![Page 1: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/1.jpg)
HYDROGEN PRODUCTION BY A THERMALLY INTEGRATED ATR BASED FUEL PROCESSOR
V. Palma1, A. Ricca1, B. Addeo1, G. Paolillo2, P. Ciambelli1
Department of Industrial EngineeringUniversity of Salerno, Fisciano (SA) - ITALY
1 Department of Industrial Engineering - University of Salerno, Fisciano (SA) - ITALY 2 R&D - SOL S.p.A, Monza (MB), ITALY
![Page 2: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/2.jpg)
o Growing world energy demando Depletion of fossil fuels
ALTERNATIVE ENERGY SOURCES ARE NEEDED
Solar Nuclear GeologicalEolic
Hydrogen=
Energetic vector
Water hydrolysis
Hydrocarbons reforming
H2 Gree
n En
ergy
Fuel cells
Introduction
Hydrogen and Energy
Hydrogen
![Page 3: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/3.jpg)
Steam ReformingPartial OxidationAutothermal Reforming
Preliminary syngas purification
Preferential oxidationMembrane separationPressure swing adsorption
Introduction
Hydrogen from hydrocarbons
HCAir H2O
Reformer
Water Gas Shift
Further purification
HYDROGEN
H2
![Page 4: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/4.jpg)
Introduction
The AutoThermal Reforming
CH4 + y H2O + x O2 = a CO + b CO2 + c CH4 + d H2O + e H2 + f C(S)
Advantages• Easy to design Thermal integration of the reaction• Quick start-up Quick response to feed changes• Reactor compactness Feed versatility
Distributed H2 production for heat and energy power generation
High compactness and thermal efficiency of the reactor
Auto-Thermal Reforming (ATR)
Partial Oxidation
molKJH 3.206 molKJH 6.35
Steam ReformingCH4 + H2O = CO + 3 H2 CH4 + ½ O2 = CO + 2 H2
![Page 5: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/5.jpg)
Aims
Aims of the work
To design and set-up a fuel processor based on auto-thermal reforming (H2 productivity 10 Nm3/h)
ATR – WGS Integration Compactness Thermal Integration
To perform preliminary tests Methane Natural Gas
AIMS OF THIS WORK
![Page 6: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/6.jpg)
EXPERIMENTAL APPARATUS
![Page 7: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/7.jpg)
Experimental Apparatus
Design Concept
Mix
ATR
Water
Air
Methane
WGS
SYNGAS
Heat
Exc
hang
er
SteamAir
REACTANT PREHEATING UP TO 300 ÷ 400°C
Integrated heat exchange system
No external exchangers Plant compactness Cost lowering
![Page 8: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/8.jpg)
Plant layout
Experimental apparatus
FEED
SE
CTIO
N
ANAL
YSIS
SY
STEM
REACTION SECTION
![Page 9: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/9.jpg)
Experimental apparatus
ATR module
Temperature and composition measured close to the inner and outer sections of the catalytic bed
ATR CatalystGHSV 15000 h-1
Catalyst Volume 1000 cm3 (D 3.66 in)
Catalyst Shape Honeycomb monolith400 CPSI - WT 6.5 mil
Catalyst Supplier Johnson Matthey
Catalyst
Insulating Foam
![Page 10: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/10.jpg)
Experimental apparatus
WGS module
Temperature and composition measured close to the inner and outer sections of the catalytic bed
WGS CatalystGHSV ≈2500 h-1
Catalyst Volume 7500 cm3
Catalyst Shape PelletsD 5 mm
Catalyst Supplier KatalkoJMCatalyst
![Page 11: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/11.jpg)
Experimental apparatus
Heat exchange module
Steam Air Liquid waterCoils 5 9 10Tube per coils 9 5 9Surface (m2) 0.032 0.032 0.065
The use of coils increases heat exchange efficiency
Several coils mounted parallel-way to reduce pressure drops
Exchangers arrangement maximizes heat transfer and avoids methane cracking
![Page 12: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/12.jpg)
Experimental apparatus
Assembled reaction system
![Page 13: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/13.jpg)
RESULTS AND DISCUSSIONMETHANE REFORMING
![Page 14: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/14.jpg)
Results and Discussion
Methane ATR – Operating conditions
Test parameters
Fuel METHANE
H2O / O2 / CH4 0.49-0.75 / 0.60-0.65 / 1
ATR
GHSV 15,000 h-1
Catalyst Volume 1,000 cm3
Catalyst Shape Honeycomb monolith
WGS
GHSV 2,500 ÷ 3,000 h-1
Catalyst Volume 6,800 cm3
Catalyst Shape 5 mm Pellets
![Page 15: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/15.jpg)
Results and Discussion
Methane ATR - Thermal Profiles
Mixer ATR Heat Exchanger
WGS
Reactants pre-heating up to 360°C
Heat exchange module able to cool process stream to around 300°C in all conditions
Relevant heat loss in the WGS module
![Page 16: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/16.jpg)
Results and Discussion
Methane ATR – Catalytic Stages Performances
H2O:O2:CH4 = 0.49:0.6:1
H2O:O2:CH4 = 0.6:0.65:1
H2O:O2:CH4 = 0.65:0.65:1
H2O:O2:CH4 = 0.75:0.65:1
0%
20%
40%
60%
80%
100%96
.7%
99.0
%
99.5
%
99.5
%
X_CH4 Eq. Therm
CH4
Conv
ersio
n
H2O:O2:CH4 = 0.49:0.6:1
H2O:O2:CH4 = 0.6:0.65:1
H2O:O2:CH4 = 0.65:0.65:1
H2O:O2:CH4 = 0.75:0.65:1
0%
20%
40%
60%
80%
X_CO WGS1 X_CO Therm. Eq
CO C
onve
rsio
n
Methane conversion very close to thermodynamic equilibrium
Full conversion in the last 3 tests
CO conversion less performant
WGS catalyst kinetic issues
H2O / CH4 O2 / CH4
Case 1 0.49 0.60
Case 2 0.60 0.65
Case 3 0.65 0.65
Case 4 0.75 0.65
![Page 17: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/17.jpg)
H2O/CO T out CH4 H2 CO2 CO X_COExp. Therm. Eq. Exp. Therm. Eq. Exp. Therm. Eq. Exp. Therm. Eq. Exp. Therm. Eq.
Case 1 0.74 300°C 1.9% 2.0% 39.6% 39.6% 9.2% 12.2% 8.4% 4.4% 36.7% 66.9%
Case 2 0.70 327°C 0.4% 0.6% 40.3% 40.1% 11.0% 12.3% 6.5% 4.5% 52.1% 67.1%
Case 3 0.70 366°C 0.3% 0.3% 41.2% 40.3% 10.3% 11.7% 6.6% 5.3% 51.1% 61.3%
Case 4 0.85 372°C 0.3% 0.3% 41.5% 40.6% 11.1% 12.2% 6.2% 4.8% 52.5% 63.9%
Results and Discussion
Methane ATR – Stages compositions
H2O/C O2/C CH4 H2 CO2 CO X_CH4Exp. Therm. Eq. Exp. Therm. Eq. Exp. Therm. Eq. Exp. Therm. Eq. Exp. Therm. Eq.
Case 1 0.49 0.6 2.1% 1.6% 36.8% 36.1% 4.8% 5.5% 13.9% 12.5% 96.7% 97.6%
Case 2 0.60 0.65 0.6% 0.7% 37.1% 35.5% 4.9% 5.7% 14.3% 12.3% 99.0% 98.9%
Case 3 0.65 0.65 0.3% 0.4% 37.7% 36.0% 4.8% 5.5% 14.3% 12.7% 99.5% 99.4%
Case 4 0.75 0.65 0.3% 0.3% 37.7% 36.4% 5.3% 5.8% 13.9% 12.4% 99.5% 99.6%
ATR Composition
WGS CompositionAll composition are «dry-base»
![Page 18: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/18.jpg)
Results and Discussion
Methane ATR – Overall system performances
o Hydrogen production above 7 Nm3/h
o Thermal efficiency approaching 75%o Threshold of 80% easily reachable
![Page 19: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/19.jpg)
RESULTS AND DISCUSSIONNATURAL GAS REFORMING
![Page 20: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/20.jpg)
Results and Discussion
Natural Gas ATR – Operating conditions
Test parameters
Fuel NATURAL GAS
H2O / O2 / Fuel 0.60-1.00 / 0.55-0.60 / 1
ATR
GHSV 15,000 – 22,500 h-1
Catalyst Volume 1,000 cm3
Catalyst Shape Honeycomb monolith
WGS
GHSV 2,000 ÷ 3,500 h-1
Catalyst Volume 8,400 cm3
Catalyst Shape 5 mm Pellets
NATURAL GAS COMPOSITION
CH4 85.249%
C2H6 7.570%
C3H8 1.825%
C4H10 0.561%
C5H12 0.131%
C6H14 0.062%
He 0.102%
N2 4.022%
CO2 0.479%
![Page 21: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/21.jpg)
Results and Discussion
Natural Gas ATR - Thermal Profiles
Mixer ATR Heat Exchanger
WGS O2/Fuel ratio < 0.6
critical for the system
Steam to feed ratio = 0.8 showed highest performances
![Page 22: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/22.jpg)
Results and Discussiuon
Natural Gas ATR – Catalytic Stages Performances
o ATR quite approached equilibrium
o O2/fuel ratio effected performances
o WGS stage far from equilibrium
o Both kinetic and thermodynamic issues
o H2 production quite constant in investigated conditions
H2O/CO
0.78H2O/CO
1.67H2O/CO
0.85H2O/CO
1.17H2O/CO
1.30
Fuel
![Page 23: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/23.jpg)
Results and Discussion
Natural Gas ATR - Thermal Profiles
Mixer ATR Heat Exchanger
WGS Feed rate seems to not
effect temperature profile
System adiabaticity
Heat exchangers well balanced
![Page 24: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/24.jpg)
Results and Discussion
Natural Gas ATR – Catalytic Stages Performances
o GHSV didn’t effect ATR performances
o Increasing GHSV evidenced WGS kinetic limitations
o H2 production clearly increased with feed rate
o 10 Nm3/h of produced hydrogen achieved
H2O/CO
0.85H2O/CO
0.97H2O/CO
0.96H2O/CO
1.03
Fuel
![Page 25: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/25.jpg)
Results and Discussion
Natural Gas ATR - Thermal Efficiency
Centralize
d
Distrubuted
Experim
ental Te
st
Catalys
t optimiza
ton0%
20%
40%
60%
80%
70%
63% 68
%
71%
Ther
mal
Effi
cien
cy, L
HV b
ased
GHSV = 15,000 h-1 - H2O : O2 : Fuel = 0.80 : 0.60 : 1
![Page 26: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/26.jpg)
CONCLUSIONS
![Page 27: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/27.jpg)
Conclusions
A compact auto-thermal reforming based fuel processor was designed for hydrogen production from methane and natural gas
Preliminary tests were performed on the system, evidencing:
o System able to sustain very high feed rates
o Good ATR system performances
o Natural gas weakly inhibited ATR catalysts
o Tested WGS catalyst not optimal for the operating conditions
To optimize WGS catalyst
To recover heat from WGS
exhaust stream
System SCALE-UP(50-100 Nm3/h H2)
CON
CLU
SIO
NS
Nex
t Ac
tiviti
es
![Page 28: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/28.jpg)
Acknowledgement
Acknowledgement
The research leading to those results has received funding from the PON 01_02545 “Sviluppo di sistemi per la produzione distribuita di idrogeno e syngas basati su reforming auto termico catalitico multifuel” project.
![Page 29: Hydrogen production by a thermally integrated ATR based fuel processor](https://reader030.vdocuments.mx/reader030/viewer/2022020108/58f9ad3d760da3da068b9644/html5/thumbnails/29.jpg)
www.unisa.itAntonio RiccaPhD, Chemical Engineer--------------------------------------------------------------Department of Industrial EngineeringUniversity of Salerno
Thank youfor your kind attention