Conversion Process Metal Wastes

A number of refinery processes require the use of a fixed-bed catalyst These processes include catalytic reforming, hydrodesulfurization, hydrotreating, hydro-cracking, and others. These catalysts become inactive in six months to three years and are eventually replaced in the reactors with fresh catalyst during a unit shutdown. Many of these catalysts contain valuable metals which can be recovered economically. Some of these metals, such as platinum and palladium, represent the active catalytic component other metals such as nickel and vanadium are contaminants in the feed which are deposited on the catalyst during use. After valuable metals are recovered (a service usually performed by the outside companies), the residuals are expected to be disposed of as solid waste. 

The major contaminating metals found on catalytic cracking catalyst are vanadium, nickel, copper, chromium, and iron. Small amounts of these metals are present in the crude petroleum and, except for some of the iron, all are in the form of metal-organic compounds. Some of these compounds are volatile and when the vacuum gas oil feed to the catalytic cracking units is prepared, they appear in the gas oil. A fraction of the iron, and probably chromium, found on the catalyst is the result of erosion and corrosion either in the lines or in the equipment. 

Operators try to control conversion processes such that the fines production rate about equals the poisoning rate in order to avoid a net removal of equilibrium catalyst. Source reduction strategies for reducing FCC catalyst losses include  

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High density tungsten alloy machine chips are recovered by oxidation at about 850°C, foUowed by reduction in hydrogen at 700—900°C. Typically, the resultant powders are about 3-p.m grain size and resinter readily. There can be some pickup of refractory materials used in furnace constmction, which must be controUed. This process is important commercially. Eor materials that may be contaminated with other metals or impurities, the preferred recovery process is the wet chemical conversion process used for recovery of tungsten from ores and process wastes. Materials can always be considered for use as additions in alloy steel melting. 

Ceramic Bonding has embarked on a program to develop versatile equipment to aid metal fabricators in their efforts to eliminate hazardous waste generation. Because of the applicability of the CBI process to a variety of hazardous, heavy metal wastes, the CBI equipment is also a natural solution for site cleanup and municipal hazardous waste conversion. With this innovative technology, continued release of fugitive heavy metals into the environment can be halted. 

Waste products from many industrial processes contain at times significant concentrations of metals which are objectionable on environmental grounds and yet constitute an appreciable economic asset. The presence of toxic metals in such wastes constitutes an environmental hazard, particularly because the ever-decreasing pH of the rainwater makes their leachability and contamination of the ground water more likely. Careful and costly waste-disposal procedures are thus mandatory so as to prevent this from occurring. A preferred alternative is the cost-effective conversion of such waste into useful products. This provides an optimal solution to the waste-disposal problem because (a) it eliminates the need for a safe and costly disposal of the hazardous waste (b) it maximizes resource utilization and conservation through recycling, and (c) it derives an economic benefit from the sale of the obtained products. 

Processes involving the use of solid acid catalysts have also been patented. According to Chen and Yan,40 plastic and/or rubber wastes are first subjected to a size reduction step, followed by separation of any metals present and washing to remove any non-plastic material such as paper, labels, etc. Subsequently, the polymer wastes are dissolved or dispersed in a petroleum oil, with a high content of polycyclic aromatic compounds at 300 °C, and catalytically transformed in an FCC reactor at temperatures of about 500 °C. Details are given for the conversion of different wastes used whole tyres, PE bags and PS foam. 

At least two catalytic processes have been used to purify halogenated streams. Both utilize fluidized beds of probably noimoble metal catalyst particles. One has been estimated to oxidize >9000 t/yr of chlorinated wastes from a vinyl chloride monomer plant (45). Several companies have commercialized catalysts which are reported to resist deactivation from a wider range of halogens. These newer catalysts may allow the required operating temperatures to be reduced, and stiU convert over 95% of the halocarbon, such as trichlorethylene, from an exhaust stream. Conversions of C-1 chlorocarbons utilizing an Englehardt HDC catalyst are shown in Figure 8. For this system, as the number of chlorine atoms increases, the temperatures required for destmction decreases. 

The most efficient processes in Table I are for steel and alumintim, mainly because these metals are produced in large amounts, and much technological development has been lavished on them. Magnesium and titanium require chloride intermediates, decreasing their efficiencies of production lead, copper, and nickel require extra processing to remove unwanted impurities. Sulfide ores produce sulfur dioxide (SO2), a pollutant, which must be removed from smokestack gases. For example, in copper production the removal of SO, and its conversion to sulfuric acid adds up to 8(10) JA g of additional process energy consumption. In aluminum production disposal of waste ciyolite must be controlled because of possible fiuoride contamination. 

Two principal conclusions are drawn from the experiments. The acid solubility of metals bonded in the CBI ceramic aggregate is very low, typically a few percent of the California TTLC and STLC limits and the physical properties of the CBI ceramic aggregate are very suitable for use as specialized construction materials. The CBI process is not merely a treatment or encapsulation of wastes it is a physical and chemical conversion which creates a product of genuine commercial value. 

Alkali metal alkoxides such as KOH, NaOH, and CH3ONa are the most effective catalysts in alkali-catalyst transesterification. When using KOH, NaOH, and CH3ONa alkali-catalyst for FAME conversion, the active catalytic species were the methoxide anion (CH 0 ), formed by the reaction between methanol and hydroxide ions of KOH and NaOH. In addition, the methoxide anion was formed by dissolution of sodium methoxide. Sodium methoxide causes the formation of several byproducts, mainly sodium salts, that have to be treated as waste and additionally require high-quality oil (16). However, KOH has an advantage because it can be converted into KOH by reaction with phosphoric acid, which can serve as a fertilizer. Since KOH is more economical than sodium methoxide, it is the preferred choice for large-scale FAME production process. 

The reactions are catalyzed by transition metals (cobalt, iron, and ruthenium) on high-surface-area silica, alumina, or zeolite supports. However, the exact chemical identity of the catalysts is unknown, and their characterization presents challenges as these transformations are carried out under very harsh reaction conditions. Typically, the Fischer-Tropsch process is operated in the temperature range of 150°C-300°C and in the pressure range of one to several tens of atmospheres [66], Thus, the entire process is costly and inefficient and even produces waste [67]. Hence, development of more economical and sustainable strategies for the gas-to-liquid conversion of methane is highly desirable. 

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