Pulping and Bleaching

PSE 476

Lecture #6
Kraft Pulping Chemicals

PSE 476: Lecture 6

Chemical Pulping
Agenda

Basic Description of Liquors & Process

White, Black & Green Liquors

Definition of Terms
Total alkali, Effective Alkali, Sulfidity, etc.

Why is everything on a Na2O basis?

PSE 476: Lecture 6

Kraft Pulping:

Definition of Terms
White liquor.
Fresh pulping liquor for the kraft process containing
NaOH, Na2S, and a variety of impurities.

Black liquor.
The waste liquor from the kraft pulping process.
Contains most of the original inorganic components (most
in different forms) and a high concentration of dissolved
organics.

Green liquor.
Partially recovered kraft liquor (intermediate liquor in
recovery sequence).

PSE 476: Lecture 6

Simplified Liquor Scheme

White Liquor

Lime
Kilm

Digester

Green Liquor

Black Liquor

Recovery
Furnace
PSE 476: Lecture 6

This is a very
simplified
diagram. There
are several steps
between each
box. We will
discuss this
whole sequence
in depth in a
later lecture.
4

Typical Composition of
Kraft Liquors
Chemical
Chemical

White*
White*

Black*
Black*

Green*
Green*

NaOH
NaOH
Na
Na22SS

95
95(53%)
(53%)
38
38(21%)
(21%)

1.4
1.4(7%)
(7%)
4.2
4.2(19%)
(19%)

15
15(8%)
(8%)
37
37(20%)
(20%)

Na
Na22CO
CO33
Na
Na22SO
SO33

26
26(15%)
(15%)
4.8
4.8(3%)
(3%)

7.8
7.8(36%)
(36%)
22(9%)
(9%)

107
107(60%)
(60%)
6.1
6.1(3%)
(3%)

Na
Na22SO
SO44
Na
Na22SS22OO33

9.1
9.1(5%)
(5%)
66(3%)
(3%)

2.8
2.8(13%)
(13%)
3.4
3.4(16%)
(16%)

11
11(6%)
(6%)
5.5
5.5(3%)
(3%)

Organics
Organics

None
None

Lots
Lots

None
None

* Median concentrations as g/l as Na2O

PSE 476: Lecture 6

Typical White Liquor

Composition
Chemical
Chemical
NaOH
NaOH

Amount
Amount
(as
(asNa
Na22O)
O)
81
81--120
120g/l
g/l

Na
Na22SS

30
30--40
40g/l
g/l Active
Active

NA
NA

Na
Na22CO
CO33

11
11--44
44g/l
g/l Inactive
Inactive

Incomplete
IncompleteCaustizing
Caustizing

Na
Na22SO
SO33

Active
Active

Source
Sourceof
ofunwanteds:
unwanteds:
(Recovery
(RecoverySystem)
System)
NA
NA

Inactive
Inactive

Incomplete
IncompleteReduction
Reduction

Na
Na22SO
SO44

4.4
4.4--18
18g/l
g/l Inactive
Inactive

Incomplete
IncompleteReduction
Reduction

Na
Na22SS22OO33

44--8.9
8.9g/l
g/l Inactive
Inactive

Oxidation
Oxidationof
ofSulfide
Sulfide

Notes Page

22--6.9
6.9

Class*
Class*

PSE 476: Lecture 6

Definition of Terms (US)

All chemicals are reported as concentrations in
liquor (g/l) or as charge (%) on dry wood.
Total Chemical: All sodium salts (as Na2O).
Total Alkali: NaOH + Na2S + Na2CO3 +
1/2Na2SO3 (as Na2O).
This is the sum of the sodium salts that contribute to
or are converted during kraft cooking to chemicals
which contribute to active alkali.

Active Alkali: Na2S + NaOH (as Na2O) 100g/L

PSE 476: Lecture 6

Definition of Terms (US)

Sulfidity: 24-28%

Causticity:

Sulfidity =

Causticity =

Na2S
NaOH + Na2S

NaOH
NaOH + Na2S

* 100%

* 100%

PSE 476: Lecture 6

Definition of Terms (US)

Effective Alkali: NaOH + 1/2 Na2S (as Na2O) no more
than 55 g/L
Activity: % ratio of Active to Total Alkali
Causticizing Efficiency: 78-80%

Causticizing eff. =

NaOH

NaOH + Na2CO3

* 100%

Reduction Efficiency: 95%

Na2S

Reduction eff. =
* 100%
Na2S + Na2SO4 + Na2SO3 + Na2S2O3
PSE 476: Lecture 6

Why Na2O? (1)

Expressions such as sulfidity, causticity, effective
alkali, etc best describe the conditions in a
kraft cook.
These expressions contain information on the
amounts (g/liter or %) of different chemicals
such as NaOH, Na2S, etc which have different
degrees of effectiveness
Reporting on a Na2O basis indicates the actual
chemical relationship between these chemicals
PSE 476: Lecture 6

10

Why Na2O? (2)

Na2O + H2O = 2NaOH
1 mole Na2O creates 2 moles of NaOH
62 grams Na2O is equivalent to 80 grams of NaOH
Therefore, 1 mole of NaOH is equal to 1/2 mole of Na 2O
40 g/l NaOH = 0.5 * 62 g/l Na2O = 31 g/l on Na2O basis
PSE 476: Lecture 6

11

Why Na2O? (3)

Na2O + H2S

Na2S + H2O (hypothetical equation)

1 mole Na2O creates 1 moles of Na2S

Therefore, 1 mole of Na2S is equal to 1 mole of Na2O
62 grams Na2O is equivalent to 78.1 grams of Na2S
78.1 g/l Na2S = 62 g/l Na2O

Na2O + H2CO3
Na2O + H2SO4
Na2O + H2SO3

Na2CO3 + H2O
Na2SO4 + H2O
Na2SO3 + H2O
PSE 476: Lecture 6

12

Kraft Pulping Liquor

Sample Calculation

PSE 476: Lecture 6

13

Kraft Pulping Liquor

In-Class Example Calculations (1)

50 Tons Chips
50% Moisture Content
Liquor Charge to Digester:
1200 ft3 white liquor
- EA = 13% (alkali charge on OD wood as Na2O)
- Sulfidity = 25.2%

1300 ft3 black liquor

Question: How many lbs./ft3 of NaOH and Na2S

were charged to the digester in the white liquor?
(assume no chemical contribution from black liquor)

PSE 476: Lecture 6

14

Kraft Pulping Liquor

In-Class Example Calculations (2)

Step 1: Calculate the amount of oven dry wood
50 tons chips 2000 lbs./ton 0.5 (m.c.) = 50,000 lbs. o.d. wood
Step 2: Calculate the amount of NaOH and Na2S as Na2O in the
white liquor using the EA and Sulfidity numbers
EA = NaOH + 1/2 Na2S = 13% on od wood.
NaOH + 1/2 Na2S = 0.13 50,000 = 6500 lbs.
NaOH = 6500 lbs. - 1/2 Na2S
PSE 476: Lecture 6

15

Kraft Pulping Liquor

In-Class Example Calculations (3)

Na2S
100 = 25.2%
Sulfidity =
Na2S + NaOH
Na2S
Na2S
= 0.252 =
Na2S + (6500 - 1/2Na2S)
0.5 Na2S + 6500 lbs.
Na2S = 0.126 Na2S + 1638 lbs.

0.874 Na2S = 1638 lbs.

Na2S = 1874 lbs. (Na2O)

NaOH = 6500 lbs. - (0.5)(1874 lbs.) = 5563 lbs. (Na2O)
PSE 476: Lecture 6

16

Kraft Pulping Liquor

In-Class Example Calculations (4)

Step 3: Convert NaOH and Na2S values from Na2O
Na2O = 62 g/mole or lbs./mole for this exercise
NaOH = 40 g/mole
Na2S = 78.1 g/mole

As we discussed in class, these calculations are based on

an equivalence in sodium (Na). This means that Na2S and NaOH
are equivalents but that NaOH is equal to 1/2 Na2O.
Na2S = 1874 lbs. (Na2O) 1mole/62 lbs. 78.1 lbs./mole = 2360.6 lbs.
NaOH = 5563 lbs. 1 mole/62 lbs. 2.0 40 lbs./mole = 7178 lbs.
So: Na2S = 2360.6/1200 ft3 = 1.97 lbs./ft3
NaOH = 7178/1200 ft3 = 5.98 lbs./ft3
PSE 476: Lecture 6

17