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Chemical Recovery at the Sulphate Pulp Mill

During the cook the cooking chemicals have been transformed. Recovery of these chemicals is absolutely essential for both environmental and economic reasons. This is accomplished in the chemical recovery department at the mill. The black liquor coming from the pulp wash also contains lignin from wood and other dissolved organic matter. This, too, is taken care of in the mill's chemical recovery system and is used as fuel in the recovery boilers The sulphate process, then, is based on a cycle principle ensuring that the raw materials are used efficiently and that emissions and energy losses are minimized. The recovery system at the sulphate pulp mill concist of: Evaporation, in course of which the black liquor is thickened into so-called concentrated or thick waste liquor. The soda recovery boiler, where the organic matter in the thick waste liquor is converted into steam, with the chemicals being recovered at the same time. White liquor preparation (with causticization and lime sludge reburning kiln), in which the chemicals are converted so that they once again become cooking chemicals.

Figure: Fibre line and

recovery system in the sulphate pulp mill. The chemicals used in the cook and in oxygen gas delignification are put to use thanks to the recovery system. They are returned to the digester plant in the form of white liquor from the white liquor preparation process. Evaporation: The black liquor from the washing department has a dry solids content of about 15 per cent. To make this liquor combustible it is evaporated. On combustion it is important for the dry solids content to be as high as possible, as this results in better thermal economy, smaller emissions of sulphurous gases and more efficient conversion of the chemicals into active cooking chemicals. During evaporation the water in the liquor is boiled off, using steam as the heating medium. If evaporation takes place in one stage, then just as much steam is consumed as the amount of water evaporated. Because of this, evaporation is usually divided up into five or six stages, thus reducing the steam requirement to approximately one fifth. The evaporation process is carried out in evaporators which are a type of heat exchanger. Figure 9 shows an evaporation plant with five stages. Fresh steam (steam produced in a steam boiler) is used in the first stage. The liquor boils and expels liquor vapour which is conveyed as heating steam to the second stage. The liquor vapour from the second stage heats the third stage and so on. Fresh steam is thus required only in the first stage.

Figure: Arrangement sketch illustrating the path of the liquor and steam in a five-stage evaporation plant.

In order for the evaporation plant to function properly the heating steam in each stage must have a higher temperature than the liquor in the same stage. This means that temperature and pressure successively go down in the stages, counted from the first stage. The temperature and pressure of the fresh steam in the first stage may be about 135 C and 25 kPa (75 kPa vacuum) in the liquor vapour from the last stage. The pressure reduction is accomplished with the aid of a condenser that is cooled with cold water and delivers hot water. A vacuum pump after the condenser sucks out noncondensible gases. These comprise partly air and partly foul-smelling sulphurous gases which are passed on for combustion. The vapours are condensed against the heat surfaces of the stages and condenser, the condensate being led out. The condensate from the first stage is clean and passes via the feed water cleaning plant to the steam boilers. The second condensate. liquor vapour condensate, is contaminated with methanol, among other things. The condensates from stages two and three are clean enough to be used in white liquor preparation and pulp washing, whereas the condensate from the final stages and condenser must be cleaned. The separated methanol can be used as fuel in the lime sludge reburning kiln. The entering liquor, i.e. thin liquor and/or black liquor, is pumped to stage three and proceeds from there to stages four and five. The liquor from stage five is partially thickened and for this reason is known as semi-thickened or intermediate liquor. This is stored in a tank and pumped to stage one. The liquor then goes to stage two and is finally removed as ready-evaporated concentrated (thick) waste liquor. The heating surface consists of a large number of vertical tubes, all encased in a cylindrical sheet-steel shell. The liquor enters at the bottom and flows inside the tubes. The vapour which is formed when the liquor boils rises and pulls with it a layer (film) of liquor along the inside walls of the tubes, which is why we have the name rising film. The rising film evaporator has the limitation that it cannot be used to evaporate to a dry solids content of more than 60-62 per cent. High dry solids contents give rise to coatings and clogging of the tubes. A couple of final thickeners can be connected in order to increase the dry solids content to 70 per cent.As the name suggests, the mode of operation is the opposite to the rising film - the liquor flows as a film along the walls of the heating surface. To prevent the latter from 'running dry', liquor is circulated from the bottom to the top of the apparatus. By using special falling film evaporators as final evaporators the liquor can be evaporated to a dry solids content of 75-80 per cent. The extractive substances in softwood are dissolved during the cook and remain in the black liquor as black (sulphate) soap. This flows to the top in the liquor tanks and forms a sticky and foul-smelling substance. This substance is skimmed off and used in the production of tall oil. This takes place in the resin cooking department where the soap is boiled with sulphuric acid or residual solution from the chlorine dioxide production facility. Tall oil is a raw material for the manufacture of detergents, paints and varnishes. It is occasionally also used as fuel in the lime sludge reburning kiln instead of oil. The soda recovery boiler is a steam boiler which has been modified to burn black liquor. It is also a chemical reactor - the first stage in conversion of the chemicals recovered during pulp washing into new cooking chemicals.

Figure: Soda recovery boiler with ancillary equipment.

The evaporated liquor (concentrated waste liquor) is sprayed into the furnace of the soda recovery boiler through special nozzles. The combustion air is blown into the furnace at several levels and the liquor is dried by the hot flue gases to form a bed on the bottom of the furnace. Here, the organic compounds are gasified and finally burned higher up in the furnace. Emitted carbon dioxide forms, together with some of the sodium in the dry solids, sodium carbonate (Na2CO3) - soda which has given the boiler its name. The sodium sulphate (Na2SO4) formed - as well as any sodium sulphate added as a make-up chemical - is converted by reduction with the aid of carbon in the charred dry solids into sodium sulphide (Na2S). Sodium sulphide is an active cooking chemical. The degree of reduction is a measure of how large a proportion of the sodium sulphate has been converted into sulphide. This is usually between 90 and 92 per cent and is a measure of the efficiency of the soda recovery boiler as a reactor. Sodium carbonate, sodium sulphide and some ballast chemicals flow out from the bottom of the furnace in the form of a melt via the chutes belonging to the soda recovery boiler into the melt dissolver. Here the melt is dissolved into so-called weak liquor from the white liquor preparation plant and is now called green liquor. The dry solids content of the concentrated waste liquor is of importance for the operation of the soda recovery boiler. The higher the dry solids contents the higher the temperature in the furnace. This increases the degree of reduction and lowers the contents of environmentally harmful sulphur dioxide (SO2) and hydrogen sulphide (H2S) in the outgoing flue gas. A high dry solids content also increases steam production. Developments in evaporation techniques in recent years, leading towards high dry solids contents, will therefore be beneficial in several ways. The soda recovery boiler, in principle, is a traditional steam boiler with tubes in the walls, bottom and ceiling of the furnace and with superheaters and convection tubes after the furnace. Feed water is supplied which boils off the heat from combustion. The steam is superheated to about 450 G. The steam pressure is normally about 6 MPa. The melt and the flue gases are corrosive. A water leak can cause an explosion if the water comes into contact with the melt. Because of this the tubes in the lower part of the boiler usually have a protective coat of stainless steel (compound tubes). To prevent dust accompanying the flue gases from passing out through the chimney and dirtying the surroundings it is trapped in electrostatic precipitators. The dust is returned to the soda recovery boiler via the mixing tank. Sometimes there is also a flue gas scrubber after the filters. Here, any remaining dust is washed away, together with sulphur dioxide and foul-smelling hydrogen sulphide, with water. At the same time, hot water is obtained from the scrubber. White liquor preparation. Green liquor from the soda recovery boiler continues to the white liquor preparation facility which is the final process stage in the recovery system. White liquor preparation: Green liquor from the melt dissolvers is first cleaned to remove sludged contaminants. In the arrangement sketch. This is done in a green liquor clarifier which separates the sludge by sedimentation. Pressure filters have also come into use in recent years. One recently developed apparatus is a disc filter with rotating felt-clad filter discs. Any green liquor remaining in the separated sludge is washed out on a sludge filter. The filtrate (weak liquor) is pumped to the melt dissolver in the soda recovery boiler.

Figure: White liquor preparation. Green liquor from the soda recovery boiler is converted into white liquor which is returned to the cooking plant.

The cleaned liquor is conveyed to the lime slaker where it is mixed with burnt lime. The water in the liquor reacts with (slakes) the lime which becomes calcium hydroxide. Sand and non-reacted pieces of lime are scraped out and disposed of on a rubbish tip. From the lime slaker, the mixture of liquor and lime proceeds to a number of causticization vessels connected together in series. Here sodium carbonate reacts with calcium hydroxide and is converted into sodium hydroxide and calcium carbonate (CaCO2). Sodium hydroxide is also known as caustic soda, which explains the name causticization, as the reaction is called. After causticization the sodium hydroxide has been restored and the liquor is once again white liquor. Before this can be re-used the other product of the reaction, calcium carbonate, called lime sludge, must be separated off. Lime sludge is a grey substance that looks like mud or clay. When it has been removed the white liquor is ready for use again in the cooking plant. Separation of lime sludge, white liquor clarification, is usually done nowadays by pressure filtration in tube filters. The lime sludge is diluted with returned filtrate (hot water) and washed in pressure filters. It is then finally washed and thickened on a lime sludge filter of drum type. The lime sludge is reburned to lime in a lime sludge reburning kiln. This is a rotary furnace consisting of a very long slightly sloping pipe (the longest one in the world is 135 metres!). The lime sludge is admitted at the upper end of the furnace. Fuel, which can be oil, gas, tall oil, methanol from condensate cleaning or biofuel, is supplied at the lower end. The lime sludge is fed by rotation down towards the burning zone where the temperature is about 1,200 C. The calcination process takes place here, converting the calcium carbonate into calcium oxide (slaked lime). The cycle for lime recovery has now gone full circle. The lime sludge reburning kiln is one of the major oil consumers at the sulphite pulp mill. In recent years, however, the oil has been replaced in several cases with bark and forest waste which is dried, ground into powder and burned. The powder can also be gasified into generator gas and then burned. The lime sludge reburning kiln also serves a useful purpose with regard to the environment, in that it is often used as a destruction furnace for foul-smelling gases from the digester house and evaporation plant. These gases do have some value as a fuel and reduce the need of other fuels for the furnace. Lime and lime sludge dust accompanying the flue gas is separated in electrostatic precipitators or scrubbers before the gas goes out through the chimney. Reference: http://www.skogssverige.se/MassaPapper/Faktaom/eng/massaopapptillv/sulfkemi.cfm