Many plants employ fixed- or moving-bed catalytic reactions for hydrogenation of intermediates and for controlling or abating emissions. These operations rely on precious metal catalysts (PMCs) containing platinum group metals (PGMs), including platinum, palladium, ruthenium and rhodium.
PMCs, whether in the form of monolithic structures, beads, pellets, powders or extrudates, have finite useful lives. Catalyst lifetimes depend upon how and where the materials are used, but typically extend to five to six years. Afterward, the spent catalysts should be processed to recover their remaining precious metals.
The process of reclaiming the remaining precious metals is referred to as “recovery and refining.” It includes individual procedures, such as materials documentation, pre-burning, sampling and assaying. In addition, environmental considerations and turnaround time can markedly impact economics. Each of these is independent; together, however, they significantly affect how much remaining PGMs are recovered, their returned value, the speed at which they are reclaimed and environmental compliance.
While each of these functions is important, sampling procedures for spent catalyst materials are perhaps the most critical elements for achieving maximum return. As a user of the catalysts, it is in your best interest to understand how sampling helps determine the precious metals content of spent catalysts and, ultimately, the value of these metals that is returned to their owners.
The problem in sampling is that even new catalysts on substrates or carriers, such as soluble and insoluble alumina, silica-alumina, zeolite or carbon supports, are not homogenous masses. During use, the materials accumulate many contaminants of various densities, including sulfur, carbon, solvents and water. Therefore, spent catalysts are even less homogenous.
Three different techniques — dry sampling, melt sampling and solution sampling — are employed. Each uses different methods and equipment; each also offers specific advantages. Determining the most appropriate sampling method depends upon the type of material being processed as well as its estimated precious-metals content.
However, because of their composition and chemistry, PMCs usually undergo dry sampling. This method is used whenever materials cannot be put in solution or melted either because of their structure or the cost associated with melting versus the possible return. Since it is difficult to achieve homogeneity, dry sampling is more complex and potentially less precise than solution or melt sampling. This method requires more judgmental skills than the others do. An ideal dry system would be capable of drawing representative samples from free-flowing catalyst at a rate of 2,000 lb/hr to 3,000 lb/hr.
To determine the quantity and quality of remaining PGMs as accurately as possible, the spent catalysts first must be “reduced.” This involves taking large quantities, up to many tons, of the materials and reducing it into smaller quantities of as little as a few grams, while also eliminating contaminants. The goal is to achieve an accurate determination of the actual value of recoverable precious metals within the lot by getting a precise representative sample of the overall lot after it has been made homogenous. In essence, when the material cannot be broken down any further, the result of sampling (or reducing) the homogenous mass represents a highly accurate ratio of the precious metal content in the overall matrix.
Dry sampling procedures are tedious and complex. However, before the actual sampling, the entire spent catalyst lot first must be “decontaminated” — contaminants that have accumulated over the years must be removed.
Contaminants are eliminated in a rotary kiln (or a multiple-hearth or fluidized-bed furnace), which removes up to 25% of the sulfur content and up to 40% of the carbon. This first step, or pre-burning, is critical to the sampling process and is best handled at the refiner’s facility. This is because doing so eliminates the possibility that the materials could mix with an unrelated lot and also affords the materials’ owners substantial cost savings by obviating trans-shipment charges to independent “regenerators” for what typically are many tons of spent catalyst.
After processing in the rotary kiln, materials containing large agglomerates are crushed and subsequently blended in with the lot for further reduction.
This provides homogenous, consistent and reproducible intermediate samples. One of these samples is divided into about 1-lb. portions and retained in hermetically sealed aluminum cans for loss on ignition (LOI) determination. This involves heating the catalyst in the presence of air to burn off any remaining volatile components and oxidizable materials, such as carbon or sulfur. The procedure permits the precise determination of a “settlement weight” through laboratory analysis.
The materials’ owner and the refiner usually assay these small samples (on an ignited basis) independently. If these assays agree to within predetermined limits, they simply are averaged to arrive at a final settlement. If they do not agree, a sealed “umpire” sample is sent to an independent laboratory (i.e., the umpire). The three resulting assays are used, again by an agreed-upon procedure, to determine the settlement. Many times this procedure involves averaging the two closest assays or using the middle assay to determine the final settlement. “Reserve” samples (usually sealed by both the materials’ owner and the refiner) are held back to cover any possible irregularities during the sampling procedures.
When sampling procedures are completed, the spent catalyst lot is blended with a mix of flux and a carrier metal, such as copper or iron. The proportions in this mix are determined by the calculated concentration of recoverable precious metals in the lot and the desired chemistry of the slag, which takes into account its electrical conductivity, corrosivity, morphology, melting temperature and other parameters.
Throughout the sampling procedure, the refiner must adhere to applicable environmental codes and standards for effluent disposal and atmospheric emissions. Therefore, an ideal sampling system typically should be enclosed for dust control and evacuated under a low volume flow into a dedicated baghouse. The dust collected during this sampling process is also recovered and sampled separately. Its value — which can be substantial — is returned to the catalyst owners.
Other process issues
Accurate and repeatable assaying methods also play a major role in properly determining the values of remaining precious metals. Once the final samples are obtained, sophisticated instrumentation is used to measure their precise precious metals’ content. Among the equipment and methods employed in a well-equipped analytical laboratory is X-ray fluorescence to determine the approximate grade of recoverable precious metals. X-ray fluorescence helps fix the amount of copper to be added to the mix to obtain the desired bullion grade, and to provide information on the matrix or non-precious-metal constitution. Other assay procedures employ atomic absorption, inductively coupled plasma-emission spectroscopy and classic volumetric, gravimetric and fire assay techniques.
After sampling and analysis, the value of the precious metals in the entire spent catalyst lot, or “reject” as it is called after the pre-burning step, is determined and agreed upon between the refiner and its customer. Finally, the spent catalyst lot is loaded into an electric arc furnace (EAF) for refining. The EAF helps maximize precious metals recovery, essentially producing two end products: molten precious metals and slag, which contains trace amounts of precious metals and is also subsequently refined. The molten precious metals are made into ingots, which weigh about 500 lb each, and go to storage vaults.
The reclamation turnaround time also is a key factor in achieving the maximum return. Logically, a shorter turnaround minimizes interest charges a user accrues for leasing replacement precious metals (a common practice) or the necessity of purchasing PGMs on the volatile spot market.
You also must consider your legal exposure. Choosing a refiner that does not provide maximum recovery and fastest possible turnaround is costly, but choosing a refiner that follows marginal pollution-abatement procedures could become even more costly.
When selecting a refiner, find out how your materials and those of other customers will be processed. Determine how any solid, liquid or gaseous byproduct is handled and whether the plant uses state-of-the-art equipment, including afterburners, baghouses, wet scrubbers and liquid-effluent treatment equipment.
Ideally, no hazardous waste materials should be shipped from a precious-metals-processing facility. At a minimum, though, make sure the plant ships them properly and to approved treatment facilities.
Requesting detailed documentation on environmental compliance may also help you determine that the refiner does not violate any applicable law or regulation. In the United States, the Superfund Act (CERCLA) addresses the direct responsibility of customer and refiner. This law mandates that both the catalyst owner and refiner share in the “cradle-to-grave” responsibility, as well as future liability, for the proper treatment or disposal of any materials. Essentially, a refiner’s violation of environmental laws or regulations could result in heavy fines and legal costs for you.
Also, evaluate the refiner’s approval status with applicable agencies at local, state and federal levels. Most precious metals refiners are willing to provide copies of all required documentation. This could include permits under the Clean Air and Water Acts and proof that the company qualifies as a bona fide precious metals refiner as specified in the preamble to the Boiler and Industrial Furnace Rule and its amendments.
Obtaining maximum value from spent catalysts depends foremost on the thoroughness and accuracy of the materials’ sampling process, with assaying of the sample lots close behind. You must look carefully into these areas and work closely with the refiner whenever possible.
It’s also crucial that all environmental compliance regulations are adhered to fully. All else being equal, choose a refiner based on its pollution-abatement performance.
These steps should provide you with the knowledge and confidence to select or work with the proper refiner. Remember, too, that your relationship with the refiner should be viewed as a partnership and based upon mutual trust and fair treatment.
Richard J. DeSantis is vice president of corporate operations at Sabin Metal Corp., East Hampton, N.Y. He has extensive experience in the precious metals industry, and currently is president of the International Precious Metals Institute. E-mail him at firstname.lastname@example.org.