The document summarizes research on sorption-enhanced steam reforming of ethanol (SE-SRE) for hydrogen production. The key points are:
1) Preliminary investigations identified reaction pathways and kinetics for SRE on Ni/Al2O3 catalyst. Thermodynamic modeling determined optimal steam-to-ethanol ratios to maximize hydrogen yield while minimizing carbon deposition.
2) Initial experiments on SE-SRE used Ni/Al2O3 catalyst and hydrotalcite sorbent, achieving high purity hydrogen. Further work developed Cu-based catalysts to prevent carbon deposition and hybrid catalyst-sorbent materials.
3) K-promoted hydrotalcite was synthesized and showed higher CO2 sorption
Studies on Nitration of Phenol over Solid Acid Catalyst | Crimson PublishersDanesBlake
Phenol was selectively nitrated in liquid phase to produce ortho-nitrophenol using dilute nitric acid (30%) at room temperature in presence of hydrochloric acid treated γ-alumina. Initially Al(NO3) and NH4HCO3 were reacted to prepare Al (OH)3 which on successive calcinations at 550 ᴼC for 5h produce γ-alumina. The γ-alumina was characterized by BET, XRD, SEM and NH3-TPD analysis. The XRD profile confirmed the crystalline structure of the solid acid catalyst γ-alumina. The NH3-TPD analysis showed the development of lewis acidity on the surface of hydrochloric acid treated γ-alumina. The effects of various parameters such as concentration of reactants, types of catalyst, weight of the catalyst, solvent, temperature and time of reaction have been studied. The kinetics of the reaction was also investigated.
Studies on Nitration of Phenol over Solid Acid Catalyst by Lipika Das, Koushi...crimsonpublisherspps
Phenol was selectively nitrated in liquid phase to produce ortho-nitrophenol using dilute nitric acid (30%) at room temperature in presence of hydrochloric acid treated γ-alumina. Initially Al (NO3) and NH4HCO3 were reacted to prepare Al (OH)3 which on successive calcinations at 550 0C for 5h produce γ-alumina. The γ-alumina was characterized by BET, XRD, SEM and NH3-TPD analysis. The XRD profile confirmed the crystalline structure of the solid acid catalyst γ-alumina. The NH3-TPD analysis showed the development of lewis acidity on the surface of hydrochloric acid treated γ-alumina. The effects of various parameters such as concentration of reactants, types of catalyst, weight of the catalyst, solvent, temperature and time of reaction have been studied. The kinetics of the reaction was also investigated
https://crimsonpublishers.com/pps/fulltext/PPS.000505.php
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Please click on link: https://crimsonpublishers.com
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PTC IS THE PHASE TRANSFER CATALYSIS HERE TYPES OF PTC ARE DISCUSSED , THEORIES OF CATALYSIS AND MECHANISM OF PTC, ADVANTAGES OF PTC, APPLICATION OF PTC
Visible light assisted photocatalytic reduction of CO2 using a graphene oxide...Pawan Kumar
A new heteroleptic ruthenium complex containing 2-thiophenyl benzimidazole ligands was synthesized
using a microwave technique and was immobilized to graphene oxide via covalent attachment. The synthesized
catalyst was used for the photoreduction of carbon dioxide under visible light irradiation without
using a sacrificial agent, which gave 2050 μmol g−1 cat methanol after 24 h of irradiation
Removal of Coke during Steam Reforming of Ethanol over La-CoOx Catalystinventy
Research Inventy : International Journal of Engineering and Science is published by the group of young academic and industrial researchers with 12 Issues per year. It is an online as well as print version open access journal that provides rapid publication (monthly) of articles in all areas of the subject such as: civil, mechanical, chemical, electronic and computer engineering as well as production and information technology. The Journal welcomes the submission of manuscripts that meet the general criteria of significance and scientific excellence. Papers will be published by rapid process within 20 days after acceptance and peer review process takes only 7 days. All articles published in Research Inventy will be peer-reviewed.
Studies on Nitration of Phenol over Solid Acid Catalyst | Crimson PublishersDanesBlake
Phenol was selectively nitrated in liquid phase to produce ortho-nitrophenol using dilute nitric acid (30%) at room temperature in presence of hydrochloric acid treated γ-alumina. Initially Al(NO3) and NH4HCO3 were reacted to prepare Al (OH)3 which on successive calcinations at 550 ᴼC for 5h produce γ-alumina. The γ-alumina was characterized by BET, XRD, SEM and NH3-TPD analysis. The XRD profile confirmed the crystalline structure of the solid acid catalyst γ-alumina. The NH3-TPD analysis showed the development of lewis acidity on the surface of hydrochloric acid treated γ-alumina. The effects of various parameters such as concentration of reactants, types of catalyst, weight of the catalyst, solvent, temperature and time of reaction have been studied. The kinetics of the reaction was also investigated.
Studies on Nitration of Phenol over Solid Acid Catalyst by Lipika Das, Koushi...crimsonpublisherspps
Phenol was selectively nitrated in liquid phase to produce ortho-nitrophenol using dilute nitric acid (30%) at room temperature in presence of hydrochloric acid treated γ-alumina. Initially Al (NO3) and NH4HCO3 were reacted to prepare Al (OH)3 which on successive calcinations at 550 0C for 5h produce γ-alumina. The γ-alumina was characterized by BET, XRD, SEM and NH3-TPD analysis. The XRD profile confirmed the crystalline structure of the solid acid catalyst γ-alumina. The NH3-TPD analysis showed the development of lewis acidity on the surface of hydrochloric acid treated γ-alumina. The effects of various parameters such as concentration of reactants, types of catalyst, weight of the catalyst, solvent, temperature and time of reaction have been studied. The kinetics of the reaction was also investigated
https://crimsonpublishers.com/pps/fulltext/PPS.000505.php
For more open access journals in Crimson Publishers
Please click on link: https://crimsonpublishers.com
For More Articles on Prime research material
Please click on: https://crimsonpublishers.com/pps/
PTC IS THE PHASE TRANSFER CATALYSIS HERE TYPES OF PTC ARE DISCUSSED , THEORIES OF CATALYSIS AND MECHANISM OF PTC, ADVANTAGES OF PTC, APPLICATION OF PTC
Visible light assisted photocatalytic reduction of CO2 using a graphene oxide...Pawan Kumar
A new heteroleptic ruthenium complex containing 2-thiophenyl benzimidazole ligands was synthesized
using a microwave technique and was immobilized to graphene oxide via covalent attachment. The synthesized
catalyst was used for the photoreduction of carbon dioxide under visible light irradiation without
using a sacrificial agent, which gave 2050 μmol g−1 cat methanol after 24 h of irradiation
Removal of Coke during Steam Reforming of Ethanol over La-CoOx Catalystinventy
Research Inventy : International Journal of Engineering and Science is published by the group of young academic and industrial researchers with 12 Issues per year. It is an online as well as print version open access journal that provides rapid publication (monthly) of articles in all areas of the subject such as: civil, mechanical, chemical, electronic and computer engineering as well as production and information technology. The Journal welcomes the submission of manuscripts that meet the general criteria of significance and scientific excellence. Papers will be published by rapid process within 20 days after acceptance and peer review process takes only 7 days. All articles published in Research Inventy will be peer-reviewed.
Thermo catalytic decomposition of methane over Pd/AC and Pd/CB catalysts for ...IJERA Editor
Hydrogen production studies have been carried using Thermo Catalytic Decomposition (TCD) Unit. Thermo catalytic decomposition of methane is an attractive route for COx free production of hydrogen required in fuel cells. Although metal based catalysts produce hydrogen at low temperatures, carbon formed during methane decomposition reaction rapidly deactivates the catalyst. The present work compares the results of 10 wt% Pd supported on commercially available activated carbon and carbon black catalysts (samples coded as Pd10/AC and Pd10/CB respectively) for methane decomposition reaction. Hydrogen has been produced by thermo catalytic decomposition of methane at 1123K and Volume Hourly Space Velocity (VHSV) of 1.62 L/h g on the activity of both the catalysts has been studied. XRD of the above catalysts revealed, moderately crystalline peaks of Pd which may be responsible for the increase in catalytic life and formation of carbon fibers. Also during life studies (850°C and 54 sccm of methane) it has been observed that the activity of carbon black is sustainable for a longer time compared to that of activated carbon.
Study of the Influence of Nickel Content and Reaction Temperature on Glycerol...IJRESJOURNAL
ABSTRACT: La2O3-SiO2-supported nickel catalysts were evaluated in glycerol steam reforming. The samples (30wt% La and 5, 10 and 15wt% of Ni on 70wt% commercial SiO2), prepared by the simultaneous impregnation method, were characterized by EDX, nitrogen physisorption, XRD, in-situ XRD, XANES and TPR. The analyses revealed NiO species weakly interact with the support and the different metallic surface areas of the catalysts. Catalytic tests were performed in a fixed bed reactor at 600oC and 15Ni catalyst, which showed the best performance, was also evaluated at 500oC and 700oC. According to the results, the Ni content on the catalyst surface interferes in the distribution of gaseous products H2, CO, CO2 and CH4. The increase in the Ni content increases the carbon formation during reaction. The reaction temperature affected the catalytic performance and the best results were obtained with the 15Ni catalyst at 600oC, which was also tested for 20 hours for the analysis of its stability.
Reaction of aniline with ammonium persulphate and concentrated hydrochloric a...Maciej Przybyłek
In this paper, the reaction of aniline with ammonium persulphate and concentrated HCl was studied. As a result of our experimental studies, 2,4,6-trichlorophenylamine was identified as the main product. This shows that a high concentration of HCl does not favour oxidative polymerisation of phenylamine, even though the ammonium persulphate/HCl system is widely used in polyaniline synthesis. On the basis of the experimental data and density functional theory for reaction path modelling, we proposed a mechanism for oxidative chlorination of aniline. We assumed that this reaction proceeded in three cyclically repeated steps; protonation of aniline, formation of singlet ground state phenylnitrenium cation, and nucleophilic substitution. In order to confirm this mechanism, kinetic, thermochemical, and natural bond orbital population analyses were performed.
Hydrogenation of sugars over supported metal catalyst - effect of supportpbpbms6
A process of hydrogenation of sugars into sugar alcohol is described in presence of supported metal catalysts. Influence of support in reaction is also shown.
An Update on Gas CCS Project: Effective Adsorbents for Establishing Solids Looping as a Next Generation NG PCC Technology - presentation by Colin Snape in the Natural Gas CCS session at the UKCCSRC Cardiff Biannual Meeting, 10-11 September 2014
OXIDATION OF POLYETHYLENE GLYCOL-200 BY POTASSIUM PERIODATE IN ALKALINE MEDIU...Ratnakaram Venkata Nadh
Kinetics of PEG-200 oxidation by potassium periodatewas studied in alkaline medium. First-order dependence of
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An inverse fractional order with respect to alkaliwas shown. Arrhenius parameters were calculated. Rate law was
postulated taking into consideration of experimental results.
International Journal of Engineering Research and DevelopmentIJERD Editor
Electrical, Electronics and Computer Engineering,
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Automation and Mechatronics Engineering,
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Aerospace Engineering.
Paladio soportado sobre hidrotalcita como un catalizador para la reacción de ...52900339
Resumen
Se estudió la eficacia de diversas sales de paladio como catalizador en la reacción de acoplamiento cruzado de Suzuki, y la influencia de la base y de temperatura utilizados en su conversión, El uso de PdCl2 soportado sobre hidrotalcita como catalizador en presencia de carbonato de potasio como se encontró base para proporcionar los mejores resultados. Las temperaturas de reacción superiores a 90 °C garantizarse niveles de conversión a la par con los de muchos catalizadores homogéneos.
Paladio soportado sobre hidrotalcita como un catalizador para la reacción de ...
Thesis Defense
1. Departamento de Engenharia Química
Rua Dr. Roberto Frias, S/N | 4200-465 Porto| Portugal lsre@fe.up.pt
http://lsre.fe.up.pt
Sorption-Enhanced Steam Reforming
of Ethanol for Hydrogen Production
By: Yi-Jiang Wu
Supervisor: Prof. Alirio E. Rodrigues
Co-advisor: Dr. Adelino F. Cunha
11 July 2014
3. 1. Background
Hydrogen
Clean
– Low environmental impact
High energy density
– 120.7 kJ/g
High efficiency
– Hydrogen fuel cell
Production
– Electrolysis
– Photobiological
– Water-gas-shift
– Steam reforming
• (natural gas, bio-ethanol...)
*U.S. Department of energy, http://www.hydrogen.energy.gov/
Figure 1. The integration of a hydrogen economy.*
2
4. 1. Background
Standard methane reforming process
– High temperature reaction
• energy supply, construction material, catalyst deactivation
– Purification
• H2 purity, H2 recovery
3
Harrison, Ind. Eng. Chem. Res., 2008, 47, 6486–6501.
Reforming
Reactor
CH4/H2O
Feed
Flue gas
WGS
Reactor
PSA
units
99.5 + % H2
CO2
absorption
Methanator
or PROX
95 + % H2
Trace CO,CO2
PSA Off-gasFuel/Air
Reaction Purification
CH4+H2O⇌CO+3H2 CO+H2O⇌CO2+3H2
5. 1. Background
Sorption-enhanced reaction process (SERP)
– Le Chatelier’s principle
Old and new
– Concept proposed in 1868*
– SERP named in 1996**
4
CH4 g + 2H2O g
catalyst
4H2 g + CO2(g) CH4 g + 2H2O g
catalyst and sorbent
4H2 g + CO2 ∙ sorbent(s)
Reaction
Catalyst
CO2
Sorbent
CH4 + H2O CO2
H2
H2
H2
CO2
CO2
CO2
CO2
H2
CO2
C2H6O + H2O
6CO2+12H2O
Photosynthesis
ΔH0 = +2540kJ/mol
ΔG0 = +2830kJ/mol
C6H12O6+6H2O
Distillation & Combustion
(Low efficiency)
Fermentation
ΔH0= +20 kJ/mol
ΔG0= -210 kJ/mol
Hydrogen Fuel Cell
ΔH0= -2904 kJ/mol
ΔG0= -2748 kJ/mol
Steam Reforming
ΔH0= +344 kJ/mol
ΔG0= +128 kJ/mol
2CO2+2C2H5OH+6H2O
6CO2(s)+12H2
6O2
* Motay et al., Bull. Soc. Chim. Fr., 1868, 9, 334.
** Sircar et al., AICHE J., 1996, 42(10), 2765-2772.
6. 2. Objectives
High purity hydrogen production from ethanol at
intermediate temperature (673 K – 773 K)
Sorption-enhanced steam reforming of ethanol (SE-SRE)
Materials requirements:
– Catalysts
• activity, selectivity and stability
– Sorbents
• capacity, selectivity, kinetics, regeneration and stability
Numerical simulation for improvement
– Reaction condition
– Operating parameter
5
H2O,
C2H5OH
H2, H2O
Catalyst
Sorbent
22 5 2 2( ) 3 ( ) 2( ( )6 )catalyst
sorbent
C H OH g CO Sorbent sH O g H g
7. 3. Preliminary Investigation
Experimental setup
He N2 H2 CO2
Mass
Spectrometer
Vent
1
2
3
54
6
7
8 9
Figure 1 Schematic and picture of the experimental unit: (1) feeding
gases; (2) mass-flow controllers; (3) feeding mixture; (4)
pump for liquids; (5) mixing valve; (6) reforming reactor; (7)
heating furnace; (8) back pressure valve; (9) mass
spectrometer.
6
8. Ethanol Acetaldehyde
Dehydrogenation
Hydrogen
Steam Methane Reforming
Dehydration
Coke
Ethane
Dehydrogenation Steam Ethylene Reforming*
Ethylene
Boudouard Reaction
Methane Decomposition
Water Gas Shift
Carbon monoxide
4 22CH C H
2 2C CO CO
2 2 2CO H O CO H
4 2 6 22CH C H H
4 2 23CH H O CO H
4 2 2 22 4CH H O CO H
2 2C H O CO H
2 4 2
1
2
C H C H
3 2 2 4 2CH CH OH C H H O
Methane
3 4CH CHO CH CO
Decomposition
3 2 4 2CH CH OH CH CO H
3 2 3 2CH CH OH CH CHO H
Decomposition
2 6 2 4 2C H C H H
Ethylene
Polymerisation
Coke Gasification
Steam Ethane Reforming**
3. Preliminary Investigation
Reaction pathway for steam reforming of ethanol (SRE)
– Reaction conditions
• temperature, pressure, steam-to-ethanol molar ratio (RS/E)…
– Catalysts compositions
• active metal, support, structure…
7
Wu et al., Can. J. Chem. Eng., 2014, 92 (1), 116-130.
9. 3. Preliminary Investigation
Reaction mechanism on Ni/Al2O3(Degussa 1001)
– Langmuir-Hinshelwood Hougen-Watson (LHHW)
Reaction kinetics
– Power-rate law and LHHW expressions
8
0 1 2 3 4 5
0
8
16
24
32
40
pEtOH
[kPa]
473 K
573 K
673 K
773 K
873 K
rSRE
[mol·kg-1
h-1
]
Figure 2 Kinetic model vs. Experimental results
(filled spots) at ptotal = 1 bar with a RS/E of
10 in the feed. Power rate model (dashed
lines); LHHW model (solid lines).
Wu et al., Can. J. Chem. Eng., 2014, 92 (1), 116-130.
10. 3. Preliminary Investigation
Thermodynamic analysis
– Gibbs free energy minimization
– Real gas vs. ideal gas for SRE
• Virial model
– Steam-to-ethanol (RS/E) molar ratio
• Carbon deposition
• Hydrogen yield
9
SRE (real gas) SRE (ideal gas)
T XH2O YH2 YCO XH2O YH2 YCO
K % mol/molEtOH % mol/molEtOH
773 12.7 5.21 0.11 13.6 5.48 0.06
Table 1. Equilibrium of SRE at 100 kPa, H2O/Ethanol = 20 [mol/mol]
Wu et al., Chem. Eng. Technol. 2012, 35 (5), 847-858.
min 1 2( , , , ,... )NG G T p n n n
500 600 700 800 900
4
6
8
10
12
14
16
18
20
YH2
[mol/molEtOH,0
]
T [K]
0.0
0.4
0.7
1.4
2.1
2.8
3.4
4.0
4.4
4.9
5.2
5.5
5.8
6.0
b)
RS/E
[mol/mol]
Figure 3 The effects of steam-to-ethanol ratio on
carbon deposition (a) and hydrogen yield (b).
500 625 750 875 1000 1125 1250
0
1
2
3
4
5
H2
yield
Carbon deposition
3
2.5
2
1.5
1
0.5
0
3 2.5
2
1.5 1
0.5
Y[mol/molEtOH,0
]
T [K]
0
RS/E
a)
11. 3. Preliminary Investigation
High temperature CO2 sorbent
– SE-SRE reaction performance
– Hydrogen product with HTlc
• High purity > 99 mol %
• CO content < 30 ppm
• Direct fuel cell application
10
Wu et al., Chem. Eng. Technol. 2012, 35 (5), 847-858.
CaO Li2ZrO3 HTlc
T
[K] [mol %] [ppm] [mol %] [ppm] [mol %] [ppm]
773 84 915 78 1460 99 11
Figure 4 CO2 adsorption Li2ZrO3 (a) and HTlc (b).
2Hy COy COy COy2Hy 2Hy
Materials Capacity Stability Kinetics
CaO Good Poor Fair
Li2ZrO3 Fair Good Poor
Hydrotalcite (HTlc) Poor Good Good
Li2ZrO3
Adsorption at
773 K
Li2ZrO3
ZrO2
Li2CO3
(Solid)
Li2ZrO3
Li+
ZrO2 Shell O2-
Li2CO3 Shell
co2
ZrO2 ZrO2ZrO2
Desorption at
1053 K
Li2CO3
(Liquid)
Li+
CO2 O2-
Li2ZrO3
ZrO2
Li2ZrO3
co2
a)
b)
Table 2 Equilibrium of SE-SRE at 100 kPa, H2O/Ethanol = 20 [mol/mol].
12. 3. Preliminary Investigation
Sorption enhanced reaction performance
– Ni/Al2O3 catalyst (Degussa 1001)
– Hydrotalcite sorbent (Sasol MG30)
Figure 5 Product distribution vs. Reaction time.
Reaction conditions: T = 673 K; p = 100 kPa;
RS/E = 10; mcat = 4×1.25 g; msorb = 3×25.0 g.
H2O,
C2H5OH
H2, H2O
Nickel-based
Catalyst
(1001)
Hydrotalcite
Sorbent
(MG30)
11
Cunha et al., Can. J. Chem. Eng. 2012, 90(6), 1514-1526.
He N2 H2 CO2
Mass
Spectrometer
Vent
0 10 20 30 40 50 60
0
20
40
60
80
100
yCO
[mol%]
yH2
,CH4
,CO2
[mol%]
t [min]
H2
CO2
CH4
CO 0
1
2
13. 4. Material Development
Compatibility of catalyst and sorbent
– Layered system
– Ideal mixture
– Hybrid material
H2
Catalyst (active phase)
H2C2H5OH/CH4
H2O
Adsorbent
H2 Yield CO2 Yield
H2C2H5OH/CH4
H2O
C2H5OH/CH4
H2O
Cunha et al., Chem. Eng. Res. Des., 2013, 91(3), 581-592.
12
14. 4. Material Development
Deactivation due to the carbon deposition
– Ni-based catalyst at high temperature
Cu-based catalysts for dehydrogenation
– Avoid carbon deposition
Cu-Catalyst
H2C2H5OH, H2O
Adsorbent
C2H4O, H2O
CH4, H2,COX
Ni-Catalyst
1st
Layer 2nd
Layer
Ni-catalyst polymerisation
2 5 2 2 4high-temperature
CarbonC H OH H O C H
Cu-catalyst Ni-catalyst
2 5 2 2 4 4C H OH H C H O CH CO
P. D. Vaidya, A. E. Rodrigues, Chem. Eng. J., 2006, 117(1), 39-49.
13
Cunha et al., Chem. Eng. Res. Des., 2013, 91(3), 581-592.
15. 4. Material Development
Preparation of the hybrid materials
14
HTlc
Solution of
Ni(NO3)2 or Cu(NO3)2
Impregnation
Dried at 383 K
overnight
Calcination and reduction at
higher temperature (548 - 723 K)
Cu-HTlc / Ni-HTlc materials
16. SE-SRE with Cu (5 wt. %) and Ni (6 wt. %)-HTlc materials
– High purity H2 during initial period
– Low CO2 sorption capacity
• ~ 0.15 mol/kg…
4. Material Development
15
Figure 6 Product distribution on dry basis as function of reaction time on Cu-HTlc material (a) and Ni-HTlc
material (b) at 773 K, p = 101.3 kPa with a RS/E of 10 in the feed.
Wu et al., Chem. Eng. J.,2013, 231, 36-48.
Cunha et al., Chem. Eng. Res. Des., 2013, 91 (3), 581–592.
0 600 1200 1800 2400 3000
0
15
30
45
60
yH2
[mol%]
t [s]
H2
CO2
CH4
CO
b)Ni-HTlc Material for SE-SRE
yCO,CH4
,CO2
[mol%]
0
20
40
60
80
100
0 600 1200 1800 2400 3000
0
5
10
15
20
25
30
yH2
[mol%]
t [s]
H2
CO2
CH4
CO
a)Cu-HTlc Material for SE-SRE
yCO,CH4
,CO2
[mol%]
50
60
70
80
90
100
17. 4. Material Development
K-promoted (20 wt. %) HTlc with KNO3 as K precursor
– Impregnation
• MG30 hydrotalcite + KNO3, Ultrasonic 6h, 110 ºC 24h
– Calcination
• 2KNO3 → K2O + O2 + NO + NO2, 485 ºC 48h
K-promoter effect**
O Mg K
16
0.0
0.2
0.4
0.6
0.8
1.0
1.2
MG30-KNO3
MG30-Cs2
CO3
MG30-K2
CO3
CO2
sorptioncapacity[mol/kg]
MG30
Figure 7 Comparison of the sorption capacity of CO2 for pure and
alkali-modified HTlc at 676 K, pCO2 of 0.40 bar. *
*Oliveira et al., Sep. Purif. Technol., 2008, 62, 137–147.
Wu et al., Chem. Eng. Technol., 2013, 36(4), 567-574.
**Meis et al., Ind. Eng. Chem. Res., 2010, 49, 8086–8093.
18. 4. Material Development
K-Cu-Ni-HTlc (20-5-5 wt. %) hybrid material preparation
– Impregnation
• MG30 HTlc+ Ni(NO3)2 + Cu(NO3)2 + KNO3, Ultrasonic 6h, 483 K 24h
– Calcination
• Ni(NO3)2 + Cu(NO3)2 + 2KNO3 → NiO + CuO + K2O + 6NO2 + 3/2O2, 723 K 48h
– Reduction
• NiO + CuO + 2H2 → 2Ni0.5Cu0.5 + 2H2O, 723 K ~3h
17
40 42 44 46 48
Cu-HTlc
K-HTlcCu Ni
K-Cu-Ni-HTlc
Ni-HTlc
2 [o
]
Cu-Ni
a)
Figure 8 Comparison of XRD patterns (a) and the SEM graph of the K-Cu-Ni-HTlc material (b).
Cunha et al., Ind. Eng. Chem. Res., 2014, 53 (10), 3842–3853.
19. 4. Material Development
K-Cu-Ni-HTlc hybrid material for tests
– Adsorption and SE-SRE reaction performance
18
Cunha et al., Ind. Eng. Chem. Res., 2014, 53 (10), 3842–3853.
0 10 20 30 40 50
0.0
0.2
0.4
0.6
0.8
1.0
T = 669 K
T = 721 K
T = 763 K
qCO2
[mol/kg]
pCO2
[kPa]
a)
0 500 1000 1500 2000 2500 3000
0
20
40
60
80
100
T = 773 K
mcat
/nEtOH,0
= 43.7 gcat
.hmol-1
t [s]
yCH4
yH2
yCO2
b)
.
yH2
,CO2
,CH4
[mol%]
0
4
8
12
16
20
yCO
yCO
[mol%]
Figure 9 CO2 adsorption isotherms (a) and SE-SRE reaction (b) over K-Ni-Cu-HTlc material at
773 K, 101 kPa, RS/E = 10.
Cu-particles
H2C2H5OH,
H2O
K-Promoted HTlcNi-particles
H2 Yield CO2 Yield
20. 5. Process Study
SE-SRE operation in a single column
– Column arrangement
– Reaction conditions
19
0 2 4 6 8 10
0
1500
3000
4500
6000
7500
time[s]
RS/C
[mol/mol]
CO content limit (< 30 ppm)
H2
purity limit (> 99%)
Allowable operation region
a)
0 2 4 6 8 10
0.0
0.3
0.6
0.9
1.2
1.5
H2
produced[mol/kg]
RS/C
[mol/mol]
b)
0.0
0.2
0.4
0.6
0.8
1.0
H2
productivity
Thermal efficiency
Thermalefficiency[kJ/kJ]
Figure 10 The effect of RS/C conditions on operation window (a) and hydrogen production
performance (b) with u0 = 0.1 m∙s-1, p = 101.3 kPa at 773 K.
Wu et al., Ind. Eng. Chem. Res., 2014, 53 (20), 8515–8527.
21. q'L pL
qH
pH
qL
PSA+TSA
TSA
H = high
L = low
TH
TL
PSA
.
..
.
5. Process Study
Pressure effect
– Volume increase reaction
– Enhance sorbent performance
Periodically regeneration
– Pressure swing (PSA)
– Thermal swing (TSA)
– Inert purge (concentration swing)
20
Figure 12 Methods for sorbent regeneration.
p
[kPa]
Operation time
[s]
H2 produced
[mol∙kg-1]
Thermal efficiency
[kJ/kJ]
101.3 2410 0.761 0.799
304.0 930 0.853 0.791
506.6 485 0.717 0.778
Table 3 Operating performance in SE-SRE under different pressure
conditions with CO content (< 30 ppm) limit.
0 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
1.0 Adsorbed
101.3 kPa
202.7 kPa
304.0 kPa
405.3 kPa
506.6 kPa
qCO2
[mol/kg]
z [m]
Equilibrium
Figure 11 SE-SRE performance under different
pressure conditions.
22. 5. Process Study
Operating scheme for continuous H2 production
SE-SRE vs. SRE performance
21
Operation
H2 yield
[mol %]
CO2 yield
[mol %]
Thermal
efficiency
[kJ∙kJ-1]
H2
productivity
[mol∙kg-1h-1]
SE-SRE 78.5 75.0 0.45 0.51
SRE 38.3 51.0 0.47 0.93
Table 4 Comparison of hydrogen production performance for SRE
process and cyclic SE-SRE process under CSS.
EtOH
H2O
H2
CO2
H2O
H2O
H2O
H2
Reaction
Rinse Regeneration
Purge
CO2(gas)CO2(ads)
H2(gas)
CO2(ads)CO2(gas)
CH4, H2
COX, H2O
H2O
CO2(gas)CO2(ads)
tinitial treaction trinse tregeneration tpurge
Pressure
pH
pL
Time
H2O, H2
Wu et al., Ind. Eng. Chem. Res., 2014, 53 (20), 8515–8527.
23. 5. Process Study
Two-dimensional adsorptive reactor
– Model validation (dR = 3.3 cm)
22
Figure 13 Product distributions as a function of time. Operating conditions: T = 773 K, p = 101 kPa
and RS/E = 10. nEtOH,0 = 4∙10-5 mol∙s-1 (a) and 8∙10-5 mol∙s-1 (b).
0 500 1000 1500 2000 2500 3000 3500
0
20
40
60
80
100
yH2
yCO2
t [s]
yCH4
a)
yH2
,CO2
,CH4
[mol%]
0
10
20
30
40
50
PostbreakthroughBreakthrough
yCO
yCO
[mol%]
Pre-
Breakthrough
0 500 1000 1500 2000 2500 3000 3500
0
20
40
60
80
100
yCH4
yH2
yCO2
PostbreakthroughBreakthrough
Prebreakthrough
yH2
,CO2
,CH4
[mol%]
t [s]
b)
0
10
20
30
40
50
yCO
yCO
[mol%]
,
1
t t
Radial Axial
i i i
r r z zi i
ConvectiveConvective
Diffusive Diffusive fluxflux
flux flux
i r
C r C
C y y
D u C r D u C
t r r r z z
r
,eaction i adsorptionr
Wu et al., Chem. Eng. Sci.., 2014, DOI: 10.1016/j.ces.2014.07.005.
24. 5. Process Study
Reactor dynamics (dR = 10 cm)
23
Figure 14 The temperature profiles of the pellet (a,b) and CO2 reaction/adsorption rate (c,d)
during the SE-SRE reaction at 773 K, 304 kPa, RS/C = 4 and n0= 0.05 mol∙s-1.
0 1 2 3 4 5 6
-0.04
-0.02
0.00
0.02
0.04
z [m]
r[m]
763.0
764.0
765.0
766.0
767.0
768.0
769.0
771.0
772.0
773.0
Tp
[K]a)
t = 1200 s
0 1 2 3 4 5 6
-0.04
-0.02
0.00
0.02
0.04
z [m]
r[m]
763.0
764.0
765.0
766.0
767.0
768.0
769.0
771.0
772.0
773.0
Tp
[K]b)
t = 2400 s
0 1 2 3 4 5 6
0
1
2
3
4
CO2
Forming CO2
Adsorbing
at r = 0 m
at r = 0.05 m
rCO2
[mol/(m3
pellet
s)]
z [m]
c)
at t = 1200 s
0 1 2 3 4 5 6
0
1
2
3
4
CO2
Forming CO2
Adsorbing
at r = 0 m
at r = 0.05 m
rCO2
[mol/(m3
pellet
s)]
z [m]
d)
at t = 2400 s
25. 5. Process Study
Continuous hydrogen production process
24
Figure 15 Four-column schemes and cyclic configurations
employed SE-SRE process.
Figure 16 SE-SRE performance (a) and the CO2
loading profile at the end of reaction
step (b) during cyclic operation.
0 10 20 30 40 50
99.0
99.2
99.4
99.6
99.8
100.0
H2
purity [mol %]
Cycle number
H2
purity[mol%]
0
5
10
15
20
25
30
CO content [ppm]
COcontent[ppm]
a)
0 1 2 3 4 5 6
0.0
0.2
0.4
0.6
0.8
Cycle 1
Cycle 2
Cycle 3
CSS
qCO2
[mol/kg]
z [m]
b)
r = 0 m
fresh sorbent
Wu et al., Chem. Eng. Sci.., 2014, DOI: 10.1016/j.ces.2014.07.005.
26. 6. Conclusions
High purity H2 can be obtained from SE-SRE with HTlc
material as CO2 sorbent
Hybrid material can be prepared from the impregnation of
active phase(s) on the HTlc material as sorbent
KNO3 is found to be a good alkali promoter
Continuous high purity H2 production can be performed
with a four-column pressure swing operating scheme
Radial temperature gradient should be considered in a
large reactor for SE-SRE
25
27. 7. Future Work
Material developments
– Adsorption performance improvement
– Pellet preparation and test
– Mechanical strength
Process developments
– Kinetic model with carbon deposit
– Real-gas thermodynamic model
– Sorption enhanced oxidative and auto-thermal reforming
– Integration with fuel cell model
SERP concept for H2 production from other feedstocks
– Biogas, glycerol, syngas, biomass…
26
28. Acknowledgement
27
Supervisor: Prof. Alírio E. Rodrigues, University of Porto
Co-advisor: Dr. Adelino F. Cunha, University of Porto
Prof. Jian-Guo Yu and Prof. Ping Li, East China University
of Science and Technology
Helps from LSRE/LCM group and DEQ-FEUP.
Doctoral grant from China Scholarship Council
– CSC 2010674011