The kraft process (also known as kraft pulping or sulfate process) is a process for conversion of wood into wood pulp, which consists of almost pure cellulose fibres, the main component of paper. The kraft process involves treatment of wood chips with a hot mixture of water, sodium hydroxide (NaOH), and sodium sulfide (Na2S), known as white liquor, that breaks the bonds that link lignin, hemicellulose, and cellulose. The technology entails several steps, both mechanical and chemical. It is the dominant method for producing paper. In some situations, the process has been controversial because kraft plants can release odorous products and in some situations produce substantial liquid wastes.
The process name is derived from the German word Kraft, meaning "strength" in this context, due to the strength of the kraft paper produced using this process.
History
A precursor of the kraft process was used during the Napoleonic Wars in England. The kraft process was invented by Carl F. Dahl in 1879 in Danzig, Prussia, Germany. was issued in 1884, and a pulp mill using this technology began in Sweden in 1890. The invention of the recovery boiler by G. H. Tomlinson in the early 1930s was a milestone in the advancement of the kraft process. It enabled the recovery and reuse of the inorganic pulping chemicals such that a kraft mill is a nearly closed-cycle process with respect to inorganic chemicals, apart from those used in the bleaching process. For this reason, in the 1940s, the kraft process superseded the sulfite process as the dominant method for producing wood pulp.
The process
Impregnation
Common wood chips used in pulp production are long and thick. The chips normally first enter the presteaming where they are wetted and preheated with steam. Cavities inside fresh wood chips are partly filled with liquid and partly with air. The steam treatment causes the air to expand and about 25% of the air to be expelled from the chips. The next step is to saturate the chips with black and white liquor. Air remaining in chips at the beginning of liquor impregnation is trapped within the chips. The impregnation can be done before or after the chips enter the digester and is normally done below . The cooking liquors consist of a mixture of white liquor, water in chips, condensed steam and weak black liquor. In the impregnation, cooking liquor penetrates into the capillary structure of the chips and low temperature chemical reactions with the wood begin. A good impregnation is important to get a homogeneous cook and low rejects. About 40–60% of all alkali consumption, in the continuous process, occurs in the impregnation zone.
Cooking
The wood chips are then cooked in pressurized digesters. Some digesters operate in a batch manner and some in a continuous process. Digesters producing 1,000 tonnes or more of pulp per day are common, with the largest producing more than 3,500 tonnes per day. Typically, delignification requires around two hours at . Under digesting conditions, lignin and hemicellulose degrade to give fragments that are soluble in the strongly basic liquid. The solid pulp (about 50% by weight of the dry wood chips) is collected and washed. At this point the pulp is known as brown stock because of its color. The combined liquids, known as black liquor (because of its color), contain lignin fragments, carbohydrates from the breakdown of hemicellulose, sodium carbonate, sodium sulfate and other inorganic salts.
One of the main chemical reactions that underpin the kraft process is the scission of ether bonds by the nucleophilic sulfide (S2−) or bisulfide (HS−) ions.
Recovery process
The excess black liquor contains about 15% solids and is concentrated in a multiple effect evaporator. After the first step the black liquor has about 20–30% solids. At this concentration the rosin soap rises to the surface and is skimmed off. The collected soap is further processed to tall oil. Removal of the soap improves the evaporation operation of the later effects.
The weak black liquor is further evaporated to 65% or even 80% solids ("heavy black liquor") and burned in the recovery boiler to recover the inorganic chemicals for reuse in the pulping process. Higher solids in the concentrated black liquor increases the energy and chemical efficiency of the recovery cycle, but also gives higher viscosity and precipitation of solids (plugging and fouling of equipment). During combustion, sodium sulfate is reduced to sodium sulfide by the organic carbon in the mixture:
1. Na2SO4 + 2 C → Na2S + 2 CO2
This reaction is similar to thermochemical sulfate reduction in geochemistry.