C23: Need for standardisation of test methods for sorbent ... septiembre/C23.pdf• Systems Analysis...
Transcript of C23: Need for standardisation of test methods for sorbent ... septiembre/C23.pdf• Systems Analysis...
Ulrich Zuberbuehler
Centre for Solar Energy and Hydrogen Research (ZSW) Stuttgart, Germany
Department: Renewable Fuels and Processes
C23: Need for standardisation of test methods for sorbent/material characterisation
1st Meeting of theHigh Temperature Solid Looping Cycles Network
INCAR-CSIC, Oviedo, Spain15.-17. September 2009
Centre for Solar Energy and Hydrogen Research (ZSW): New Energy Technologies
• Applied Research & Development• Close Cooperation with Industry and Universities• 20 Million € Turnover, 150 Employees
• Photovoltaic – Thin Film Technologies (CIS) & Application Systems• Renewable Fuels and Processes• Systems Analysis and Policy Consulting• Fuel Cells – Technology, Systems, Test Centre• Batteries & Super Capacitors – Materials, Systems, Qualification
Stuttgart Widderstall Ulm
Requirements for Chemical Looping materials in Fluidized Bed Applications
Reactivity: CO2 - Absorption Capacity (gCO2 / gOxide)Reaction Rate: CO2 Absorption & Release (gCO2 / gOxide• s)Chemical and Thermal Stability (number of cycles)Mechanical Stability (amount of attrition, purge)Catalytic Effects (tar)Availability: Grain Size, Cost; Non-Toxic, Easy to Dispose
1. Common material characterisation for trading and quality control (quick, low cost)
2. Standardisation of test methods
Material Characterisation Methods
• Origin- geological information: stone quarry, age, layer, formation,morphology (thin section)
• Chemical properties- composition- capacity- reaction rate dX/dt = f(X(t), T, P, dP)
• Physical properties- grain size- density (bulk, particle, material)- treatment
grinding, fractionating, washingcalcination, sintering, impregnation
- mechanical stability definition, measurement
Carbonate quarry at Swabian Alb (South of Germany)
Upper Jurassic (Source LGRB 2006)
Material Characterisation Methods
• Origin- geological information: stone quarry, age, layer, formation,morphology (thin section)
• Chemical properties- composition- capacity- reaction rate dX/dt = f(X(t), T, P, dP)
• Physical properties- grain size- density (bulk, particle, material)- treatment
grinding, fractionating, washingcalcination, sintering, impregnation
- mechanical stability definition, measurement
CO2 - Capacity (TGA)Procedure
0
100
200
300
400
500
600
700
800
900
0 100 200 300
Time [min]
Tem
pera
ture
[°C
]
28
32
36
40
44
48
52
56
60
64
Mas
s [m
g]
Calcit A3
CaCO3
CaO
CaCO3
)n(m)n(m
)n(COxid
abs,CO2=
mOxide
mCarbonate
mCO2
mStart
TGA Conditions:
d = 0.6 – 0.71 mm, m0 = 50 mg (CaCO3)m0 = 28 mg (CaO)T = 650 / 840°CΔT/Δt = 10 K/minGas: 10% CO2,
30% H2O in N2
CO2- Capacity:
Absorption Capacity with ongoing CyclesRaw and Sintered Sorbent
Absorption Capacity of raw & burnt limestonesdp = 600-710 µm, m0 = 30 mg
TGA atmosphere: 10 % CO2, 30 % H2O in N2
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 5 10 15 20 25
Cycle-No.
Abs
orpt
ion
Cap
acity
g CO
2/g O
xide
C58_1_08 (raw)
C14_1_06 (raw)
C14_3_07_005 (1200°C burnt, 3h)
C14_3_07_003 (1300°C burnt, 3h)
Material Characterisation Methods
• Origin- geological information: stone quarry, age, layer, formation,morphology (thin section)
• Chemical properties- composition- capacity- reaction rate dX/dt = f(X(t), T, P, dP)
• Physical properties- grain size- density (bulk, particle, material)- treatment
grinding, fractionating, washingcalcination, sintering, impregnation
- mechanical stability definition, measurement
ZSW – Sorbent Screening: Mechanical Stability AND CO2 Sorption Reaction in FB
Raw material (200 g, 200-710µm):attrition: 3.5 w.%
0
0.001
0.002
0.003
0.004
0.005
0 100 200 300 400 500 600 700 800
Particle Size / µm
q / (
1/µm
)
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Sum
Q
q raw / 1/µmq FB / 1/µmQ3 (raw)Q3 (FB)
S34_B007_C1_2_06
Particle Size Distribution Effects on “Attrition” value
0
0.001
0.002
0.003
0.004
0.005
0 100 200 300 400 500 600 700 800
Particle Size / µm
q / (
1/µm
)
0.0
0.10.2
0.3
0.4
0.5
0.6
0.70.8
0.9
1.0
Sum
Q
q raw / 1/µmq FB / 1/µmQ3 (raw)Q3 (FB)
S31_B004_C14_1_06
0
0.001
0.002
0.003
0.004
0.005
0.006
0 100 200 300 400 500 600 700 800
Particle Size / µmq
/ (1/
µm)
0.0
0.10.2
0.3
0.4
0.5
0.6
0.70.8
0.9
1.0
Sum
Q
q raw / 1/µmq FB / 1/µmQ3 (raw)Q3 (FB)
S24b_B001_D4_1_06
(A) bigger particles (B) smaller particles
Definition: Attrition wt% < 200µm of initial sample
Handbook of Fluidization and Fluid-Particle SystemsSources of Attrition in a FB System
tm
mr
beda Δ
Δ⋅=
1
3
2
:
:
:
urjet
urcyclone
urbed
a
a
a
≈
≈
≈
Source: Handbook of Fluidization and Fluid-Particle Systems. Dekker 2003
Handbook of Fluidization and Fluid-Particle SystemsExample of different Attrition Indexes
Source: Handbook of Fluidization and Fluid-Particle Systems. Dekker 2003
• Hardgrove Index (HGI) for the grindability of coals• Fluidized Bed Attrition Test (ASTM D-5757-95) for FCC Catalysts
Solids impaction principleDavidson jet cup
Mechanical Stability in Milling TestProcedure
MillType Fritsch pulverisette 6Grinding beaker 80 ml, steelTransmission ratio irelative 1 : -1.82Balls 5 Achate (d=20mm)Turns 440/minTime 5 minSample32 ml (volumetric dosing)Grain size 600 - 710 µm
Sieve analysis (duration 10 min, amplitude 2.5 mm)Attrition = the fraction of fines (d < 200µm) / total sample mass
Milling-Test Method (ZSW)Comparison of Attrition Values
0102030405060708090
100
Q2 Quarz
sand
X2 Oliv
ineD4 D
olomite
C1 Gree
k Limes
tone (raw
)
C1 Gree
k Limes
tone (pre-
treate
d)
C58 G
erman
Limes
tone (raw)
C58 G
erman
Limes
tone Oxide
Attr
ition
in w
t.% (<
200µ
m)
Summary Material Characterisationfor Future Trading and Quality Control
• OriginQuality control, material screening
• Chemical properties Composition, TGA, Process development, basic engineering
not every batch• Physical properties
Size distribution, density, porosity, Mechanical stability
Different individual test methodsNo reliable prediction of attrition in DFB reactorsDefine a fast, simple, and meaningful test method