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Isbn: 3-527-30999-3

©2006 WILEY-VCHVerlag GmbH&Co .

Handbook of Pulp

Edited by Herbert Sixta

Tab. 9.1 Composition of the dry matter of pine (Pinus sylvestris)

and birch (Betula pendula) kraft black liquors. Values are % of

total dry matter [2,3].

Component Pine Birch

Lignin

Aliphatic carboxylic acids

Formic acid

Acetic acid

Glycolic acid

Lactic acid

2-Hydroxybutanoic acid

3,4-Dideoxypentonic acid

3-Deoxypentonic acid

Xyloisosaccharinic acid

Glucoisosacharinic acid

Others

33

31

6

4

2

3

1

2

1

1

7

4

27

32

4

9

2

2

5

1

1

2

3

3

Other Oganics 8 12

Inorganicsa

Sodium bound to organics

Inorganic compounds

28

12

16

29

12

17

Total 100 100

a. Including sodium bound to organic material.

weight in the range 17–19 kDa. During pulping, the black liquor xylans are progressively

enriched in hexenuronic acid.

Black liquor is concentrated by evaporation and then combusted in the recovery

furnace for the recovery of cooking chemicals and the generation of energy. The

heating value of black liquor has a major impact on the steam generation rate,

knowledge of which is essential in the design and operation of a recovery boiler.

The higher heating (gross calorific) value (HHV) is determined by oxidizing the

black liquor quantitatively, condensing the water vapor produced, and cooling the

products to 25 °C (TAPPI method T 684 om-90). The net heating (net calorific)

Value (nhv), which better reflects the actual energy release, accounts for the fact

that the generated water is not condensed during combustion and steam generation.

NHV is obtained by subtracting the heat of vaporization of the water from

the HHV value. In addition, any sulfur is completely oxidized in the oxygen bomb

calorimeter, whereas with kraft black liquor it always appears as sodium sulfide

(Na2S). The reduction process of Na2S to Na2SO4 is endothermic by 13 090 kJ kg–1

of Na2S. The NHV can be calculated according to the following expression:

NHV _ HHV _ 2440 _

18

_2 _ H__ 13090 _

78

32 _ S _ g_ RED_ _1_

968 9 Recovery

where NHV is the net heating value of black liquor solids (BLS; in kJ kg–1 BLS);

HHV is the higher heating value of BLS (in kJ kg–1 BLS); H and S are the weight

fractions of hydrogen (H) and sulfur (S) in BLS; and gRED is the degree of reduction

given as a weight fraction.

Typical values for the HHV of kraft black liquor range between 13 MJ kg–1 BLS

(predominantly derived from hardwoods) and 15.5 MJ kg–1 BLS (predominantly

derived from softwoods), as indicated in Tab. 9.2.

It should be noted that the recycling of bleach (e.G., oxygen delignification) and

purification (e.g., cold caustic extraction) filtrates has an impact on the composition

and heating value of the BLS due to a generally lower content of organic compounds.

Tab. 9.2 Chemical analysis and heating values of black liquor solids [5–8].

Components A B C D E F G

Wood species Unit hardwood hardwod hardwood softwood softwood softwood softwood

Elemental analysis

C wt% on DS 32.3 33.3 33.4 35.8 37.8 35.8 38.0

H wt% on DS 3.8 3.6 3.9 3.5 4.2 3.6 3.8

N wt% on DS 0.2 0.1 0.1 0.2 0.1

O wt% on DS 35.8 33.6

S wt% on DS 3.0 5.4 4.4 4.1 4.8 4.6 3.7

Na wt% on DS 18.2 19.9 20.7 19.9 17.9 19.6 19.2

K wt% on DS 3.0 1.5 1.7 1.1 1.2 1.8 0.6

Cl wt% on DS 0.7 0.6 0.3 0.2 2.9 0.5 1.0

HHV MJ kg–1 13.2 13.2 13.2 14.1 15.4 15.1

NHV (calculateda) MJkg–1 11.5 10.9 11.1 12.2 13.1 13.2

Reference [5] [6] [6] [6] [6] [7] [8]

a. Assuming a degree of reduction of 90%.