1. Introduction
What is my research topic?y p
• Hydrogen production from bio-oil
• High temperature, catalysts, steam (catalytic steam reforming)
• Catalyst synthesis
• Highly catalytic activity durability• Highly catalytic activity, durability
• Carbon deposition, metal sintering
Bio-oil is not what we used for reforming process.
1. Introduction (cont)
• Active metal:
• Noble metals: Pd, Pt, Rh, Ru, Ir
• Base metals: Ni Co CuBase metals: Ni, Co, Cu
• Support material:
• Al2O3, MgO, ZrO2, Zeolite, CeO2
• Ni as a active compound (Cheap and available)
• MgO as a support material (basic material could restrain coke deposition from directly craking of hydrocarbon)
• Ni/MgO
2. Catalyst synthesis-SEM
ImpregnationImpregnation
Hydrothermal treatment
Co-precipitation + hydrothermal treatment
2. Catalyst synthesis-BET
NixMgyO-impre NixMgyO-hydro NixMgyO-copre
BET Surface Area: 49.7 m2/g 79.8 m2/g 54.0 m2/gBET Surface Area: 49.7 m /g 79.8 m /g 54.0 m /g
t-Plot microporevolume:
0.00469 cm3/g 0.00657 cm3/g 0.00392 cm3/g
Total pore volume 0.343 cm3/g 0.841 cm3/g 0.364 cm3/g
3. Steam reforming of Methanol
Methanol conversion & H2 selectivity results of support performance testing
Catalysts S/C Methanol conversion
H2 selectivity H2+CO %
NixMgyO-impre 3 55.3% 30.0% 92.3%x y
NixMgyO -hydro 3 97.4% 58.5% 90.6%
NixMgyO -copre 3 66.2% 38.0% 94.2%x gy p
NixAlyO 3 97.1% 61.6% 79.8%
NixMgyO-impre 1 51.4% 29.0% 84.0%x gy p
NixMgyO -hydro 1 58.3% 33.8% 86.7%
Ni Mg O -copre 1 57.5% 33.6% 88.9%NixMgyO copre 1 57.5% 33.6% 88.9%
NixAlyO 1 51.1% 28.8% 81.0%
4. Catalyst characterization-TGA
Catalysts S/C Weight percent loss (%)
TG-Carbon mass loss percentage
NixMgyO-impre
S/C=3
N/A
NixMgyO -hydro N/A
NixMgyO -copre N/A
NixAlyO 4.9%
NixMgyO-impre
S/C 1
3.9%
NixMgyO -hydro 1.5%100
24S/C=1
NixMgyO -copre 4.2%
NixAlyO 28.8%
80
90
100
NixMgyO-impre
%) 16
18
20
22
Exo
them
ic
60
70
80 NixMgyO-hydro NixMgyO-copre NixAlyO NixMgyO-impre NixMgyO-hydroNi Mg O-copreei
ght L
oss
(%620C
8
10
12
14
sed
(mV
/mg)
40
50
60 NixMgyO-copre NixAlyO
TG-W
e
0
2
4
6
Hea
t Rel
eas
570C
400 500 600 700 800 900
40
Temperature (C)
-2
4. Catalyst characterization-TPH
X. Luo et al., Appl. Catal. B-Environ, 194 (2016) 84-97.
4. Catalyst characterization-CO2-TPD
CO2-Temperature programmed deposition
NixAlyO
172C
413C
203C
540C
308C112C
NixMgyO-copre
213C324C
118C
x gy p
245C 316C
557CNixMgyO-hydro
245C
520C
118C
NixMgyO-impre
0 100 200 300 400 500 600
Temperature (C)
5. Catalyst promotion
Theoretical element molar ratio Measured element molar ratioa
Catalyst name NiPromoted element
(Ce/La/Co)Mg+O Ni
Promoted element
(Ce/La/Co)Mg
NiMgO 10% N/A 90% 8.4% N/A 51.7%
Ni1CeMgO 10% 1% 89% 8.7% 0.6% 49.0%
Ni2CeMgO 10% 2% 88% 8.7% 1.7% 47.9%
Ni3CeMgO 10% 3% 87% 8.3% 2.3% 45.0%
Ni4CeMgO 10% 4% 86% 8.0% 3.0% 40.9%
Ni2LaMgO 10% 2% 88% 7 6% 1 7% 45 7%Ni2LaMgO 10% 2% 88% 7.6% 1.7% 45.7%
Ni4LaMgO 10% 4% 86% 8.2% 3.6% 46.5%
Ni6LaMgO 10% 6% 84% 7.9% 5.4% 44.9%
Ni2CoMgO 10% 2% 88% 8.2% 1.7% 45.4%
Ni4CoMgO 10% 4% 86% 8.3% 3.4% 47.3%
Ni6CoMgO 10% 6% 84% 8.6% 5.2% 44.7%a Measured by ICP-MS for the bulk composition, balanced by oxygen.
6. Steam reforming of ethanol
Catalyst H yield (%) X (%)CO2
selectivityCH4
SelectivityCO Selectivity
Catalyst H2 yield (%) Xethanol (%) selectivity (%)
Selectivity (%)
(%)
NiMgO 700(30h) 62.2 90.7 29.8 12.1 48.9g ( )
Ni1CeMgO 700(30h) 77.2 87.7 52.9 4.9 30.1
Ni2CeMgO 700(30h) 79.5 86.4 54.3 1.3 30.9
Ni3CeMgO 700(30h) 80.3 87.1 55.9 2.1 29.1
Ni4CeMgO 700(30h) 75.7 88.5 47.1 4.3 37.1
Ni2LaMgO 700(30h) 74.3 84.4 53.2 5.7 25.6
Ni4LaMgO 700(30h) 70.7 88.5 49.2 10.6 28.7
Ni6LaMgO 700(30h) 70.8 87.9 48.3 10.2 29.4
Ni2CoMgO 700(30h) 81.8 89.5 56.1 2.3 31.1
Ni4CoMgO 700(30h) 78.8 89.1 53.9 4.8 30.4
Ni6CoMgO 700(30h) 62.0 90.1 26.5 11.1 52.4
6. Steam reforming of ethanol
6. Steam reforming of ethanol
CO55.9
53.256.1
48.950
60
%)
CO2
CH4
CO
29.9 29 1 31.1
40
gas
yiel
d (%
29.9
12 1
29.125.6
20
30
rbon
aceo
us
12.1
2.15.7
2.30
10Car
NiMgO 3%Ce/NiMgO 2%La/NiMgO 2%Co/NiMgO
7. Steam reforming of Acetic acid
C t l t H i ld (%)Xacetic acid
CO2
l ti itCH4
S l ti itCO
S l ti itCatalyst H2 yield (%) acetic acid
(%)selectivity
(%)Selectivity
(%)Selectivity
(%)
NiMgO 700(30h) 61.9 81.7 44.3 2.2 35.2
Ni1CeMgO 700(30h) 86.2 99.5 75.6 1.0 22.9
Ni2CeMgO 700(30h) 74.7 84.0 66.5 0.5 17.0
Ni3CeMgO 700(30h) 76.1 84.9 68.8 0.4 15.7
Ni4CeMgO 700(30h) 85.2 97.1 76.0 1.0 20.1
Ni2LaMgO 700(30h) 86.5 96.5 79.4 0.3 16.8
Ni4LaMgO 700(30h) 82.3 96.0 75.1 1.7 19.2
Ni6L M O 700(30h) 86 7 100 5 78 1 1 6 20 8Ni6LaMgO 700(30h) 86.7 100.5 78.1 1.6 20.8
Ni2CoMgO 700(30h) 86.9 99.1 79.0 1.1% 19.0
Ni4CoMgO 700(30h) 49 8 61 7 41 3 1 9 18 5Ni4CoMgO 700(30h) 49.8 61.7 41.3 1.9 18.5
Ni6CoMgO 700(30h) 10.6 19.4 9.6 3.3 6.5
8. Steam reforming of Phenol
C t l t H i ld (%)Xethanol
CO2
l ti itCH4
S l ti itCO
S l ti itCatalyst H2 yield (%) ethanol
(%)selectivity
(%)Selectivity
(%)Selectivity
(%)
NiMgO 800(30h) 73.7 94.1 45.7 0.1 48.3
Ni1CeMgO 800(30h) 85.3 94.3 75.7 0.1% 18.4
Ni2CeMgO 800(30h) 83.0 93.3 71.8 0.1% 21.4
Ni3CeMgO 800(30h) 80.0 95.0 62.5 0.1% 32.4
Ni4CeMgO 800(30h) 81.5 90.1 72.7 0.1% 17.2
Ni2LaMgO 800(30h) 84.3 93.9 72.5 0.27% 21.1
Ni4LaMgO 800(30h) 84.8 92.7 75.5 0.06% 17.2
Ni6LaMgO 800(30h) 85.2 94.0 77.2 0.12% 16.7
Ni2CoMgO 800(30h) 73.8 100.1 38.1 0.1 61.9
Ni4C M O 800(30h) 87 4 100 0 70 0 0 1 31 7Ni4CoMgO 800(30h) 87.4 100.0 70.0 0.1 31.7
Ni6CoMgO 800(30h) 87.7 98.6 74.5 0.1 24.0
9. Steam reforming of model bio-oil
• Refer to the real bio-oil from Yan’s group in East China University of Science and Technology: C1H1.695O0.439S0.004N0.025
• Use ethanol, acetic acid, Phenol to synthesis a model bio-oil
• Our model bio-oil: C1H1.696O0.439
• Combine the previous experiment results: NiMgO Ni1CeMgO Ni2LaMgO• Combine the previous experiment results: NiMgO, Ni1CeMgO, Ni2LaMgO, Ni2CoMgO
9. Steam reforming of model bio-oil
THANK YOU &THANK YOU &QUESTIONS
Please feel free to contact me if you have any question: Xiang.luo@Nottingham.edu.cn
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