How

should the spent catalyst be treated and disposed of?

A catalyst is a substance that increases the rate of a chemical reaction without itself undergoing any permanent chemical
change. This is made possible by altering the reaction pathway, pre-exponential factor or both. The catalyst used in this reactor
is a Solid Phosphoric Acid (SPA) catalyst and has been used since the 1930s. SPA is a versatile and robust solid acid catalyst that
is used in the petroleum industry (1). More specifically in the oligomerization of light olefins, especially synthetic fuels refining
and ethylene and propylene hydration. SPA is manufactured by adding concentrated phosphoric acid to diatomaceous earth
(kieselguhr), extrusion, calcination at high temperature and screening (2). The spent SPA is not regenerated and the lifetime of
the catalyst is determined by pressure drop constraints (3). The spent catalyst is a hazardous waste that is corrosive and toxic,
that is why it has to be treated and disposed of by landfill. However, a more eco-friendly method can be used to deal with the
catalyst and that is to convert it to a phosphorus-rich fertilizer.

SPA can be disposed of as landfill in approved dump-sites as long as the landfill has met non-hazardous criteria. The landfills
should be ideally built with double liners as well as with leachate collection and ground water monitoring faculties as shown in
Figure 1.

Figure 1 – Diagram of Municipal Solid Waste Landfill
http://www.re3.org/docs/LandfillDiagram.jpg

As time goes on it is becoming more expensive to dispose of these catalysts in landfills. In addition to this some catalysts have to
be treated before they can be disposed of. There are alternatives to disposal as landfill such as regeneration and reclamation (4).
It is also possible to store the spent catalysts on specially designed sites and waiting till there are more efficient ways to dispose
of the catalyst but this is only a temporary solution. Before catalyst are placed in landfills they must be treated properly for
stability. There are two processes that have been patented and developed to reduce leachability: Maectite process and
Sealosafe (5). The Maectite process coverts reactive metals in solid wastes into non-leachable minerals in the apatite and barite
group. These minerals are able to resist acidity and degradation by chemical and geological chemical conditions which are
present in landfills. The Sealosafe method involves producing an impermeable solid by adding a mixture of calcium, cement
powder and aluminosilicate powder to the waste product in water. These processes can be applicable to the SPA catalyst. The
SPA catalyst can also be treated and disposed by encapsulation. In encapsulation, the waste is treated with bitumen, vitreous
silicates, concrete or polymers and then sealed in a thermoplastic agent (6). These methods can be successful but they require a
lot of energy and are quite expensive so they are not the ideal solutions for disposal.

SPA can also be turned into an environmentally fertilizer, however there is a presence of carbonaceous deposits on the catalyst
which present a potential environmental hazard. These deposits are mostly polyaromatic with tinier amounts of oxygenates and
aliphatics. The chemical makeup, physical structure and presence of coke does not stop it from being used to make fertilizer.
The spent catalyst has to be milled, neutralized with lime and ammonium hydroxide, and then calcined to produce a phosphate-
rich fertilizer. Toxicity characteristic leaching tests can be conducted to show low levels of harmful compounds (metals and
organics) which means that they won’t be absorbed into plant life or groundwater. Studies have shown that in alkaline soil the
spent catalyst fertilizer is as effective as the superphosphate fertilizer (7). When comparing how the spent catalyst should be
dealt with, turning it into a fertilizer is more environmentally friendly and economically efficient than the landfill option.


Literature Cited
1) Egloff, G.; Weinert, P. C. Polymerisation with solid phosphoric acid catalyst. Proc. World Pet. Congr. 1951, IV, 201.
2) (2) De Klerk, A.; Engelbrecht, D. J.; Boikanyo, H. Oligomerization of Fischer-Tropsch olefins: Effect of feed and operating conditions on hydrogenated motor-gasoline quality. Ind. Eng. Chem. Res. 2004,
43, 7449. 

3) Coetzee, J. H.; Mashapa, T. N.; Prinsloo, N. M.; Rademan, J. D. An improved solid phosphoric acid catalyst for alkene oligo- merization in a Fischer-Tropsch refinery. Appl. Catal., A, 2006, 308, 204.
4) S. Shelly, Environ. Eng. World (March–April) (1995) 40. 

5) J.T. Schofield, Sealosafe process, in: Toxic and Hazardous Waste Disposal. Process for Stabilization/ 
Solidification, vol. 1, Ann Arbor Science, Ann Arbor, MI, USA, 1979, pp. 297–319. 

6) D.L. Trimm, Stud. Surf. Sci. Catal. 53 (1990) 41–60.
7) Merwe, W.V.D., 2010. Conversion of spent solid phosphoric acid catalyst to environmentally friendly fertilizer. Environmental science & technology, 44(5), pp.1806-1812.