Recycling importance

In describing reactor performance, selectivity is usually a more meaningful parameter than reactor yield. Reactor yield is based on the reactant fed to the reactor rather than on that which is consumed. Clearly, part of the reactant fed might be material that has been recycled rather than fresh feed. Because of this, reactor yield takes no account of the ability to separate and recycle unconverted raw materials. Reactor yield is only a meaningful parameter when it is not possible for one reason or another to recycle unconverted raw material to the reactor inlet. By constrast, the yield of the overall process is an extremely important parameter when describing the performance of the overall plant, as will be discussed later. 

Figure 4.9 shows a plot of Eq. (4.12). As the purge fraction a is increased, the flow rate of purge increases, but the concentration of methane in the purge and recycle decreases. This variation (along with reactor conversion) is an important degree of freedom in the optimization of reaction and separation systems, as we shall see later. 

When inerts are present in the recycle, the concentration is another important optimization variable, again influencing operations throughout the process. 

Additional separation and recycling. Once the possibilities for recycling streams directly, feed purification, and eliminating the use of extraneous materials for separation that cannot be recycled efiiciently have been exhausted, attention is turned to the fourth option, the degree of material recovery from the waste streams that are left. One very important point which should not be forgotten is that once the waste stream is rejected, any valuable material turns into a liability as an effluent material. The level of recovery in such situations needs careful consideration. It may be economical to carry out additional separation of the valuable material with a view to recycling that additional recovered material, particularly when the cost of downstream effluent treatment is taken into consideration. 

Economic tradeoffs. Interactions between the reactor and the rest of the process are extremely important. Reactor conversion is the most significant optimization variable because it tends to influence most operations through the process. Also, when inerts are present in the recycle, the concentration of inerts is another important optimization variable, again influencing operations throughout the process. ... 

Of course, the benefits gained by recycling are also important. These are summarized in Table 7 for PET and HOPE. 

Since adipic acid has been produced in commercial quantities for almost 50 years, it is not surprising that many variations and improvements have been made to the basic cyclohexane process. In general, however, the commercially important processes stiU employ two major reaction stages. The first reaction stage is the production of the intermediates cyclohexanone [108-94-1] and cyclohexanol [108-93-0], usuaHy abbreviated as KA, KA oil, ol-one, or anone-anol. The KA (ketone, alcohol), after separation from unreacted cyclohexane (which is recycled) and reaction by-products, is then converted to adipic acid by oxidation with nitric acid. An important alternative to this use of KA is its use as an intermediate in the manufacture of caprolactam, the monomer for production of nylon-6 [25038-54-4]. The latter use of KA predominates by a substantial margin on a worldwide basis, but not in the United States. 

The ammonium chloride process, developed by Asahi Glass, is a variation of the basic Solvay process (9—11). It requires the use of soHd sodium chloride but obtains higher sodium conversions (+90%) than does the Solvay process. This is especially important ia Japan, where salt is imported as a soHd. The major difference from the Solvay process is that here the ammonium chloride produced is crystallized by cooling and through the addition of soHd sodium chloride. The resulting mother Hquor is then recycled to dissolve additional sodium chloride. The ammonium chloride is removed for use as rice paddy fertilizer. Ammonia makeup is generally suppHed by an associated synthesis plant. 

Demilitarization and Disposal of Explosive Material. An important consequence of international agreements to greatiy reduce the stockpiles of conventional and nuclear munitions is the intensification of a program to develop procedures to destroy, recycle, and/or reclaim explosives, propellants, and pyrotechnic material efficientiy and without significant environmental impact. 

The ammonia values can be recycled or sold for fertilizer use. The most important consideration ia this process is the efficient elimination of the phosphoms from the product, because as Htfle as 0.01% P2 5 electrolyte causes a 1—1.5% reduction ia current efficiency for aluminum production (28). 

Liquid-phase oxidation of lower hydrocarbons has for many years been an important route to acetic acid [64-19-7]. In the United States, butane has been the preferred feedstock, whereas ia Europe naphtha has been used. Formic acid is a coproduct of such processes. Between 0.05 and 0.25 tons of formic acid are produced for every ton of acetic acid. The reaction product is a highly complex mixture, and a number of distillation steps are required to isolate the products and to recycle the iatermediates. The purification of the formic acid requires the use of a2eotropiag agents (24). Siace the early 1980s hydrocarbon oxidation routes to acetic acid have decliaed somewhat ia importance owiag to the development of the rhodium-cataly2ed route from CO and methanol (see Acetic acid). 

For example, ia the iadustriaHy important alkylation of benzene with ethylene to ethylbenzene, polyethylbenzenes are also produced. The overall formation of polysubstituted products is minimized by recycling the higher ethylation products for the ethylation of fresh benzene (14). By adding the calculated equiUbrium amount of polyethylbenzene to the benzene feed, a high conversion of ethylene to monoethylbenzene can be achieved (15) (see also... 

Total merchant shipments of DRI and HBI in 1993 reached 5.1 x 10 t. The primary DRI exporting countries were Venezuela, Russia, Malaysia, Trinidad, and India. The price of merchant HBI in 1993 was in the range of 125 to 167/1 on a deUvered basis. Although there are expectations that the value of merchant DRI should some day stand on its own, the historic price has been tied to the price of ferrous scrap. A general mle of thumb has been that the value of merchant DRI is comparable to prime scrap (No. 1 Bundles or No. 1 Bushelings) in industrial countries, and comparable to imported shredded scrap in developing countries (see RECYCLING, FERROUS METALS). 

Secondary Lead. The emphasis in technological development for the lead industry in the 1990s is on secondary or recycled lead. Recovery from scrap is an important source for the lead demands of the United States and the test of the world. In the United States, over 70% of the lead requirements are satisfied by recycled lead products. The ratio of secondary to primary lead increases with increasing lead consumption for batteries. WeU-organized collecting channels are requited for a stable future for lead (see BATTERIES, SECONDARY CELLS Recycling NONFERROUS METALS). 

Electrolytic Preparation of Chlorine and Caustic Soda. The preparation of chlorine [7782-50-5] and caustic soda [1310-73-2] is an important use for mercury metal. Since 1989, chlor—alkali production has been responsible for the largest use for mercury in the United States. In this process, mercury is used as a flowing cathode in an electrolytic cell into which a sodium chloride [7647-14-5] solution (brine) is introduced. This brine is then subjected to an electric current, and the aqueous solution of sodium chloride flows between the anode and the mercury, releasing chlorine gas at the anode. The sodium ions form an amalgam with the mercury cathode. Water is added to the amalgam to remove the sodium [7440-23-5] forming hydrogen [1333-74-0] and sodium hydroxide and relatively pure mercury metal, which is recycled into the cell (see Alkali and chlorine products). 

Many mercury compounds are labile and easily decomposed by light, heat, and reducing agents. In the presence of organic compounds of weak reducing activity, such as amines (qv), aldehydes (qv), and ketones (qv), compounds of lower oxidation state and mercury metal are often formed. Only a few mercury compounds, eg, mercuric bromide/77< 5 7-/7, mercurous chloride, mercuric s A ide[1344-48-5] and mercurous iodide [15385-57-6] are volatile and capable of purification by sublimation. This innate lack of stabiUty in mercury compounds makes the recovery of mercury from various wastes that accumulate with the production of compounds of economic and commercial importance relatively easy (see Recycling). 

Scrap is also an important raw material for the metallurgical industry. The metal produced by a recycling (qv) process is called secondary metal. 

Isopropylnaphthalenes can be prepared readily by the catalytic alkylation of naphthalene with propjiene. 2-lsopropylnaphthalene [2027-17-0] is an important intermediate used in the manufacture of 2-naphthol (see Naphthalenederivatives). The alkylation of naphthalene with propjiene, preferably in an inert solvent at 40—100°C with an aluminum chloride, hydrogen fluoride, or boron trifluoride—phosphoric acid catalyst, gives 90—95% wt % 2-isopropylnaphthalene however, a considerable amount of polyalkylate also is produced. Preferably, the propylation of naphthalene is carried out in the vapor phase in a continuous manner, over a phosphoric acid on kieselguhr catalyst under pressure at ca 220—250°C. The alkylate, which is low in di- and polyisopropylnaphthalenes, then is isomerized by recycling over the same catalyst at 240°C or by using aluminum chloride catalyst at 80°C. After distillation, a product containing >90 wt % 2-isopropylnaphthalene is obtained (47). 

Most off-quahty or scrap polypropylene fibers may be repeUetized and blended in small percentages with virgin polymer to produce first-grade spunbonded fabrics. The economics are of great importance in a process where high yields are required in order to be competitive. Some manufacturing equipment direcdy recycles edge-trim back into the extmder where it is blended back into the polymer melt (see Fibers, olefin). 

The total production of the U.S. paper industry in 1994 was ca 85 million metric tons with a compound aimual growth rate over the previous decade of 2.7%. The domestic production of paper and board plus imports and minus exports maintains a remarkably constant ratio with real gross domestic product in the United States. One sector of the paper industry that has grown at a higher rate than GDP is recycled papers and boards which is projected to grow at 6.8% aimuaHy. Over one-half of paperboard production in the United States is from recycled fiber, and the industry as a whole is expected to achieve 50% recovery rate for paper and board products by the end of the twentieth century (see Recycling, paper). 

It is also important to study the interactions of papermaking additives (4) in the paper machine water system some additives act synergisticaHy, so that the performance of each is enhanced by the presence of the other. However, some additives have a negative impact on the performance of other additives, or on other desirable paper properties. Thus, optimization of the addition points and usage rates of the entire additive system is necessary in order to maximize performance of the chemical additives and the paper sheet properties, and to minimize cost and negative interactions both on the paper machine and in the white-water system. This is especially tme as unanticipated additives enter the wet end of the paper machine from recycled furnishes, including coated broke (5). 

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