Behavior of limestone in a largescale pressurized fluidized bed combustor

- attrition, fragmentation and SO2 capture T. Shimizu

Niigata University

S.Sakuno, N. Misawa, N. Suzuki, H. Ueda, H. Sasatsu, H. Gotou

Electric Power Development Co., Ltd.

ABSTRACT
Cooperative research work between EPDC and Niigata Univ. on behavior of limestone in a 71MWe PFBC Limestone attrition rate Fragmentation of limestone Model of SO2 capture by single limestone particle under attrition condition SO2 capture model in PFBC

Structure of this work

Ca in fly ash Model of SO2 capture by CaCO3 under attrition conditions SO2 capture model of PFBC

Limestone attrition rate Limestone fragmentation

This report summarizes the investigations on limestone behavior in 71MWe PFBC listed below:
1. 2. S. Sakuno et al., Nihon-Energy-Gakkai-Shi (J. Jpn. Inst. Energy), 80, 747(2001) Ueda, H. et al., Fluidization characteristics of PFBC, attrition and fragmentation of limestone Proc. 7th SCEJ Symp. on Fluidization (Awaji, Japan), 524 (2001) T. Shimizu, et al., Chemical Engineering Science, 56, 6719 (2001) T. Shimizu et al., A mathematical model of SO2 capture in PFBC, Proc. 7th SCEJ Symp. on Fluidization (Awaji, Japan), 235 (2001) T. Shimizu et al., To be presented at ISCRE 17 (Hong Kong, 2002)

3. 4.

5.

EPDCs Wakamatsu 71MWe PFBC

Phase-1 test series: Without cyclone ash recirculation Phase-2 test series: With cyclone ash recirculation

Measurement
Coal feed rate Limestone feed rate Limestone size distribution Amount of bed material (limestone) Size distribution of bed material Fly ash drain rate Ca content in fly ash SO2 emission

Size of fed limestone Size<5mm

C um ulative weight fraction of lim estone (m easured) [% ] 100 80 60 40 20 0 10 100 D p [m ] 1000 10000 Fuel : coal

Part.1
Evaluation of solid attrition rate and fragmentation of limestone1)2)

Source of Ca in fly ash1)

(Ca in fly ash)>(fine limestone in feed)+(Ca in coal ash) fine formation by attrition
100% Run 1-15: Phase-1(W ithout fly ash recycle) Runs 16-33: Phase-2 (with fly ash recycle) Fines formed by attrition Ca fines in fed limestone Ca in coal ash

Source of C a in fly ash [% ]

80% 60% 40% 20% 0% 1 4

10

13

16

19

22

25

28

Run No.

31

Evaluation of limestone attrition rate

(fine formation by attrition) =(Drain rate of Ca in fly ash) - (fine limestone in feed) - (Ca in coal ash) Surface area of bed material was calculated from size distribution and mass of bed material (Fine formation)/(Surface area) = Rate

Attrition rate dR/dt = 1-2 m/hr1) No clear effect of coal type and load on rate. (R: radius)
Attrition rate [ m/hr]

2.0 1.5 1.0 0.5 0.0 30 40 50 60 70 Plant power output [MW e]

A model of change in limestone particle size by attrition

A model of change in particle size due to attrition assuming constant attrition rate. Particle size distribution of fed limestone

attrition

Particle size distribution of bed material (BM)

Bed material size distribution, comparison between model and experimental results1)
Some agreed but the others not. Why?
1999/3/18 Fuel: B A S orbent:T5 E xper Model 100 C umulative weight fraction of bed material [%] 80 60 40 20 0 100 1000 D p [m] 10000 100 1000 D p [m] 10000 E xper Model 1999/12/10 Fuel: B A (7)+P C (3) S orbent:F1(8)+T1.5(2)

100 C umulative weight fraction of bed material [%] 80 60 40 20 0

Effect of coarse particle content on discrepancy between model and experimental results 1) 1.2 With increasing Model = Experiment content of coarse 1.0 0.8 particles, the 0.6 discrepancy 0.4 became larger. 0.2 Fragmentation 0.0 0 0.2 0.4 0.6 0.8 of coarse W t-frac. >1.19mm in feed sorbent [-] particles by thermal shock
d p50 (est)/d p50 (meas) [-]

Fragmentation of coarse particles

Fragmentation of coarse particles was estimated by a model. Particle size distribution of fed limestone Estimation of fragmentation Estimated particle size distribution of limestone after fragmentation attrition Particle size distribution of bed material

Fragmentation of coarse particles2)

Fragmentation of coarse particles was estimated by the model. Approx. 80% of coarse (3.4- 5.7 mm) particles was broken into
1.0 Residual ratio 3.36-5.66mm [-] 0.8 0.6 0.4 0.2 0.0 20 40 60 80

small particles.

Plant power output [MW e]

Phase-1: Only little formation of 0.25 0.5mm Phase-2: Nearly all of the fragments 0.25- 0.5mm
BA coal, Open symbols: Phase-1, Closed symbols: Phase-2 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 20 40 60 80 Formation ratio 0.25-0.50mm [-]

Formation of smaller particles(0.250.5mm)

Plant power output [MW e]

Formation of smaller particles(0.5-1mm)

Phase-1: Nearly all of the fragments 0.5- 0.1 mm Phase-2: Only little formation of 0.5 1 mm
BA coal, Open symbols: Phase-1, Closed symbols: Phase-2

2.0 Formation ratio 0.5-1.19mm [-] 1.5 1.0 0.5 0.0 -0.5

20

40

60

80

Plant power output [MW e]

Summary of Part 1
Considerable attrition of limestone Attrition rate = 1 2 m/hr Fragmentation of coarse (>1.2mm ) limestone Size of smaller particles formed by fragmentation was affected by cyclone ash recycle.

Part.2
A model of SO2 capture by limestone under solid attrition conditions3)4)5)

Reaction mechanism (in TGA) TGA results (in literature): shrinking unreacted core model controlled by both reaction resistance and diffusion resistance through CaSO4 layer.
Reaction resistance at unreacted core surface Diffusion resistance through CaSO4 layer

SO2

CaCO3 unreacted core

CaSO4 (product layer)

In actual PFBCs, attrition occurs.

Role of attrition in SO2 capture by limestone unknown. Two possible effects of attrition: Attrition increases reaction rate by removing CaSO4 layer (diffusion resistance) Attrition decreases solid utilization efficiency by removal of unreacted CaCO3 Modeling work is necessary to evaluate the effect of attrition on SO2 capture rate and limestone utilization efficiency

Attrition model
Two different attrition modes: Continuous attrition: =average attrition rate Re= R0 t Intermittent (periodical) attrition: (<<particle Re = R0 int(t/) Average slope = - Radius size)

Time

Results: Initial reaction rate5)

At low SO2 concentrations (<100ppm), attrition mode affects reaction rate.
0.1 average conversion rate Conversion = 0 - 0.1

dX/dt| av [1/hr]

0.01 Continuous 2hr period 5hr period 10hr period 20hr period 10 100 SO 2 conc. [ppm ] 1000

0.001

Effect of attrition mode on removal of product layer at low SO2 concentration 5)

ContinuousOnly CaSO4 is removed. Intermittent: CaCO3 is also removed.

Continuous
250 Continuous, SO2 20ppm Re Rc Re, Rc [m] 250 240 230 220 244 0 100 200 Time [min] 300 210

Intermittent
10hr period, SO2 20ppm CaSO4 CaCO3 removed by attrition Re Rc 0 1000 Time [min] 2000

Re, Rc [m]

248

246

Effect of attrition rate on limestone utilization efficiency 5)

Continuous: No change Intermittent: Attrition decreases efficiency.
1.0 Maxim um conversion [-] 0.8 0.6 0.4 0.2 0.0 0 1 a [m /hr] 2 C ontinuous Period 2hr Period 5hr Period 10hr SO 2 100 ppm , C onv. = 0 - 0.1

Effect of attrition rate on apparent reaction rate 5)

Continuous: Attrition increases rate. Intermittent: No change in reaction rate.
0.03 SO 2 100 ppm , C onv. = 0 - 0.1 Continuous Period 2hr Period 5hr Period 10hr

dX/dt| av[1/hr]

0.02

0.01

0.00 0 1 a [m /hr] 2

IF continuous attrition occurs in PFBC

in 71MW e PFBC [mol/s] Total SO 2 capture rate

Attrition rate = SO2 capture rate However, in 71MWe PFBC SO2 capture rate was only 1/3 of attrition rate 3).

SO 2 capture =attrition rate 1

SO 2 capture =0.3x(attrition)

0.5

0 0 1 2 3 4

Intermittent attrition model is applied.

Total Ca attrition rate in PFBC [mol/s]

Simplified SO2 capture model for intermittent attrition model 3)

Assumptions:

Product layer thickness << Particle size Flat surface Diffusion resistance >> Reaction resistance Controlled by diffusion through CaSO4 Fresh surface appears when attrition occurs Product layer thickness = 0 when attrition occurs

Simplified rate expression of SO2 capture for intermittent attrition model 4)

SO2 capture rate per unit external surface area of limestone:

rS = (2De/M)1/2 C1/2
De: Effective diffusivity

: Period of attrition
C: Concentration of SO2 /M: Molar density of CaCO3 in limestone

Simplified SO2 capture model in PFBC 4) Assumptions:

VM-S forms SO2 at the bottom SO2 concentration at the bottom Char-S forms SO2 uniformly in bed SO2 formation rate per unit volume of bed Bed consists of Geldarts D particle mass transfer resistance from bubble to emulsion is sufficiently small plug flow model

Comparison between model and experimental results 4)

Attrition interval was given as a fitting parameter. By giving =5 hr, model agreed well with experimental results.
SO 2 (exper.) [ppm] 40 30 20 10 0 0 10 20 30 SO 2 (calc.) [ppm] 40
=18000s = 5h

Is =5

hr appropriate?

Best fit between model and experiments was obtained at =5 hr. = (1- 2 m/hr)x(5 hr) = 5 - 10 m << Particle size (>250 m) For further analysis, measurement of size distribution of Ca-rich fines in fly ash by CCSEM is necessary.

CONCLUSION
Behavior of limestone in 71 MWe PFBC was analyzed. Attrition rate of limestone was 1-2 m/hr. Limestone particles greater than 1.2 mm was broken when they are fed into PFBC. Limestone attrition mode (continuous or intermittent) plays significant role in SO2 capture. Continuous attrition model overestimates SO2 capture in PFBC.

CONCLUSION (continued)
Intermittent attrition model agreed PFBC results when period of attrition was given as =5hr. To establish complete model, period of attrition should be experimentally determined. Size distribution of Ca-rich particles in the fly ash is necessary for further study.

Acknowledgement
T. Shimizu thanks The Ministry of Education, Culture, Sports, Science and Technology for Grant-in-Aids (No.11218204). The authors express their thanks to The Ministry of International Trade and Industry, Agency of Natural Resources and Energy, and Center for Coal Utilization, Japan, for the financial support for 71MWe PFBC project.