Desilication of Bamboo and Straw

Black Liquors

A.K.Dixit, B.P.Thapliyal,
R.K.Jain and R.M.Mathur

IPPTA Conference
16TH- 17TH JULY, 2010
Banglore

Central Pulp & Paper Research Institute, Saharanpur, U.P.

 Structure of Presentation
• Why Desilication ?
• Desilication Technology Developed by CPPRI
-Concept of Submerse Bubble Reactor
-Process Details
• Mechanism of Silica Precipitation by lowering of pH
• Desilication of Bamboo Black Liquor
• Desilication of Rice Straw Black Liquor
• Commercial Scale Desilication of Rice Straw
• Impact of Desilication on Black Liquor Properties
• Conclusion
 Why Desilication ?
Presence of silica in black liquor causes:
• Scaling in Evaporator tubes
– Hard deposits on wall tubes- Ca–Al Silicates
• Beehives on furnace walls
• Possibly responsible for high viscosity of Black Liquors
in agro residue black liquors
• Slow settling of lime sludge due to calcium- Silicates
formed during causticization
• Low dryness of silica mud from causticizers during mud
washing leads to high oil consumption in lime kiln
• Difficulty in lime mud re-burning
Thermal analysis studies have shown that silica forms a sheath over
lime particles so the CO2 can not escape from CaCO3 molecules
during calcination in lime kiln.
Overview of Desilication Technologies
No. of researchers had tried various processes for
desilication of black liquor.

• Additions of Cations ( Ca++ , Mg++, Al+++ )

• Lowering the pH of black liquor with CO2 or acid
• Combined method by lowering pH & addition of
cations

None of these methods could succeed on commercial scale.

 CPPRI Desilication Technology
• Lowering of pH with CO2 under controlled conditions
• Only silica gets precipitated and no lignin precipitation occurs.

Concept of Submerse Bubble Reactor

• Liquor pumped in a tubular system, is treated with gas, which
on its downward path sucks the gas in the form of discreet
bubbles.
• The shearing action due to flow of the liquor, presses the gas
bubbles in a kneading fashion.
• This action continuously exposes new gas liquid interfaces
and thus ensures slow reduction of pH leading to selective
precipitation of silica.
 Schematic of CPPRI Desilication Technology
1 Flue Gas from
Boiler
2,4,6 Circulation Pump
3,5,7 Submerse
Reactor Tank
8 Hot Retention
1 Tank
Weak
9 Feed Pump to
BL From Filter
Storage 10 Clarifier
11 Belt Filter
2 3 4 5 6 7 12 Filtrate Tank
13 Feed Pump to Mix
Tank
14 Caustic Mix Tank
15 High pH Tank
Caustic 16 Feed Pump to
10 Storage
Soda 17 Foam Tank
11 18 Foam Tank
Precipitated 9 8
Liquor Pump
14 Silica

18
16
15 13 12
17
Desilicated BL
to Storage
Flow Sheet of Mill Scale Desilication Plant in Rice Straw Based Mill

TC
TC
CHEMISTRY OF DESILICATION

NaOH + SiO2 Na2SiO3 + H2O

60 122

CO2 + H2 O H2CO3
62
2NaOH + H2CO3 Na2CO3 + 2 H20
80 106

Na2SiO3 + H2CO3 Na2CO3 + SiO2 + H2O

122 + 62 106 + 60 + 18
Mechanism of Silica Precipitation by lowering of pH
• Lowering of the pH of black liquor converts silicates into
insoluble polymeric anhydrides of silicic acid.
• Lowering the pH of alkali silicate solutions results in;
– First in formation of monosilicic acid.
– This monomer undergoes polymerization, at a concentration greater
than the solubility of amorphous silica (i.e. 100-200 ppm), forming
higher molecular weight species.
• Above pH–7 stabilized particles (Sols) grow to a size of about
100 nm.
• When salts are present, to neutralize the charge on growing
particles, aggregation of particles occur with the formation of
chains and ultimately, three dimensional gel net works.
Mechanism of Silica Precipitation by lowering of pH
(Mono silicic acid)

Central Pulp & Paper Research Institute, Saharanpur, U.P., INDIA

Desilication of Bamboo Black Liquor
• Desilication of Bamboo Black liquor was carried out on
Pilot Plant in a bamboo based mill.
• 70 litres of weak black liquor was desilicated in each
trial.
• Flue gas was collected from chemical recovery Boiler
stack.
• CO2 content in flue gas was 12%.
• Desilicated black liquor was filtered under vacuum.
• Filtered desilicated black liquor was subjected to re-
alkalisation.
 Desilication of Bamboo Black Liquor
Black Liquor Characteristics Desilication
Before Desilication After Desilication (%)
pH SiO2, g/l PH SiO2, g/l

12.8 4.2 10.5 2.1 48.8

10.4 1.5 64.3
10.3 1.2 71.4
10.2 0.8 80.9
10.1 0.5 88.9
10.0 0.4 90.5
9.8 0.4 90.5
 PHYSIO-CHEMICAL ANALYSIS OF BAMBOO BLACK LIQUOR
BEFORE AND AFTER DESILICATION

ORIGINAL DESILICATED
PARAMETERS BLACK LIQUOR BLACK LIQUOR

1. pH at 30o C 12.8 12.3

2. Total Solids, %w/w 19.0 19.2

3. RAA,gpl as NaOH 7.0 4.0

4. Silica, gpl 4.2 0.4

5. Sulfur, %w/w 2.8 2.85

6. Organics, % w/w 63.2 62.3

7. In organics,% w/w 36.8 37.7

 Viscosity of Desilicated and Original
Bamboo Black liquor

190
70
240

80
65
128
% Total Solids

40
60
55
Desilicated Black
20 Liquor
55
22 Original Black Liquor

8
50 8

Viscosity , m.Pa. Sec.

Swelling Volume Ratio of Black Liquor

Carbonated Black Liquor

Realkalised Black Liquor

Original Black Liquor

 Desilication of Rice Straw Liquor
Black Liquor Characteristics Desilication
Before Desilication After Desilication (%)
pH SiO2, g/l pH SiO2, g/l

12.0 13.3 10.5 6.9 48.1

10.4 5.8 56.3
10.3 1.5 88.7
10.2 1.0 92.5
10.1 0.7 94.7
10.0 0.4 97.0
9.9 0.3 97.7
9.7 0.3 97.7
Commercial Scale Desilication of Rice Straw
• A full commercial scale desilication plant
was installed in 2006 in Coastal papers
Limited.

• Capacity of theplant is 20M3 black liquor / hr

• Flue gas is tapped from Power boiler.

• CO2 content of flue gas is 9-11%.

INPUT CONDITIONS FOR B.L. DE-SILICATION.

1. RAA IN WBL 4 – 5 gpl

2. SILICA AS SiO2 6 – 13 gpl

3. pH MAX. REMOVAL OF SILICA 9.9

4. pH OF WBL BEFORE SILICA REMOVAL 11.8 – 12.0

PHYSIO-CHEMICAL ANALYSIS OF RICE STRAW BLACK LIQUOR
BEFORE AND AFTER DESILICATION

ORIGINAL DESILICATED
PARAMETERS BLACK LIQUOR BLACK LIQUOR

1. pH at 30o C 12.0 10.3

2. Total Solids, %w/w 14.1 9.6

3. RAA,gpl as NaOH 5.0 0.8

4. Silica, gpl 13.3 0.68
5. Sulfur, %w/w 0.06 0.1
6. R2O3, % w/w 0.09 0.05

7. Organics, % w/w 67.65 71.9

8. In organics,% w/w 32.2 28.1
9. Calorific value cal/gram 2578 2940
 PHYSIO-CHEMICAL ANALYSIS OF RICE STRAW BLACK LIQUOR
BEFORE AND AFTER DESILICATION Contd…..

PARAMETERS ORIGINAL DESILICATE

BLACK LIQUOR BLACK LIQUOR

10. Carbon, % w/w 34.4 36.6

11. Hydrogen, %w/w
2.5 2.9
12. Nitrogen, % w/w
0.7 1.0
13. Sodium, % w/w
8.5 11.5
14. Calcium,% w/w
0.04 0.06
15. Sulfate, %w/w as SO4
0.15 0.15
 Viscosity Of Desilicated and Original Rice
Straw Black liquor
130
52
730

75
50
316
% Total Solids

24
45
112

12 Desilicated Black Liquor

40
56
Original Black Liquor
8
35
33

Viscosity, m .Pa. Sec.

Photographs of Mill scale desilication plant
in Rice straw based mill
DESILICATION PLANT REACTION TANKS
GAS NOZZLES ASSEMBLY
FLUE GAS NOZZLES
CLARIFIER UNDERFLOW PUMP
PRESSURE FILTER
SILICA CAKE BEING SCRAPPED
DUMPED SILICA CAKE
Impact of Desilication on Black Liquor Properties
• Colloidal stability of B.L.- High
• Lignin co-precipitation - Nil
• Foam generation during gas liquid interaction- moderate and easily
manageable.
• Settling of silica sludge- Encouraging results were obtained on
carbonated black liquor.
After three hours of settling the sludge volume stands at only 20% of total liquor
volume and supernatent black liquor has less than 20 ppm suspended solids.
• Viscosity of desilicated and realkalized black liquor is fairly close to the
original black liquor in case of bamboo black liquor.
• Viscosity of rice straw B.L. is reduced significantly after desilication.
Contd…
 Impact of Desilication on Black Liquor Properties…..
Contd…

• No precipitation observed even at 50% Concentration. Original

black liquor gets precipitated at 28% Conc.
• There is marginal reduction in the calorific value of realkalized
bamboo black liquor, due to increase in the concentration of
inorganics during realkalisation. However there is no change in
calorific value on the basis of organic content of the black liquor.
• Calorific value, however increased in case of rice straw black liquor.
• There is a remarkable improvement in the swelling volume ratio
(SVR) of carbonated & realkalized black liquor when compared to
the original black liquor, which is a pointer towards better
combustibility of desilicated black liquor.
 Conclusion
• Black liquor properties are improved & burning behaviour of black liquor
is better after desilication.
• Successful operation of full commercial scale plant since last four years
has created confidence on CPPRI Technology.
• Pilot plant and full commercial scale plant trials have shown that both
Bamboo and straw black liquors containing 2.0 to 14 gpl silica can be
desilicated to a residual silica of 0.5gpl.
• Successful demonstration of bamboo and rice straw black liquor
desilication has further confirmed the suitability of CPPRI desilication
technology in wide range of silica content of black liquor ( 2-15 gpl).
• Adoption of desilication process in bamboo and straw based chemical
recovery will help to;
– reduce operational problems caused by silica,
– save energy during evaporation and
– protect environment by making lime sludge suitable for reburning and reducing
solid waste.