High Temperature, High

Pressure Black Liquor

Gasification with Borate
Autocausticizing
Ingrid Nohlgren
Ph.D. Chem Eng, Senior Research Engineer,
Energy Technology Center, Pite

Scott Sinquefield
Ph.D. Chem Eng, Senior Research Engineer,
IPST at GT, Atlanta

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Integration of BLG influences
the kraft mill
An increased causticization demand
increased demand of lime
increased capacity in the lime kiln
increased demand of fuel

Addition of borate in the gasifier has the potential

to eliminate this increased causticization demand
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Increased causticizing demand
Sulfur is released to the gas in the gasifier
Co-absorption of CO2 in the quench

Traces of
Na, S
Na and S

H2S

Na, S
Na2CO3, Na2S Na2CO3, Na2S

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Increased causticizing demand
Formation of H2S gives formation of Na2CO3
(which in the recovery boiler is Na2S). The
causticizing demand increases with a factor 1.43
if all sulfur goes to the gas phase as H2S.

In the Chemrec (HT, HP) gasifier is approx 55%

of the sulfur estimated to be released to the gas
phase. This corresponds to an increased
causticizing demand with a factor 1.24.

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Direct and Auto Causticization

Addition of a chemical agent to the black

liquor
Reacts during combustion or gasification
Forms a sodium salt and carbon is
released as CO2

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Autocausticization
the formed sodium salt is soluble in alkaline
solutions, eg Na3BO3

Autocausticization means self-causticization, i.e.

The pulping alkali causticizes itself during combustion
or gasifiction

Direct causticization
the formed sodium salt is insoluble in alkaline
solutions, eg 4Na2O5TiO2

The causticization agent is added and subsequently

removed, and added again...

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 Full Borate Autocausticization Partial Borate Autocausticization
Wood

LIME CaO
Wood
BURNING PULPING Na, S, B
CaO NaOH
LIME Na2S, NaBO2
BURNING PULPING Na, S, B
CaCO3 Pulp
CAUSTICIZATION WASHING
Pulp
CaCO3 WASHING
CAUSTICIZATION Na2S (aq)
Na2CO3 (aq),
NaOH NaBO2 (aq)
Na2S,
NaOH
NaBO2
EVAPORATION
EVAPORATION

DISSOLUTION
DISSOLUTION
Na, S, B Na, S, B
Na2S (l) BURNING Na2S (l) BURNING
Na3BO3 (l) GASIFICATION Na2B4O7.5H2O Na2CO3 (l) GASIFICATION Na2B4O7.5H2O
Na3BO3 (l)

Full Titanate Direct Causticization Partial Titanate Direct Causticization

Wood
CaO Wood
LIME
BURNING LIME CaO
NaOH PULPING Na, S BURNING NaOH PULPING
Na2S Na, S
Na2S
CaCO3 Pulp
CAUSTICIZATION WASHING CaCO3 Pulp
CAUSTICIZATION WASHING
NaOH Na2S (aq)
Na2CO3 (aq)
SOLID SEPARATION
SOLID SEPARATION
Na2S (aq)
EVAPORATION EVAPORATION
NaOH Na2S (aq) NaOH
Na2O.3TiO2 (s) Na2CO3 (aq) Na2O.3TiO2 (s)

DISSOLUTION DISSOLUTION
Na, S Na, S
Na2S (aq) BURNING Na2S (aq) BURNING
4Na2O.5TiO2 GASIFICATION Na2CO3 (aq) GASIFICATION
4Na2O.5TiO2

Na2O.3TiO2 (s) Energy TechnologyCentre Na2O.3TiO2 (s)

Borate Autocausticization
Wood

LIME CaO
BURNING NaOH PULPING Na, S, B
Na2S, NaBO2
CaCO3 Pulp
CAUSTICIZATION WASHING

Partial Na2S (aq)

Na2CO3 (aq),

autocausticization NaBO2 (aq)

NaOH
EVAPORATION

DISSOLUTION
Na, S, B
Na2S (l) BURNING
Na2CO3 (l) GASIFICATION Na2B4O7.5H2O
Na3BO3 (l)

In a gasifier (or a recovery boiler):

NaBO2 + Na2CO3 Na3BO3 + CO2
In the smelt dissolver:
Na3BO3 + H2O 2 NaOH + NaBO2 (aq)

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Overall objective

Experimentally test if borate

autocausticization can be achieved
during High Temperature, High
Pressure Black Liquor Gasification

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Experimental
Primary gas + BLS

Flow straightener

Furnace

Collector

Secondary gas

Quench gas

To FTIR, GC
Cyclone
(3 m cut off) Fine particle filter

Atmospheric experiments, Pressurized experiments,

IPST, Atlanta, GA, USA IPST, Atlanta, GA, USA

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Experimental
Sample
Kraft BL + NaBO24H2O
Soda BL + NaBO24H2O
25% autocausticization
Expr conditions PEFR (14 expr runs)
5, 10, 15 bar
1000C
0%, 5%, 10%, 15% CO2 in N2
Expr conditions LEFR (64 expr runs)
1 bar
900C-1100C
0% - 20% CO2 in N2
Analysis
Char residue: Na, K, Ca, V, S, B, C, CO3
Dissolving the char and analysing the formed
solution for OH, CO3, S, B

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Borate Autocausticization
Aim:
Determine the reduction of carbonate in
gasification smelt due to reaction:

Na 2CO 3 + NaBO 2 Na 3BO 3 + CO 2

Two analytical possibilities:

reduction of carbonate concentration in
smelt
hydroxide formation when dissolving the
char
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Borate Autocausticization -
Analysis
In a gasifier:
NaBO2 + Na2CO3 Na3BO3 + CO2
In the smelt dissolver:
Na3BO3 + H2O 2 NaOH + NaBO2 (aq)

Hydroxide formation is based on both reactions

above
Reduction of carbonate concentration in the smelt
on the first reaction

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Temperature influence (LEFR)
3.5
Borate doped kraft liquor
3.0 Kraft liquor
Kraft liquor
CO3 *10 g / g Ca

2.5
5% CO2 in N2
2.0 Atm pressure
-4

1.5
2-

1.0 Ca as tie component

CO32- based
0.5

0.0
850 900 950 1000 1050 1100 1150

Temperature (oC)

Decreasing amount of carbonate in char with increasing temperature

No clear influence of borate addition

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CO2 influence (LEFR)
CO32- based, Ca as tie component
3.5 Kraft liquor
Borate doped kraft liquor 1000C
3.0 Kraft liquor
Atm pressure
CO3 *10 g/ g Ca

2.5

2.0
-4

1.5
2-

1.0

0.5

0.0
-5 0 5 10 15 20 25

CO2 (%) in N2

Increasing amount of carbonate in char with increasing CO2

No clear influence of borate addition

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CO2 influence (LEFR)
OH- based, Ca as tie component
0.12 Kraft liquor
Borate doped kraft liquor 1000C
0.10 Kraft liquor
Atm pressure
0.08
OH g / g Ca

0.06

0.04
-

0.02

0.00

-0.02
-5 0 5 10 15 20 25

CO2 (%) in N2

Increasing amount of hydroxide in char with increasing CO2

More hydroxide for the borate doped liquor

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 Fixed carbon conversion (LEFR)
Kraft liquor and atm pressure

1000C 5% CO2 in N2
1.00 1.00
fixed carbon conversion

fixed carbon conversion

0.95 0.95

0.90 0.90

0.85 0.85

0.80 0.80

0.75 0.75

0.70 Borate doped kraft liquor Borate doped kraft liquor

0.70
Kraft liquor Kraft liquor
0.65 0.65
-5 0 5 10 15 20 25 850 900 950 1000 1050 1100 1150
CO2 (%) in N2 Temperature (oC)

High degree of fixed carbon conversion (>99%) above 1000C

and with 5% CO2 in the gas phase

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Pressure influence (PEFR)
35

30
Soda liquor 1000C
% Autocausticization 25
(from carbonate analysis)
5% CO2 in N2
20 Kraft liquor
(from carbonate analysis)
15

10
Soda liquor
(from hydroxide analysis)
5
Kraft liquor
0 (from hydroxide analysis)

5 7 9 11 13 15

Pressure (bar)

No strong influence of pressure on autocausticization

More autocausticization for the soda liquor
trends are the same but difference in absolute numbers between the
analytical methods

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Major findings
Very small difference between doped and
undoped liquors
No strong evidence that the borate addition has
achieved the desired effect (autocausticization)
The different analytical methods (CO32- and
OH-) give different absolute numbers but the
trends are similar
More autocausticization with the soda liquor
than kraft liquor

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Acknowledgement
The group at IPST
invaluable experimental support from
Xiaoyan Zeng, Alan Ball, Christopher
Young
Dr. Kristiina Iisas patience and
willingness to work out a schedule for the
utilization of the LEFR

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Acknowledgement
Financial support
The Swedish BLG program
STEM, MISTRA, SmurfitKappa Kraftliner,
SCA, Sdra, Sveaskog, Vattenfall,
Lnsstyrelsen, Chemrec
Travel grant from IEA for the PEFR
experiments
Travel grant from The Swedish scientific
council for the LEFR experiments

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