Ethylene from Bottom Barrel Streams – Synergy between Hydrocracking and Steam Cracking Units

Introduction and Context

???????????One of the biggest challenges for the oil refining industry is raising the profitability or the so-called refining margin face to a scenario with environmental regulations increasingly restrictive, which requires high costly processes and the volatility of the crude barrel price. Restrictive regulations like IMO 2020 raised, even more, the pressure over refiners with low bottom barrel conversion capacity once requires higher capacity to add value to residual streams, especially related to sulfur content that was reduced from 3,5 % (in mass) to 0,5 %. Refiners with easy access to low sulfur crude oils present relative competitive advantage in this scenario, these players can rely on relatively low cost residue upgrading technologies to produce the new marine fuel oil (Bunker) as carbon rejection technologies (Solvent Deasphalting, Delayed Coking, etc.), but they are the minority in the market. The most part of the players need to look for sources of low sulfur crudes, which present higher cost putting under pressure his refining margins or look for deep bottom barrel conversion technologies to ensure more value addition to processed crude oils and avoid to loss competitiveness in the downstream market. For these refiners, deepest residue upgrading like hydrocracking technologies can offer great operational flexibility, despite the high capital spending.

Furthermore, despite be more frequently related to bottom barrel value addition and residue upgrading issues, the hydrocracking technologies can offer better conditions to closer integration with petrochemical assets though the improvement of intermediates streams, an interesting case is the synergy of hydrocracking and naphtha steam cracking units aiming to maximize the petrochemicals production in the refining hardware. Recent forecasts indicate a trend of reduction in transportation fuels demand accompanied by the growth of petrochemicals demand as presented in Figure 1.

Figure 1 – Change in the Profile of Global Crude Oil Demand (Wood Mackenzie, 2019)

???????????The improvement in fuel efficiency, growing market of electric vehicles tends to decline the participation of transportation fuels in the global crude oil demand. New technologies like additive manufacturing (3D printing) have the potential to produce great impact to the transportation demands, leading to even more impact over the transportation fuels demand. Furthermore, the higher availability of lighter crude oils favors the oversupply of lighter derivatives that facilitate the production of petrochemicals against transportation fuels as well as the higher added value of petrochemicals in comparison with fuels.

Facing these challenges, search for alternatives that ensure survival and sustainability of the refining industry became constant by refiners and technology developers. Due to his similarities, better integration between refining and petrochemical production processes appears as an attractive alternative. According to Figure 2, the demand by petrochemicals tends to rise in the next years and can be an attract way to refiners keep his protagonism in the market.

Figure 2 – Growing Trend in the Demand by Petrochemical Intermediates (Wood Mackenzie, 2020)

???????????According to data presented in Figure 2, is expected a significant growth in the market of petrochemicals intermediates, and a refining hardware capable to maximize the yield of these derivatives can offer significant competitive advantage through closer integration with petrochemical assets and higher value addition to processed crude oil.

???????????This scenario requires even more conversion capacity in the refining hardware as well as profitable routes to convert these hydrocarbons into petrochemicals in compliance with market demand, in this sense, hydrocracking technologies and their synergies with petrochemical processes like steam cracking can be an attractive route to some refiners.???????

Synergies between Refining and Petrochemical Assets – Petrochemical Integration

The focus of the closer integration between refining and petrochemical industries is to promote and seize the synergies existing opportunities between both downstream sectors to generate value to the whole crude oil production chain. Table 1 presents the main characteristics of the refining and petrochemical industry and the synergies potential.

As aforementioned, the petrochemical industry has been growing at considerably higher rates when compared with the transportation fuels market in the last years, additionally, represent a noblest destiny and less environmental aggressive to crude oil derivatives. The technological bases of the refining and petrochemical industries are similar which lead to possibilities of synergies capable to reduce operational costs and add value to derivatives produced in the refineries.?

Figure 3 presents a block diagram that shows some integration possibilities between refining processes and the petrochemical industry.?

Figure 3 – Synergies between Refining and Petrochemical Processes

???????????Process streams considered with low added value to refiners like fuel gas (C2) are attractive raw materials to the petrochemical industry, as well as streams considered residual to petrochemical industries (butanes, pyrolisis gasoline, and heavy aromatics) can be applied to refiners to produce high quality transportation fuels, this can help the refining industry meet the environmental and quality regulations to derivatives.

???????????The integration potential and the synergy among the processes rely on the refining scheme adopted by the refinery and the consumer market, process units as Fluid Catalytic Cracking (FCC) and Catalytic Reforming can be optimized to produce petrochemical intermediates to the detriment of streams that will be incorporated to fuels pool. In the case of FCC, installation of units dedicated to produce petrochemical intermediates, called petrochemical FCC, aims to reduce to the minimum the generation of streams to produce transportation fuels, however, the capital investment is high once the severity of the process requires the use of material with noblest metallurgical characteristics. ?

???????????The IHS Markit Company proposed a classification of the petrochemical integration grades, as presented in Figure 4.?

Figure 4 – Petrochemical Integration Levels (IHS Markit, 2018)

???????????According to the classification proposed, the crude to chemicals refineries is considered the maximum level of petrochemical integration where the processed crude oil is totally converted into petrochemicals intermediates like ethylene, propylene, and BTX. In these refining schemes, the combination of hydrocracking and steam cracking units are fundamental to allow the conversion of bottom barrel streams to petrochemicals in order to maximize the added value to the processed crude.

Hydrocracking Technologies

Despite the high investment for hydrocracking units construction, this process is what gives more flexibility to refineries to processing heavy oils, so with lower cost, on the other hand, these oils produce a high quantity of derivates with lower value added and with restricted markets like fuel oils and asphalt. The Table 2 presents the main differences between hydrotreating and hydrocracking technologies.

The hydrocracking process is normally conducted under severe reaction conditions with temperatures that vary to 300 to 480 oC and pressures between 35 to 260 bar.?Due to process severity, hydrocracking units can process a large variety of feed streams, which can vary from gas oils to residues that can be converted into light and medium derivates, with high value added.

Among the feed streams normally processed in hydrocracking units are the vacuum gas oils, Light Cycle Oil (LCO), decanted oil, coke gas oils, etc. Some of these streams would be hard to process in Fluid Catalytic Cracking Units (FCCU) because of the high contaminants content and the higher carbon residue, wich quickly deactivates the catalyst, in the hydrocracking process the presence of hydrogen minimizes these effects.

According to the catalyst applied in the process and the reaction conditions, the hydrocracking can maximize the feed stream conversion in middle derivates (Diesel and Kerosene), high-quality lubricant production (lower severity process).

Catalysts applied in hydrocracking processes can be amorphous (alumina and silica-alumina) and crystalline (zeolites) and have bifunctional characteristics once the cracking reactions (in the acid sites) and hydrogenation (in the metals sites) occurs simultaneously. The active metals used to this process are normally Ni, Co, Mo and W in combination with noble metals like Pt and Pd.

It’s necessary a synergic effect between the catalyst and the hydrogen because the cracking reactions are exothermic and the hydrogenation reactions are endothermic, so the reaction is conducted under high partial hydrogen pressures and the temperature is controlled in the minimum necessary to convert the feed stream. Despite these characteristics, the hydrocracking global process is exothermic, and the reaction temperature control is normally made through cold hydrogen injection between the catalytic beds.

Figure 5 shows a typical arrangement for hydrocracking process unit with two reactions stages, dedicated to producing medium distilled products (diesel and kerosene).?

Figure 5 – Basic Process Flow Diagram for Two stages Hydrocracking Units

According to the feed stream quality (contaminant content), is necessary hydrotreating reactors installation upstream of the hydrocracking reactors, these reactors act like guard bed to protect the hydrocracking catalyst.

The principal contaminant of hydrocracking catalyst is nitrogen, which can be present in two forms: Ammonia and organic nitrogen.

Ammonia (NH3), produced during the hydrotreating step, have temporary effect reducing the activity of the acid sites, mainly damaging the cracking reactions. In some cases, the increase of ammonia concentration in the catalytic bed is used like an operational variable to control the hydrocracking catalyst activity. The organic nitrogen has permanent effect blocking the catalytic sites and leading to coke deposits on the catalyst.

As in the hydrotreating cases (HDS, HDN, etc.), the most important operational variables are temperature, hydrogen partial pressure, space velocity and hydrogen/feed ratio.

Depending on feed stream characteristics (mainly contaminants content) and the process objective (maximize middle distillates or lubricant production) the hydrocracking units can assume different configurations.

For feed streams with low nitrogen content where the objective is to produce lubricants (partial conversion) is possible adopt a single stage configuration and without the intermediate gas separation, produced during the hydrotreating step. ?The main disadvantage of this configuration is the reduction of the hydrocracking catalyst activity caused by the high concentration of ammonia in the reactor, but this configuration requires lower capital investment.

The application of hydrocracking route to produce lubricating oils offers great competitive advantage once the alternative routes, based on solvent extraction units are capable to produce only Group I and II lubricating oils that present falling demand.

Due to the accelerated technological development, especially in the automotive market, the Group I lubricating oil tend to lose market in the next years this fact tends to lead the refiners to look for capital investment aiming to sustain their competitiveness in the lubricating market. Another side effect for lubricating producers based on solvent routes due to the competitiveness loss is raising the imports to supply the internal market, leading to an external dependence of critical production input as well as negative effects on the balance of payments.?

Normally for feed streams with low nitrogen content where the objective is to produce middle distillates (diesel and kerosene), the configuration with two reaction stages without intermediate gas separation is the most common.

Like aforementioned, the disadvantage, in this case, is the high concentration of ammonia and H2S in the hydrocracking reactors, which reduces the catalyst activity.

The higher costly units are the plants with double stages and intermediate gás separation. These units are employed when the feed stream has high contaminant content (mainly nitrogen) and the refinery looks for the total conversion (to produce middle distillates), this configuration is presented in Figure 6.?

Figure 6 – Typical Arrangement for Two Stage Hydrocracking Units with Intermediate Gas Separation

In this case, the catalytic deactivation process is minimized by the reduction in the NH3 and H2S concentration in the hydrocracking reactor. It’s important to consider the feedstock quality to define the better residue upgrading technology to the refining hardware, once the hydroprocessing of residual streams presents additional challenges when compared with the treating of lighter streams, mainly due to the higher contaminants content and residual carbon (RCR) related with the high concentration of resins and asphaltenes in the bottom barrel streams.

Higher metals and asphaltenes content led to a quick deactivation of the catalysts through high coke deposition rate, catalytic matrix degradation by metals like nickel and vanadium or even by the plugging of catalyst pores produced by the adsorption of metals and high molecular weight molecules in the catalyst surface. By this reason, according to the content of asphaltenes and metals in the feed stream are adopted more versatile technologies aiming to ensure an adequate operational campaign and an effective treatment.

Like quoted earlier, the hydrocracking units demand high capital investments, mainly to operate under high hydrogen partial pressures, it’s necessary to install larger hydrogen production units, which is another high costly process. However, face of the crescent demand for high-quality derivates, the investment can be economically attractive.

The Residue Hydrocracking Units have severity even greater than units dedicated to treating lighter feed streams (gas oils). These units aim to improve the residues quality either by reducing the contaminant content (mainly metals) like an upstream step to other processes, as Residue Fluid Catalytic Cracking (RFCC) or to produce derivates like fuel oil with low sulfur content.

Residue hydrocracking demand even greater capital investment than gas oils hydrocrackers because these units operate under more severe conditions and furthermore, the operational costs are so higher, mainly due to the high hydrogen consumption and the frequent catalyst replacement.

??Hydrocracking technologies have been widely studied over the years, mainly by countries with large heavy oil reserves like Mexico and Venezuela. The main difference between the available technologies is the reactor characteristics.

?Among the Hydrocracking Technologies which applies fixed bed reactors, it can be highlighted the RHU? technology, licensed by Shell company, Hyvahl? technology developed by Axens and the UnionFining? and Unicracking? Processes, developed by UOP. These processes normally operate with low conversion rates with temperatures higher than 400 oC and pressures above 150 bar. Figure 7 presents a basic process arrangement for the Unicracking? process by UOP Company.

Figure 7 – Process Arrangement for Unicracking? hydrocracking technology by UOP Company.

Technologies that apply ebullated bed reactors and continuum catalyst replacement allow higher campaign period and higher conversion rates, among these technologies the most known are the H-Oil? technology developed by Axens and the LC-Fining? Process by Chevron-Lummus. These reactors operate at temperatures above of 450 oC and pressures until 250 bar. Figure 8 presents a typical process flow diagram for a LC-Fining? process unit, developed by Chevron Lummus Company while the H-Oil? process by Axens Company is presented in Figure 9.

Figure 8 – Process Flow Diagram for LC-Fining? Technology by CLG Company (MUKHERJEE & GILLIS, 2018)

Catalysts applied in hydrocracking processes can be amorphous (alumina and silica-alumina) and crystalline (zeolites) and have bifunctional characteristics, once the cracking reactions (in the acid sites) and hydrogenation (in the metals sites) occurs simultaneously.?

Figure 9 – Process Flow Diagram for H-Oil? Process by Axens Company (FRECON et. al, 2019)

An improvement in relation of ebullated bed technologies is the slurry phase reactors, which can achieve conversions higher than 95 %. In this case, the main available technologies are the HDH? process (Hydrocracking-Distillation-Hydrotreatment), developed by PDVSA-Intevep, VEBA-Combicracking Process (VCC)? commercialized by KBR Company, the EST? process (Eni Slurry Technology) developed by Italian state oil company ENI, and the Uniflex? technology developed by UOP Company. Figure 10 presents a basic process flow diagram for the VCC? technology by KBR Company.

Figure 10 – Basic Process Arrangement for VCC? Slurry Hydrocracking by KBR Company (KBR Company, 2019)

???????????In the slurry phase hydrocracking units, the catalysts in injected with the feedstock and activated in situ while the reactions are carried out in slurry phase reactors, minimizing the reactivation issue, and ensuring higher conversions and operating lifecycle. Figure 11 presents a basic process flow diagram for the Uniflex? slurry hydrocracking technology by UOP Company.

Figure 11 – Process Flow Diagram for Uniflex? Slurry Phase Hydrocracking Technology by UOP Company (UOP Company, 2019).

???????????Other commercial technologies to slurry hydrocracking process are the LC-Slurry? technology developed by Chevron Lummus Company and the Microcat-RC? process by Exxon Mobil Company. Aiming to meet the new bunker quality requirements, noblest streams, normally directed to produce middle distillates can be applied to produce low sulfur fuel oil, this can lead to a shortage of intermediate streams to produce these derivatives, raising his prices. The market of high sulfur content fuel oil should strongly be reduced, due to the higher prices gap when compared with diesel, his production tends to be economically unattractive.

Despite the high capital investment and the high operational cost, hydrocracking Technologies produces high-quality derivates and can make feasible the production of added value product from residues, which is extremely attractive, mainly for countries that have difficult access to light oils with low contaminants.

?In countries, with a high dependency of middle distillates like Brazil (because his dimensions and the high dependency for road transport), the high-quality middle distillate production from oils with high nitrogen content, indicate that the hydrocracking technology can be a good way to reduce the external dependency of these products.

Naphtha Steam Cracking Process – Naphtha to Olefins

???????????The Steam cracking process has a fundamental role in the petrochemical industry, nowadays the most part of light olefins light ethylene and propylene is produced through steam cracking route. The steam cracking consists of a thermal cracking process that can use gas or naphtha to produce olefins, in this review we will describe the naphtha steam cracking process.

???????????The naphtha to steam cracking is composed basically of straight run naphtha from crude oil distillation units, normally to meet the requirements as petrochemical naphtha the stream need to present high paraffin content (higher than 66 %). Figure 12 presents a typical steam cracking unit applying naphtha as raw material to produce olefins.

Figure 12 – Typical Naphtha Steam Cracking Unit (Encyclopedia of Hydrocarbons, 2006)

???????????Due to his relevance, great technology developers have dedicated his efforts to improve the steam cracking technologies over the years, especially related to the steam cracking furnaces. Companies like Stone & Webster, Lummus, KBR, Linde, and Technip develop technologies to steam cracking process. One of the most known steam cracking technology is the SRT? process (Short Residence Time), developed by Lummus Company, that applies a reduce residence time to minimize the coking process and ensure higher operational lifecycle.

????????????The cracking reactions occurs in the furnace tubes, the main concern and limitation to operating lifecycle of steam cracking units is the coke formation in the furnace tubes. The reactions carry out under high temperatures, between 500 oC to 700 oC according to the characteristics of the feed. For heavier feeds like gas oil, is applied lower temperature aiming to minimize the coke formation, the combination of high temperatures and low residence time are the main characteristic of the steam cracking process.

The Synergy between Hydrocracking and Steam Cracking – Residue to Chemicals

???????????As aforementioned the hydrocracking units are capable to improve the quality of bottom barrel streams, the main advantage of the integration between hydrocracking and steam cracking units is the higher availability of feeds with better crackability characteristics.

???????????Bottom barrel streams tend to concentrate aromatics and polyaromatics compounds that present uneconomically performance in steam cracking units due the high yield of fuel oil that presents low added value, furthermore, the aromatics tends to suffer condensation reaction in the steam cracking furnaces, leading to high rates of coke deposition that reduces the operation lifecycle and raises the operating costs.

Once cracking potential is better to paraffinic molecules, and the hydrocracking technologies can improve the H/C in the molecules converting low added value bottom streams like vacuum gasoil to high quality naphtha, kerosene, and diesel the synergy between hydrocracking and steam cracking units can improve the yield of petrochemical intermediates in the refining hardware, an example of refining configuration relying on hydrocracking and steam cracking units is presented in Figure 13.

Figure 13 – Integrated Refining Scheme Base on Hydrocracking and Steam Cracking Units (UOP, 2019)

???????????In Figure 13, a slurry hydrocracking unit is applied to achieve deep conversion of bottom barrel streams while a diesel hydrocracking unit is applied to destroy diesel and improve the yield of naphtha in the refining hardware, the light naphtha is directed to steam cracking unit to produce olefins, like ethylene and propylene while the heavier fraction is pumped to a catalytic reforming unit where is converted in light aromatics (BTX), achieving high added value to the processed crude oil. It’s interesting to observe the synergy between deep hydrocracking (slurry) and FCC units, where the residual stream from FCC is applied as feed to the hydrocracking unit, raising the bottom barrel conversion of the refinery. Sometimes the hydrocracking and FCC technologies are faced by competitors technologies in the refining hardware due to the similarities of feed streams that are processed in these units. In some refining schemes, the mild hydrocracking units can be applied as pretreatment step to FCC units, especially to bottom barrel streams with high metals content that are severe poison to FCC catalysts, furthermore the mild hydrocracking process can reduce the residual carbon to FCC feed, raising the performance of FCC unit and improving the yield of light products like naphtha, LPG, and olefins.

Considering the great flexibility of deep hydrocracking technologies that are capable to convert feed stream varying from gas oils to residue, an attractive alternative to improve the bottom barrel conversion capacity is to process in the hydrocracking units the uncracked residue in FCC unit aiming to improve the yield of high added value derivatives in the refining hardware, mainly middle distillates like diesel and kerosene.

Another alternative to reduce the fuel production near to zero is presented in Figure 14.

Figure 14 – Refining Configuration with near Zero Fuels Production (UOP Company, 2019).

In the refining configuration presented in Figure 14, the kerosene is cracked to naphtha in a hydrocracking unit, in this case, the naphtha is sent to the aromatic complex aiming to produce even more aromatics (BTX) which has higher added value than olefins which is maximized in the alternative of Figure 13. Considering the recent trend of reduction in transportation fuels demand followed by the growth of petrochemicals market makes the synergy between hydrocracking and steam cracking units an attractive way to maximize the petrochemicals production in the refining hardware.

Crude Oil to Chemicals Strategy – The Relevance of Hydrocracking and Steam Cracking Units

???????????Due to the increasing market and higher added value as well as the trend of reduction in transportation fuels demand, some refiners and technology developers has dedicated his efforts to develop crude to chemicals refining assets.

???????????The combination of hydrocracking and steam cracking technologies is fundamental to the crude to chemicals refineries once allows a deep conversion of bottom barrel streams into high added value petrochemicals, Figure 15 presents an example of a crude to chemicals refinery based on the synergy between hydrocracking and steam cracking units, in this case licensed by Lummus Company.

Figure 15 – Crude to Chemicals Concept by Chevron Lummus Company (Chevron Lummus Global Company, 2019)

Another great refining technology developers like UOP, Shell Global Solutions, ExxonMobil, Axens, Saudi Aramco and others are developing crude to chemicals technologies, reinforcing that this is a trend in the downstream market. In any case, is applied the combination of hydrocracking and steam cracking units. Figure 16 presents the crude to chemicals concept developed by UOP Company.?

Figure 16 – Integrated Refining Configuration Based in Crude to Chemicals Concept by UOP Company.

Again, it’s possible to see in Figure 16 the relevance of hydrocracking and steam cracking units to maximize the yield of petrochemicals.

Closing the Sustainability Cycle – Plastics Recycling Technologies

???????????As described above, we are facing a continuous growing of petrochemicals demand and a great part of these crude oil derivatives have been applied to produce common use plastics. Despite the higher added value and significant economic advantages in comparison with transportation fuels, the main side effect of the growth of plastics consumption is the growth of plastic waste.

???????????Despite the efforts related to the mechanic recycling of plastics, the increasing volumes of plastics waste demand most effective recycling routes to ensure the sustainability of the petrochemical industry through the regeneration of the raw material, in this sense, some technology developers have been dedicated investments and efforts to develop competitive and efficient chemical recycling technologies of plastics.

???????????One of the most applied technology for plastics recycling in the catalytic pyrolysis where the long chain polymeric are converted into smaller hydrocarbon molecules which can be fed to steam cracking units to reach a real circular petrochemical industry. Another route is the thermal pyrolysis of plastics, is this case, its possible to quote the Rewind? Mix technology developed by Axens Company.

???????????Another promising chemical recycling route for plastics in the hydrocracking of plastics waste, in this case the chemical principle involves the cracking of carbon-carbon bonds of the polymer under high hydrogen pressure which lead to the production of stable low boiling point hydrocarbons. The hydrocracking route present some advantages in comparison with thermal or catalytic pyrolysis, once the amount of aromatics or unsaturated molecules is lower than the achieved in the pyrolysis processes, leading to a most stable feedstock to steam cracking or another downstream processes as well as is more selective, producing gasoline range hydrocarbons which can be easily applied in the highly integrated refining hardware.

???????????The chemical recycling of plastics is a great opportunity to technology developers and scientists, especially related to the development of effective catalysts to promote depolymerization reactions which can ensure the recovery of high added value molecules like BTX. More than that, the chemical recycling of plastics is a urgent necessity to close the sustainability cycle of an essential industry to our society.

Conclusion

???????????The scenario faced by the players of the downstream industry requires even more competitive capacity to ensure higher value addition to the processed crude oils, mainly considering the current trend of reduction in transportation fuels demand followed by the growing market of petrochemicals that requires a higher conversion capacity in the refining hardware aiming to ensure higher yields of added value derivatives. In this scenario, high integrated refining configurations based on residue upgrading and flexible refining technologies can be economically attractive, despite the high capital investment and the hydrocracking unit can improve the offer of high quality naphtha to steam cracking units, allowing higher yields of light olefins in the refining hardware and closer integration with petrochemical assets, which is a relevant competitive advantage in the current and short term scenario of the downstream industry.

Despite the advantages, it’s important to consider that integrated processes lead to a higher operational complexity, however, given current and middle term scenarios to refining industry, a better integration between refining and petrochemical processes is fundamental to the economic sustainability of the downstream industry.

In the digital transformation environment, the companies need to find new ways to ensure added value to the costumers and creative ways to destroy his current businesses through the discovering of new markets. To the downstream industry, the closer integration between refining and petrochemical assets ensures both goals with higher revenues and lower operating costs to refiners as well as the high added value to the processed crude oils while offers lower environmental footprint and needed materials to the society. The combination of adequate bottom barrel conversion capacity and the maximization of petrochemicals in the refining hardware can offer a highlighted competitive positioning in the current and future scenarios of the downstream industry helping the players to build an antifragile profile in a highly competitive market.

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Dr. Marcio Wagner da Silva is Process Engineer and Stockpiling Manager on Crude Oil Refining Industry based in S?o José dos Campos, Brazil. Bachelor’s in chemical engineering from University of Maringa (UEM), Brazil and PhD. in Chemical Engineering from University of Campinas (UNICAMP), Brazil. Has extensive experience in research, design and construction to oil and gas industry including developing and coordinating projects to operational improvements and debottlenecking to bottom barrel units, moreover Dr. Marcio Wagner have MBA in Project Management from Federal University of Rio de Janeiro (UFRJ), in Digital Transformation at PUC/RS, and is certified in Business from Getulio Vargas Foundation (FGV).?