The Kraft Process

Turpentine may also be recovered from the exhaust gas condensate. 

The role of the carbon is to reduce the sulfate ion of the salt cake to sulfide (cf. pyrometallurgy, Chapter 17). The carbon forms carbonate rather than CO2 because of the alkaline medium  

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Fig. 11. Flow diagram for the beater additive process. Kraft represents the kraft process wood pulp and NC is nitrocellulose used as starting materials...

PolysuWde Process. One modification to the kraft process being appHed commercially is the polysulfide process (38). Under alkaline conditions and relatively low temperature (100—120°C), polysulfides oxidize the active end group of the polysaccharide polymer to an alkaH-stable aldonic acid. This reaction, known for many years (39), was not produced on a commercial scale until the development of an efficient method for in situ generation of the polysulfide in kraft white Hquor. 

A high yield chemical pulp, eg, 52—53% bleached yield from softwoods, can be obtained, but strength properties ate inferior to those obtained from the kraft process. If a protector, eg, potassium iodide, is added, an additional 2—3% yield is obtained, as is an improvement in all strength properties. The gas penetration problem can be minimized if ftbetization is accompHshed before treatment with oxygen. Oxygen treatment of virtually all types of semichemical and mechanical pulps has been explored (55). Caustic, sodium bicarbonate, and sodium carbonate have been used as the source of base (56,57). In all cases, the replacement of the kraft by these other processes has not been justified over the alternative of pollution abatement procedures. 

FIG. 22-22 Schematic diagram of the Kraft process for producing decaffeinated coffee using supercritical carbon dioxide (McHugh and Ktukonis, op. cit.). 

The most widely used pulping process is the kraft process, as shown in Fig. 6-11, which results in recovery and regeneration of the chemicals. This occurs in the recovery furnace, which operates with both oxidizing and reducing zones. Emissions from such recovery furnaces include particulate matter, very odorous reduced sulfur compounds, and oxides of sulfur. If extensive and expensive control is not exercised over the kraft pulp process, the odors and aerosol emissions will affect a wide area. Odor complaints have been reported over 100 km away from these plants. A properly controlled and operated kraft plant will handle huge amounts of material and produce millions of kilograms of finished products per day, with little or no complaint regarding odor or particulate emissions. 

The kraft process has become the dominant process for pulp production throughout the world, primarily because of the recovery of the pulping chemicals. A schematic diagram of the kraft pulping process, with the location of atmospheric emission sources, is shown in Fig. 6-11. 

Three major sources in the kraft process are responsible for the majority of the H2S emissions. These involve the gaseous waste streams leaving the recovery furnace, the evaporator and the air stripper, respectively denoted by R), R2 and R3. Stream data for the gaseous wastes are summarized in Table 8.8. Several candidate MSAs are screened. These include three process MSAs and three external MSAs. The process MSAs are the white, the green and the black liquors (referred to as Si, S2 and S3, respectively). The external MSAs include diethanolamine (DBA), S4. activated carbon, Sj, and 30 wt% hot potassium carbonate solution, S6. Stream data for the MSAs is summarized in Table 8.9. Syndiesize a MOC REAMEN that can accomplish the desulfurization task for the three waste streams. 

We focused our attention on Tall oil, a by-product of the paper industry, whenever this is prepared according to the KRAFT process. Said material consists of a mixture of highly unsaturated fatty acids (many of which with conjugated diene systems) and terpene derived rosin acids. The rosin acids have the molecular formula C20H30O2 and thus belong to the diterpenes (pimaric and abietic acids). Tall Oil has an iodine number equal to approximately 170 gl2/100 g. 

The kraft process evolved from the soda process. The soda process uses an alkaline liquor of only sodium hydroxide (NaOH). The kraft process has virtually replaced the soda process due to the economic benefits of chemical recovery and improved reaction rates (the soda process has a lower yield of pulp per pound of wood furnish than the kraft process). 

Kellner process are unbalanced, and for the regeneration of waste pulping liquors in the manufacture of pulp and paper by the Kraft process. See also Lowig. 

Sulfate (2) An acid papermaking process, also known as the Kraft process. 

Delayed coking, 28 649-650 Delayed coking technology, 22 721-722 Delignification, 22 21 chemistry of, 22 23-26 in the kraft process, 22 22 in organosolv pulping, 22 30 Deliquoring, in solid-liquid separation, 22 344... 

Recovery of inorganic chemicals is crucial to the cost effectiveness of the Kraft process. The black liquor which is obtained from delignification is rich in solubilised lignin and carbohydrate degradation products and, after concentration, is combusted in a recovery furnace. The Carbon dioxide which is produced during combustion converts unused sodium hydroxide into sodium carbonate. In addition, the sodium sulfate is converted, under the reducing atmosphere of the furnace, to sodium sulfide. 

Kraft pulping involves the cooking of wood chips at 340-350°F and 100-135 psi in liquor that contains sodium hydroxide, sodium sulfide, and sodium carbonate. This process promotes cleavage of the various ether bonds in lignin and the degradative products so formed dissolve in alkaline pulping liquor. The Kraft process normally incorporates several steps to recover chemicals from the spent black liquor [3]. 

The process of pulping, degrading the lignin to a more soluble form so the cellulose fibers can be separated from it, involves some interesting chemistry. The kraft or alkaline sulfate process dominates this part of the industry. Approximately 78% of all pulp is made by the kraft process, 3%... 

The bisulfide ion present in the kraft process is even a better nucleophile than hydroxide, so when it is present it attacks the quinonemethide intermediate. An episulfide is formed that then hydrolyzes to a thiol-alcohol. 

Two other important side products of the kraft process are sulfate turpentine and tall oil. The turpentine is obtained from the gases formed in the digestion process. From 2-10 gal of turpentine can be obtained per ton of pulp. Tall oil soap is a black viscous liquid of rosin and fatty acids that can be separated from the black liquor by centrifuging. Acidification gives tall oil. These side products will be discussed later. 

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