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Hydrogen production via steam reforming of bio-oil Hydrogen production via steam reforming of bio oil model compounds over Ni x Mg y O solid solution 11 th European Conference on Coal Research and its Applications University of Sheffield, UK Presenter: Xiang Luo S i P fT W P f Ed L Supervisor: Prof . T ao Wu, Prof . Ed Lester Sep 2016
Transcript
Page 1: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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

Page 2: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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

Page 3: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of 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.

Page 4: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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

Page 5: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

2. Catalyst synthesis-SEM

ImpregnationImpregnation

Hydrothermal treatment

Co-precipitation + hydrothermal treatment

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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

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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%

Page 8: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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

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4. Catalyst characterization-TPH

X. Luo et al., Appl. Catal. B-Environ, 194 (2016) 84-97.

Page 10: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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)

Page 11: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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.

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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

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6. Steam reforming of ethanol

Page 14: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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

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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

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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

Page 17: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

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

Page 18: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

9. Steam reforming of model bio-oil

Page 19: Hydrogen production via steam reforming of bioHydrogen … Luo... · 2020. 10. 20. · Hydrogen production via steam reforming of bioHydrogen production via steam reforming of bio-oil

THANK YOU &THANK YOU &QUESTIONS

Please feel free to contact me if you have any question: [email protected]


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