RECOVERY BOILER CHEMICAL

PRINCIPLES

Mikko Hupa
Åbo Akademi University
Turku, Finland

RECOVERY BOILER CHEMICAL

PRINCIPLES - OUTLINE

• S and Na in recovery boilers

- an overview
• Lower furnace and char bed
• Flue gases and dust
• Foreign components
 KRAFT BLACK LIQUOR
ELEMENTARY COMPOSITION
(Sample before the mixing tank)

C 38.2 % in BL dry solids

H 3.4
O 31.1
N 0.1
S 5.2 S/Na2 = 0.38
Na 19.8
K 1.9
Cl 0.1
Others 0.2
(Ca,Si,Fe,Mg,Al,Mn)

SULPHUR COMPOUNDS IN KRAFT

BLACK LIQUORS
(Sample before the mixing tank)

Sulphide, S2- 11 % S of total S

Thiosulphate, S2O2-
3 36 %
2-
Sulphite, SO3 13 %
Sulphate, SO2-4 5%
Organic S (balance) 35 %
100 %
 Na AND S COMPOUNDS IN
RECOVERY FURNACE

Solids or liquids Gases

Na2S H2S (g)
Na2CO3 SO2 (g)
Na2SO4

NaOH NaOH (g)

NaHSO4

Na AND S COMPOUNDS IN
RECOVERY FURNACE

Solids or liquids Gases

Na2S mp 1180°C/2160 F H2S (g)
Na2CO3 mp 860°C/1580 F SO2 (g)
Na2SO4 mp 880°C/1620 F

NaOH mp 320°C/610 F NaOH (g)

NaHSO4 mp 180°C/360 F
RECOVERY FURNACE CHEMISTRY
(g sulphur/kg BL solids)

Na 200

S
45

Na2CO3
Na2S

SODIUM BALANCE IN A KRAFT

RECOVERY BOILER (g Na/kg BL solids)
EMISSIONS 0.04 Na2SO4 (50 mg/m3) Na2SO4
Na2CO3
0.04

18

BL

Na+ 200 225

207
7
137 Na2CO3 SMELT
MAKE UP Na2SO4 63.3 Na2S
6.7 Na2SO4
 SULPHUR BALANCE IN A KRAFT
RECOVERY BOILER (g sulphur/kg BL solids)
3
EMISSIONS 0.03 Na2SO4 (50 mg/m )
0.25 SO2 (50 ppm)
0.02 H2S (5 ppm)

0.3

Na2SO4
SO2
H2S

Na2SO4
12.3
BL

S 45 61 48.7
4
44 Na2S
4.7 Na2SO4
SMELT
MAKE UP Na2SO4

RECOVERY BOILER CHEMICAL

PRINCIPLES - OUTLINE

• S and Na in recovery boilers

- an overview
• Lower furnace and char bed
• Flue gases and dust
• Foreign components
 SODIUM BALANCE IN A KRAFT
RECOVERY BOILER (g Na/kg BL solids)
EMISSIONS 0.04 Na2SO4 (50 mg/m3) Na2SO4
Na2CO3
0.04

18

BL

Na+ 200 225

207
7
137 Na2CO3 SMELT
MAKE UP Na2SO4 63.3 Na2S
6.7 Na2SO4

SULPHATE REDUCTION IN SMELT

• Either:
CO, H2
Na2SO4 Na2S

• Or:
Csolid (char)
Na2SO4 Na2S
SULPHATE REDUCTION - SUMMARY

• Sufficient amount of char in the bed

• High enough temperature

(T = +50°C doubles the rate)

EQUILIBRIUM COMPOSITION OF LOWER

FURNACE GASES VS. TEMPERATURE
0
10 100 %
H 2O N2
-1 CO2
Volume concentration

10 10 %
Partial pressure, atm

CO
-2
H2
10 Na 1%
-3
10 OH 1000 ppm
H 2S Na
-4
10 100 ppm
CH 4

COS
-5
10 10 ppm
2
SO

NH
-6 3
10 1 ppm
600 800 1000 1200
Temperature, °C
RECOVERY BOILER CHEMICAL
PRINCIPLES - OUTLINE

• S and Na in recovery boilers

- an overview
• Lower furnace and char bed
• Flue gases and dust
• Foreign components

SODIUM BALANCE IN A KRAFT

RECOVERY BOILER (g Na/kg BL solids)
EMISSIONS 0.04 Na2SO4 (50 mg/m3) Na2SO4
Na2CO3
0.04

18

BL

Na+ 200 225

207
7
137 Na2CO3 SMELT
MAKE UP Na2SO4 63.3 Na2S
6.7 Na2SO4
 RELEASE OF S AND Na IN
LOWER FURNACE

• Mainly H2S and NaOH

• At increasing temperature:
S release decreases
Na release increases

• (S/Na2)flue gases = 0.8 - 1.5

RECOVERY FURNACE GASEOUS

SULFUR AND SODIUM – TYPICAL DATA
10 000
Concentration, ppm

Stot (actual)

5 000
1/ Na
Na2 tot tot (actual)

0
800 1000 1200
Temperature, °C
 REACTIONS OF S AND Na IN FLUE GASES
(S/Na2 = 0.8, hot bed, low sulphidity)
H2S(g) SO2(g) Na2SO4(s) Na2CO3(s)
°C

ECONO- 200
MIZER
400
BOILER
BANK
600
SUPER
800
HEATER
Na2CO3 (l,s)
1000
Na2SO4 (l,s)
CO2 (g)
TERT.
AIR SO2 (g) O2 (g)

LOWER O2 (g)
FURNACE H2S (g) 2NaOH(g)

REACTIONS OF S AND Na IN FLUE GASES

(S/Na2 = 1.5, cool bed, high sulphidity)
H2S(g) SO2(g) SO3(g) NaHSO4(s) Na2SO4(s) Na2CO3(s)
°C

ECONO- 200
MIZER 2NaHSO4
400 (l,s)
BOILER
BANK SO3 (g) H2O (g)
600
SUPER
800 O2 (g)
HEATER
Na2CO3 (l,s)
1000
Na2SO4 (l,s)
CO2 (g)
TERT.
AIR SO2 (g) O2 (g)

LOWER
FURNACE H2S (g) O2 (g) 2NaOH(g)
 DUST pH vs. DUST COMPOSITION
12 10%
pH 1%
0.1%
10
wt. fraction dust in
aqueous solution
8

2
20% 10% 0% 10% 20%
NaHSO4 Na2CO3
Weight fraction in dust, %

SO2 vs CARBONATE IN DUST

(Courtesy Kvaerner Pulping 2002)

Recovery Boiler Sulphur emissions

vs. carbonate in ash
1800
SO2 emissions [ mg/Nm3 ]

1500

1200

900

600

300

0
0 5 10 15 20 25
Carbonate in ash [ wt-% CO32- ]
RECOVERY BOILER CHEMICAL
PRINCIPLES - OUTLINE

• S and Na in recovery boilers

- an overview
• Lower furnace and char bed
• Flue gases and dust
• Foreign components

K AND Cl IN NORTH AMERICAN

BLACK LIQUORS
10
Different liquors
Average
8
K in BLS, wt-%

0
0 2 4 6 8 10
Cl in BLS, wt-%
 K AND Cl IN PRECIPITATOR DUST
10
Different boilers
Average
8
K in dust, wt-%
6

0
0 6 12 18 24
Cl in dust, wt-%

POTASSIUM AND CHLORINE IN

LOWER FURNACE

• Enrichment factors:

(Cl/Na) in gas
(Cl/Na) in smelt
- 2...4
(K/Na) in gas
(K/Na) in smelt
POTASSIUM AND CHLORINE IN
LOWER FURNACE

• Mainly NaCl
KCl
KOH

POTASSIUM AND CHLORINE

CHANGE MELTING OF Na SALTS

• Smelt freezing point decreases

(typically 850 C --> 700 C)
• Dust particle sticky temperatures
decrease (800 C --> 600 C)
 FOREIGN COMPONENTS
SUMMARY (I)

• Cl and K are enriched in gas phase

• Lower furnace: NaCl, KCl, KOH

FOREIGN COMPONENTS
SUMMARY (II)

• K and Cl make dust more "sticky"

• If (S/Na2)FG high enough:
SO2/O2
NaCl Na2SO4
 RECOVERY BOILER CHEMICAL
PRINCIPLES - OUTLINE

• S and Na in recovery boilers

- an overview
• Lower furnace and char bed
• Flue gases and dust
• Foreign components
• Conclusions

RB CHEMISTRY - CONCLUSIONS (I)

• Good reduction requires:

- char in the bed
- high enough temperature
RB CHEMISTRY - CONCLUSIONS (II)

• Dust/flue gas chemistry controlled by

S/Na2 ratio in flue gas
• Flue gas S/Na2 ratio decreases when:
- furnace temperature increases
- liquor sulphidity decreases

RB CHEMISTRY - CONCLUSIONS (III)

• Low S/Na2 gives low SO2 emissions

and alkaline dust (Na2CO3)
• High S/Na2 gives high SO2 emissions
and acidic dust (NaHSO4)
• Dust pH good indicator
RB CHEMISTRY - CONCLUSIONS (IV)

• K and Cl are enriched in the flue gases

• K and Cl in the dust lower melting
temperature range
• At high S/Na2 chlorine is released from
the dust (NaCl → HCl)