results were used to optimise unit performance during feed changes and swings in operation. Response to feedstock changes has been well demonstrated. During the first year of operation since the suc - cessful test run, the catalyst system has remained robust with respect to yields and product quality during fre - quent changes in feedstock type and at 110% throughput. As shown in Figure 12 , throughout the cycle, when running in maximum distillate mode, the catalyst system provides high selectivity to kerosene and diesel. The operational philosophy is to maximise conversion from the first stage, which contains the catalyst with higher mid-distillate selectivity. A flexible product slate is demon - strated in Figure 13 and illustrates the increase in naphtha yield, which is accomplished by increasing conver - sion in the second stage. As shown earlier in Figure 11 , an increase of 6°C in the second-stage operating tem- perature gives approximately 3 wt% higher naphtha yield. Stable HPNA levels are evident. As mentioned, the use of a zeolite- based catalyst in the second stage limits HPNA formation by operating at lower temperatures. Figure 14 shows that, to date, the HPNA content in the recycle oil has been consistently lower than the control limit. Flexibility This article demonstrates the per- formance of Topsoe catalysts in a Mediterranean refinery where the usually preferred goal is to maximise middle distillates, but the flexibility to maximise naphtha is highly desired. The key to success is the use of a zeolite-based catalyst in the second stage, allowing the second stage to incorporating a modified alumina, Grace’s optimised CO promot- ers (both platinum and palladium based technologies) can provide the same CO promotion activity at a lower metals level, with an additional benefit of lower NOx emissions. Based on this new tech - nology, Grace has commercialised Optimized CP P, a low-NOx CO promoter that contains lower palla- dium levels while maintaining CO promotion activity. Despite recent forecasts indicat - ing falling demand for transpor- tation fuels and growing demand for petrochemicals, transportation fuels are still fundamental to sus- tain the economic development 120 essing of renewable raw material in crude oil refineries is the ten - dency for water retention in the final derivatives. Due to its chem - ical structure, biodiesel for exam- ple tends to retain more than eight times more moisture than fossil diesel which can lead to issues like microbiological degra- dation of the fuel in transport and storage systems. The water con- tent in pure biodiesel can reach close to 1800 ppm while the value in diesel with 20% biodiesel can be close to 280 ppm, and diesel with 5% of biodiesel can contain up to 150 ppm. This will lead the refiners to adapt their hardware to allow water removal from the final derivatives by applying draining systems or the applica- tion of salt filters to control the moisture content. 60 0 advanced alumina used for the opti- mised CO promoters results in an even higher proportion of the met- als residing on the outer surface of the particle. The greater the percentage of either palladium or platinum at the surface of the particle, the more accessible the metals are to provide an effective activity response. By Conclusion The energy transition is not a question of choice for down- stream industry; it is demanded by society. Decarbonisation of the energy matrix requires even more flexibility and agil - ity by refiners aiming to keep and improve refining margins in the scenario of reduction in demand for transportation fuels and growing demand for petro- chemicals. However, there are technologies to enable the copro- cessing of renewables and fossil feed streams in crude oil refin - eries, reducing the environmen- tal impact of the downstream industry. A customer performed a trial comparing Grace’s Optimized CP P technology versus a competi - -75% -25% -50% 0% 25% 50% 75% Nowadays, it is difficult to imagine the global energy matrix free of fossil transportation fuels, especially in developing econo- mies. Raising the participation of renewable raw material in crude oil refineries can be an attractive strategy. The Brazilian case rein- forces this — even in nations with high demand for transportation fuels, biofuels can play a funda- mental role. provide the same CO promotion activity at a lower metals level By incorporating a modified alumina, Grace’s optimised CO promoters can
Control limit of nations, especially developing economies. This reinforces even more the need to reduce carbon emissions in the crude oil process- ing chain. Biofuels can develop a fundamental role to the achieve- ment of this goal in the down- stream industry. Optimized CP P
Actual HPNA
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operate at lower temperatures. This one solution solved three challenges: it satisfied the need for naphtha flex - ibility, it relieved limitations due to tight heat integration, and it tempered HPNA build-up. References 1 Hansen J A, Verdier S, Alkilde O F, HPNA Management in Recycle Hydrocrackers, 7th TRC-JCCP/Idemitsu Refining R&D Inter- national Symposium, Feb 7-9 2017, Abu Dhabi, UAE. tor’s lower palladium promoter. Figure 1 shows the relative CO pro- moter usage rate for Optimized CP P versus the competitor promoter. On average, the usage rate for Optimized CP P decreased by 64%. The relative change in afterburn when switching from the compet- itor promoter is shown in Figure 2 . Even though there was a lower usage rate of Optimized CP P, the afterburn was reduced by 11%. 2 Topsoe H, Clausen B S, Massoth F E, Hydro- treating Catalysis, 1996, (Springer-Verlag, Berlin), Ch 4. 3 Scherzer J, Gruia A J, Hydrocracking Science and Technology , 1996, (Marcell-Dekker, New York), Sec 6.2.4. transportation fuels, especially in developing economies Security of supply This is a time of exceptional mar - ket volatility around the materials used in CO promoters. It is also a time of uncertainty around trans - portation costs and shipping times. Grace manufactures CO promoters at its facilities in the US, Canada, and Europe, and we do not rely on tolling manufacturers. In addition, we have a skilled and experienced global team of procurement and logistic specialists. This allows us to provide a secure and timely supply of such critical FCC technologies to our customers around the world. This is a time for partnering with established, secure, and reliable FCC additive suppliers committed to refiners for the timely supply of the highest quality FCC catalyst and additive technologies. 4 Scherzer J, Gruia A J, Hydrocracking Science and Technology , 1996, (Marcel Dekker, New York) Sec 11.4. 5 Sullivan R F, Boduszynski M M, Fetzer J C, Energy and Fuels, 1989, 3:603. 6 Fetzer J C, The Role of the Scholl Condensation in the Chemistry of Catalytic Hydrocrackers, 1994, Polycyclic Aromatics, 4(1-2):19-24. Petrochemical Integration , IHS Markit, 2020. 5 Robinson P R, HSU C S, Handbook of Petroleum Technology, 1st ed. Springer, 2017. 6 Zhu F, Hoehn R, Thakkar V, Yuh E, Hydroprocessing for Clean Energy – Design, Operation, and Optimization , 1st ed. Wiley Press, 2017. 7 Robinson P R, Deactivation of Hydro- processing Catalysts: Thermochemistry of Coke Formation , 232nd American Chemical Society National Meeting, San Francisco, CA, 2006. 8 NIST PAH Database, https://pah.nist. gov/?q=pah315. 9 Hunter M, Patel R, Orange CA, and Verdier S, New process for controlling heavy poly- nuclear aromatics (HPNA) in a hydrocracker . AFPM Annual Meeting AM-12-40, 2012. Marcio Wagner da Silva is a process engineer and Transfer and Storage manager on the crude oil refining industry and based in São José dos Campos, Brazil. His experience includes research, design and construction for the oil and gas industry, including developing and coordinating projects for operational improvements and debottlenecking Devansh Dhar is Senior Technical Service Engineer at Topsoe. Pronit Lahiri is Principal Technical Service Engineer at Topsoe. Paul Ronald Robinson is Lead Technical Service Engineer at Topsoe. bottom of the barrel units. He holds a bachelor’s degree in chemical engineering from the University of Maringa, Brazil, a PhD in chemical engineering from the University of Campinas, and MBA in project management from Federal University of Rio de Janeiro. *As of March 28, 2022. Optimized CP ® P is a trademark of W. R. Grace. W. R. Grace & Co. Contact: Colin.Baillie@grace.com Further reading 1 Brazilian Petroleum Agency (ANP), Brazilian Statistical Yearbook , 2020. 2 Energy Research Company (EPE), Analysis of the Biofuels Conjuncture – Technical Report , 2020. 3 Hilbert T, Kalyanaraman M, Novak B, Gatt J, Gooding B, Mccarthy S, Maximising Premium Distillate by Catalytic Dewaxing , 2011. 4 Reinventing the Refinery through the Energy Transition and Refining- Nowadays, it is difficult to imagine the global energy matrix free of fossil
Figure 14 HPNA in the recycle oil since start-up
Figure 2 Relative change in afterburn for CP P and Optimized CP P vs a competitor promoter
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