Spent Catalysts

The palladium may be recovered by heating the spent catalyst to redness in order to remove organic impurities this treatment may reduce some of the barium sulphate to barium sulphide, which acts as a catalytic poison. The palladium is then dissolved out with aqua regia and the solution evaporated the residue is dissolved in hot water and hydrochloric acid to form palladium chloride. 

Boron trifluoride catalyst may be recovered by distillation, chemical reactions, or a combination of these methods. Ammonia or amines are frequently added to the spent catalyst to form stable coordination compounds that can be separated from the reaction products. Subsequent treatment with sulfuric acid releases boron trifluoride. An organic compound may be added that forms an adduct more stable than that formed by the desired product and boron trifluoride. In another procedure, a fluoride is added to the reaction products to precipitate the boron trifluoride which is then released by heating. Selective solvents may also be employed in recovery procedures (see Catalysts,regeneration). 

The catalyst is employed in bead, pellet, or microspherical form and can be used as a fixed bed, moving bed, or fluid bed. The fixed-bed process was the first process used commercially and employs a static bed of catalyst in several reactors, which allows a continuous flow of feedstock to be maintained. The cycle of operations consists of (/) the flow of feedstock through the catalyst bed (2) the discontinuance of feedstock flow and removal of coke from the catalyst by burning and (J) the insertion of the reactor back on-stream. The moving-bed process uses a reaction vessel, in which cracking takes place, and a kiln, in which the spent catalyst is regenerated and catalyst movement between the vessels is provided by various means. 

Improved feedstock pretreatment is important to minimize catalyst consumption and reduce subsequent spent-catalyst handling requirements. Selective hydrogenation of dienes can be used to reduce acid consumption, both in HF and H2SO4 alkylation (29). More effective adsorptive treating systems have been appHed to remove oxygen-containing contaminants that are frequently introduced in upstream processing steps. 

Typical values for mf n are 0.5 to 2.5. Gommercially used bases include sodium hydroxide, potassium hydroxide, calcium hydroxide (lime), magnesium hydroxide, sodium carbonate, sodium alurninate, calcium carbonate, or various mixtures. For certain appHcations, PAG can be made from waste grades of aluminum chloride [7446-70-0] such as spent catalyst solutions from Friedel-Grafts synthesis (see Friedel-Grafts reaction). 

Acid Leaching. DHect acid leaching for vanadium recovery is used mainly for vanadium—uranium ores and less extensively for processing spent catalyst, fly ash, and boiler residues. Although 20 in spent catalysts dissolves readily in acid solutions, the dissolution of vanadium from ores and... 

Most U.S. production (20 x 10 lbs ia 1996) of primary vanadium compounds has been as by-products or coproducts of uranium and of ferrophosphoms derived from smelting Idaho phosphates. Most of this processiag was from leaching acids, residues, and spent catalysts. The only domestic commercially mined ore, for its sole production of vanadium, is Arkansas brookite. It has contributed significantly to domestic supply siace ca 1969, however, it has not been mined siace 1992 (25). 

SoHd by-products include sludge from wastewater treatment, spent catalyst, and coke from the EDC pyrolysis process. These need to be disposed of in an environmentally sound manner, eg, by sludge digestion, incineration, landfill, etc. 

The most dominant catalytic process in the United States is the fluid catalytic cracking process. In this process, partially vaporized medium-cut petroleum fractions called gas oils are brought in contact with a hot, moving, freshly regenerated catalyst stream for a short period of time at process conditions noted above. Spent catalyst moves continuously into a regenerator where deposited coke on the catalyst is burnt off. The hot, freshly regenerated catalyst moves back to the reactor to contact the hot gas oil (see Catalysts, regeneration). 

Catalyst lifetime for contemporary ethylene oxide catalysts is 1—2 years, depending on the severity of service, ie, ethylene oxide production rate and absence of feed poisons, primarily sulfur compounds. A large percentage (>95%) of the silver in spent catalysts can be recovered and recycled the other components are usually discarded because of thek low values. 

The oxychlorination reaction is very exothermic and the catalyst is very active, which makes it necessary to mix the catalyst with an inert diluent to avoid overheating in a fixed-bed reactor. A low surface area, spherically- or ring-shaped alumina or chemical porcelain body can be used as a diluent with the ring-shaped catalyst. The density of the inert material should be similar to the catalyst to avoid segregation during loading, and the size should be slightly different to allow separation of the inert material from the spent catalyst. 

Olefin polymerization catalysts are unique in their utilization of supported catalysts in that the catalysts that have been developed are so highly active that the spent catalysts are intentionally left in the polymer where, at the extremely low parts per million concentrations used, they pose no threat to the properties of the polymer or to the well-being of the end user. 

Erom 1955—1975, the Ziegler-Natta catalyst (91), which is titanium trichloride used in combination with diethylaluminum chloride, was the catalyst system for propylene polymerization. However, its low activity, which is less than 1000 g polymer/g catalyst in most cases, and low selectivity (ca 90% to isotactic polymer) required polypropylene manufacturers to purify the reactor product by washing out spent catalyst residues and removing unwanted atactic polymer by solvent extraction. These operations added significantly to the cost of pre-1980 polypropylene. 

Coke on the catalyst is often referred to as delta coke (AC), the coke content of the spent catalyst minus the coke content of the regenerated catalyst. Delta coke directly influences the regenerator temperature and controls the catalyst circulation rate in the FCCU, thereby controlling the ratio of catalyst hydrocarbon feed (cat-to-od ratio, or C/O). The coke yield as a fraction of feed Cpis related to delta coke through the C/O ratio as ... 

Dichloroethane is produced commercially from hydrogen chloride and vinyl chloride at 20—55°C ia the presence of an aluminum, ferric, or 2iac chloride catalyst (8,9). Selectivity is nearly stoichiometric to 1,1-dichloroethane. Small amounts of 1,1,3-tfichlorobutane may be produced. Unreacted vinyl chloride and HCl exit the top of the reactor, and can be recycled or sent to vent recovery systems. The reactor product contains the Lewis acid catalyst and must be separated before distillation. Spent catalyst may be removed from the reaction mixture by contacting with a hydrocarbon or paraffin oil, which precipitates the metal chloride catalyst iato the oil (10). Other iaert Hquids such as sdoxanes and perfluorohydrocarbons have also been used (11). 

Spent catalyst maybe considered hazardous waste... 

Catalysts reduced with formaldehyde carry no adsorbed hydrogen and are less pyrophoric. Barium carbonate as a support may sometimes be advantageous in that the neutrality of the h3 drogenation mixture may be maintained. Barium sulfate or barium carbonate may be a better support than carbon, which may, in some instances, so strongly adsorb the derived product that recovery is difficult or incomplete. Palladium may be more completely and easily recovered from a spent catalyst where carbon rather than barium sulfate is the support. In general, the submitter prefers a catalyst prepared according to procedure C. 

The flow of the spent catalyst to the regenerator is typically controlled by the use of a valve that slides back and forth. This slide valve (Figure 4-50) is used to control the catalyst level in the stripper. The catalyst level in tlie stripper provides the pressure head that allows tlie catalyst to flow into tlie regenerator. The exposed surface of tlie slide valve is usually lined with a suitable refractory to withstand erosion. 

The regenerator has two main functions It restores catalyst activity and supplies heat to crack the feed. The spent catalyst entering the regenerator contains between 0.8-2.5 wt% coke, depending on the quality of the feedstocks. Components of coke are carbon, hydrogen, and trace amounts of sulfur and nitrogen, which burn according to the reactions shown in Table 4-3. 

This procedure is particularly time-saving when scrap platinum or spent catalyst is used for the preparation of platinum oxide, for after conversion to chloroplatinic acid a purification is conveniently effected by precipitating the ammonium salt, and the direct fusion of this with sodium nitrate eliminates the tedious process of reconversion to chloroplatinic acid. Furthermore ammonium chloroplatinate is not hygroscopic and can he accurately weighed. The amount of catalyst obtained is almost exactly half the weight of the ammonium salt employed. 

They may require pH adjustment and settling. These effluents should preferably be recycled or reused. Spent catalysts are usually sent for regeneration or disposed of in a secure landfill. Air emissions should be monitored aimually, except for nitrate acid plants, where nitrogen oxides should be monitored continuously. 

The spent catalyst is withdrawn from the bottom of the reactor and stripped with steam to vaporize the hydrocarbons remaining on the surface. Stripping also removes most of the hydrocarbon vapors which are entrained between the particles of catalyst. Without stripping, hydrocarbon products would be carried to the regenerator and needlessly burned consuming much of the regeneration air, and decreasing yield of useful products. 

We need to keep in mind the disposal costs in all of the mechanisms for solidification. With the first method, keep in mind that free liquids are typically not allowed in most disposal scenarios. And adding too much adsorbent can substantially add to disposal costs. Make this point clear to your field people. As far as using polymerization catalysts and chemical reagents, keep in mind disposal costs. Ensure that you are cognizant of disposal costs of spent catalyst prior to using this scenario. As far as freezing is concerned, consider the cost to keep the contaminants frozen and what the downsides are. The downsides besides cost include measures in case of power failure and use of freezing equipment after wastes have been disposed. 

Zinc oxide is usually contained in long, thin beds to lessen the chances of channeling. Pressure drop through the beds is low. Bed life is a function of gas H2S content and can vary from 6 months to in excess of 10 years. The spent catalyst is discharged by gravity flow and contains up to 20 weight percent of sulfur. 

The process has seen decreasing use due to increasing disposal problems with the spent catalyst, which is classified as a heavy metal salt. 

Reactors should not dissolve in the reaction medium. Judging by spectro-graphic analysis of spent catalysts, some attack of the reactor is more common than is generally supposed. It may be a cause of catalyst failure. Reactors are commonly made of type 316 stainless steel, but other alloys may provide better resistance to spedhc corrosive agents. 

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