Chemical recovery

As the economic value of coproducts has decreased, it has become more difficult to provide capital for environmental controls on air emissions and wastewater streams such as toxic phenoHc effluents from chemical recovery operations. Some former coke and manufactured gas sites may require remediation to clean up contaminated soil and groundwater. These difficulties will force the shutdown of some operations and discourage recovery of coproducts in future installations. 

The sequence of treatments is illustrated in Figure 4. Water consumption in washing is minimi2ed by using a countercurrent Hquor flow, clean water entering the system at the point where the fiber leaves, and dirty Hquor leaving for chemical recovery at the point where the fiber enters. 

Chemical recovery ia sodium-based sulfite pulpiag is more complicated, and a large number of processes have been proposed. The most common process iavolves liquor iaciaeration under reduciag conditions to give a smelt, which is dissolved to produce a kraft-type green liquor. Sulfide is stripped from the liquor as H2S after the pH is lowered by CO2. The H2S is oxidized to sulfur ia a separate stream by reaction with SO2, and the sulfur is subsequendy burned to reform SO2. Alternatively, ia a pyrolysis process such as SCA-Bidemd, the H2S gas is burned direcdy to SO2. A rather novel approach is the Sonoco process, ia which alumina is added to the spent liquors which are then burned ia a kiln to form sodium aluminate. In anther method, used particulady ia neutral sulfite semichemical processes, fluidized-bed combustion is employed to give a mixture of sodium carbonate and sodium sulfate, which can be sold to kraft mills as makeup chemical. 

G. Hough, ed.. Chemical Recovery in theMlkaline Pulping Process, TAPPI Press, Adanta, Ga., 1985, p. 197. 

In chemical activation processes, the precursor is first treated with a chemical activation agent, often phosphoric acid, and then heated to a temperature of 450 -700 °C in an activation kiln. The char is then washed with water to remove the acid from the carbon. The filtrate is passed to a chemical recovery unit for recycling. The carbon is dried, and the product is often screened to obtain a specific particle size range. A diagram of a process for the chemical activation of a wood precursor is shown in Fig. 3. 

EPA, 1996b. U.S. EPA, Office of Air Quality Planning and Standards, "Chemical Recovery Combustion Sources at Kraft and Soda Pulp Mills," EPA-453/R-96-012, Research Triangle Park, NC, October, 1996. 

Boilers may be used for domestic hot water heating, space heating, waste heat, or chemical recovery. They also may be used for mechanical work, electrical power generation, cogeneration, and innumerable industrial process applications using direct (live) steam or indirect steam (e.g., coil heated) processes. Both FT and WT designs are commonly employed for heat-recovery applications. 

Waste-heat and other special-purpose boilers Special designs provide boilers for waste heat and chemical recovery, waste-to-energy, and combined-cycle installations, pulverized-bed, and even biomass applications. 

Because of the instability of many of the compounds involved, it is necessary to determine the chemical recoveries in all cases. This requires the use of macro quantities (10 mg up to several hundred mg) of carriers and target compounds. This, in turn, makes it impractical to use the various thin-layer methods, such as paper and thin-layer chromatography and paper electrophoresis, although such methods have proved useful in identifying products and in checking the purity of fractions. The separation methods now most commonly used are column chromatography and sublimation. 

Foster, R., et al., Optimization of the Chemical Recovery CVcle of the Kraft Pulping Process, Laboratory for Applied Industrial Control, Report 54. Purdue University, West Lafayette, IN, 1973. 

In most alpha and mass spectrometric methods for which sample preparation is extensive and chemical recoveries can vary considerably from sample to sample, precise elemental concentrations are determined by isotope dilution methods (e.g., Faure 1977). This method is based on the determination of the isotopic composition of an element in a mixture of a known quantity of a tracer with an unknown quantity of the normal element. The tracer is a solution containing a known concentration of a particular element or elements for which isotopic composition has been changed by enrichment of one or more of its isotopes. 

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). 

FIGURE 21.4 The kraft pulping process (with chemical recovery). (Taken from U.S. EPA, Profile of the Pulp and Paper Industry, 2nd ed., report EPA/310-R-02-002, U.S. EPA, Washington, November 2002.)... 

Although newer technologies are always under development, the basic kraft chemical recovery process has not been fundamentally changed since the issue of its patent in 1884. The stepwise progression of chemical reactions has been refined for example, black liquor gasification processes are now in use in an experimental phase. The precise details of the chemical processes at work in the chemical recovery process can be found in Smook s Handbook.12 The kraft chemical recovery process consists of the following general steps ... 

Power boilers at pulp and paper mills are sources of particulate emissions, S02, and NOx. Pollutants emitted from chemical recovery boilers include S02 and total reduced sulfur compounds (TRS). 

---