Recovery of Chemicals from Kraft Pulping Process
Chemical recovery system is an integral part of pulp and paper units and the efficiency of chemical recovery plays an important role in economics. Efficiency of chemical recovery units in terms of thermal efficiency, energy recovery and conversion of thermal energy to electrical energy has tremendous impact on overall economy of pulp production . Although earlier agro-based mills were not having recovery furnace due to high silica content of black liquor and smaller capacity, however now chemical recovery in agro-based mills have been made mandatory. Important terms in recovery of chemicals are given in Table M-TTT 3.1.
Table M-III 3.1: Important terms in Recovery of Chemicals
Total titratable alkal
NaOH/ NaOH +Na2S
[NaOH/ NaOH +Na2S )] x 100
Na2S/( Na2S04 + Na2S )
Over all recovery
Recovery = black liquor stock/ fresh liquor consumed
Recovery of chemicals from black liquor is very important for overall economy of paper industry. Kraft recovery process flow diagram is shown in Figure M-III 3.1. Various sections in kraft recovery plant are
Figure M-III 3.1: Kraft Recovery Process
Figure M-III 3.2: Kraft Recovery Furnace
Black Liquor Oxidation: Black liquor oxidation has become integral part of recovery section for reducing the emission of volatile sulphur compounds. Oxidation of black liquor by air reduces the emission of odorous sulphur compounds. Mecrcaptans and other sulphur compounds are oxidized into less volatile chemicals. Both weak black liquor and concentrated black liquor oxidation has been reported. Typical Composition of Black Liquor from Wheat Straw Pulping is given in Table M-III 3.2.
Various steps involved in kraft recovery section are
Reactions in recovery of chemicals from black liquor
The main reactions are (1-3 predominantly)
Na+ + H+ + S2-→NaHS
Na + OH-→NaOH
and other reactions:
Na2CO3+CaO +H2O 2NaOH+ CaCO3
CaCO3 → CaO + CO2
Table M-III 3.2: Typical Composition of Black Liquor from Wheat Straw Pulping
Wheat straw Black liquor
Swelling volume ratio ml/g
Gross calorific value
Silica as SiO2% , w/w
Acid insoluble as SiO2 %, w/w
Chloride as Cl, %, w/w
Potassium as K, %w/w
Sodium as Na%, w/w
Calcium as Ca %, w/w
Inorganic as NaOH%, w/w
Typical Characteristics of Black liquor
1 ton of black liquor - 2.2 ton of steam
Black liquor solid=1.30 ton /ton of pulp.
Weak black liquor per ton of pulp -10 -12 m3
Calorific value of black liquor: 3080 cal/gm
Black liquor-Organic 70%, Inorganic 30%
Weak black liquor: Na 28 gm/lit
Recovery of Chemicals in Agro-Based Mill
With the shortage of forest based raw material and to preserve the forest, the paper industry in Asia and other parts of the world is forced to use non woody fibrous raw materials. India is one of the leading countries using substantial proportion of non wood materials which constitute about 50% of total raw material furnish . Non-wood raw materials are characterized by high silica content which varies from 1.5 to 20%. Most of the silica present in raw material passes into black liquor. Presence of silica in relatively high concentration creates numerous problems in chemical recovery plants. Evaporator, recovery furnace, and lime kiln operation are adversely affected by presence of silica in black liquor .The process of distillation of bamboo and straw black liquors by carbonation has been developed by central Pulp and paper Research institute, Saharanpur,
Due to high silica content of the agricultural residues recovery of chemical from agrobased mills have caused major concern in Indian paper mills. Table M-III 3.3 gives the details of processes for recovery of chemicals from agricultural residues black liquor. Black liquor from cooking agricultural residues has high silica content and cannot be concentrated to high solid contents to enable its burning in conventional recovery
systems. Although, technologies are available and being practiced in many mills in other part of world; however, due to poor infrastructure still recovery of chemicals is not being practiced by majority of mills in Indian posing serious environmental pollution problems. Pollution load in agro-based small mills having no chemical recovery is almost three times to that of pollution load in large integrated mills
Some of the currently accepted technologies for recovery of chemicals for agro-based black liquor are: Rotary roaster, Roaster cum smelter, Broby smelter, Dry pyrolysis Process, Wet air oxidation process, Copeland reactor. Some of the emerging technologies are Wet cracking process, Chemsec process, Thermo chemical conversion reactor system, Super critical wet oxidation process, Direct causticization process, ABC process, Direct alkali recovery system (DARS) or Ferrite process. In the fluidized bed soda recovery system where the weak black liquor containing high silica content is concentrated to about 45percent concentration in multiple effect evaporator, venturi scrubber and cyclone system and is sprayed in the fluidized bed combustion system.
Table M-III 3.3: Processes for Recovery of Chemicals from Agricultural Residues Black liquor
Ferrite process (DARS process)
30% conc. Black liquor burnt with ferric oxide at temp 850 0c.
Na2CO3 +Fe2O3 2NaFeO3 +CO2
2NaFeO3 +H2O 2NaOH + Fe2O3
Wet air oxidation process
Oxidation of organic matter at high temp 320-320 0c pressure 175-250 kg/cm2.
Ultra Filtration and
Sodium compound is removed as permeate. High molecules
weight lignin fraction is rejected in interface.
COPE LAND process
34-35% Solid liquor is burnt in fluidized bed reactor. 650-
Evaporation 35-37% in evaporator. Last two effect falling
film. Upto 50% in direct contact evaporator, then concentrated
black liquor is burnt.
18-20% evaporation in multiple effect evaporator upto 50%
inn cyclone evaporators. Concentrated black liquor is fired in
Similar to Smelter cyclone process
Burning of Black liquor
Removal of silica by carbonation followed by concentration