Innovations in Producing Light Olefins by Fluid Catalytic Cracking

P.OConnor, Akzo Nobel Catalysts, Amersfoort, The Netherlands; P.Imhof and M.Baas, Akzo Nobel Catalysts, Amsterdam, The Netherlands Abstract
The Fluid Catalytic Cracking (FCC) process has been evolving continuously, starting in the 1940s as the main Gasoline machine, taking on the additional task of converting residual feedstocks in the 1970s, and now also playing an increasing role in the production of light Olefins. Recent innovations in FCC Process and FCC Catalysis and synergistic combinations thereof are emerging which enhance the capabilities for the production of light Olefins, while maintaining the robustness of the process for resid conversion and/or distillate fuels production. The increasing importance of the production of Olefins in the FCC must and can be made congruent with the trends in future specifications and compositions of transportation fuels, of which the FCC remains an important producer of intermediates (Alkylate, MTBE, Isomerate, FCC Gasoline, FCC Light Cycle oil)

Introduction Propylene Demand and Supply

Several drivers are affecting the growing need for the production of Propylene by Fluid Catalytic Cracking. On one hand the need for Propylene is growing faster than that of ethylene, while on the other hand the co-production of Propylene from steam crackers (~70% of supply) is expected to decline as plants are optimized to produce higher-value ethylene. Also Ethylene, Butylenes and possibly in future also C5 (iso)olefins are or will become higher valued specialty products from the refinery and hence the FCC. The bulk of the additional Propylene will need to be produced from changing the ratios of FCC product streams. This involves optimization of the base catalyst system and the application of small pore zeolites containing additives and catalysts in order to at least double the Propylene yields. Moreover, addition of new technologies will be needed to further increase the Propylene production. It has been even suggested that on-purpose Propylene technologies may become economically viable, including dehydrogenation and the conversion of methanol to Olefins1.

Shifts in transportation fuels

Changes in fuels and fuels specifications are having a great impact on the refinery. In Europe for instance due to the growth of diesel consumption there are several refineries, which are attempting to reduce their Gasoline yield because of structural over supply. Also the traditional quality of FCC Gasoline is no longer acceptable for the Gasoline pool due to the tighter Sulfur and Olefins specifications being introduced2. In Europe because of the dieselization the drive to reduce Gasoline has many refiners working on ways to convert FCC to lighter Olefins (C3=, C4=). In certain cases Gasoline may be re-constructed via high severity Catalytic Cracking to Light Olefins and iC4 followed by

Alkylation, Isomerization and/or Polymerization yielding really green (low Sulfur, Low Aromatics) Gasoline components. Longer term2, the Aromatics content of fuels will become a very important quality constraint. Also in the case of Gasoline, the trend is that improved (injection etc) internal combustion engines (ICE) and certainly Gasoline or naphtha based fuel cells (Gsln FC) will run more 3,4 efficiently with lower Aromatics, while the demand for octane will become far less critical .

FCC as a robust process producing light Olefins and clean fuels

In this paper we address the co-evolution of process and catalysis, leading up to the present state-of-the-art in producing light Olefins by FCC. Recent innovations in FCC Process and Catalysis and synergistic combinations thereof are introduced which enhance the capabilities for the production of light Olefins, while maintaining the robustness of the process for resid conversion and/or distillate fuels production. Particularly the latest developments in catalyst research and design are highlighted. We emphasize that the increasing importance of the production of light Olefins in the FCC must and can be made congruent with the trends in future specifications and compositions of transportation fuels. Specifically for FCC this means that the light Olefins production needs to be maximized, while minimizing the Sulfur and Aromatics to the transportation fuel pools2.

The evolving FCC process FCC Process Developments

The FCC process has been evolving continuously, starting in the 1940s as the main Gasoline machine, taking on the additional task of converting residual feedstocks in the 1970s, and now also playing an increasing role in the production of light Olefins. The FCC process hardware and operation have co-evolved with the catalyst and the changing economical and environmental requirements. Key recent developments in the FCC process and hardware 5, 6 are : Short contact time riser reactor. Improved Feed distribution and atomization Feed pre vaporization or supercritical injection. Multiple feed injection. Quick product disengaging and separation from catalyst. Quick product quench More efficient stripping Downer (down flow) reactor. Improved regenerator efficiency, lower inventory. Improved control of combustion (CO, CO2, SOx, NOx). Improved air grid designs. Catalyst coolers (internal and external heat-removal). Power recovery from flue gas. Improved high flux standpipes. High efficiency cyclone separators. Cyclones without diplegs. Third-, Fourth- and Fifth- stage particulate capture systems. Erosion and high temperature resistant metallurgy.

These developments have lead to dramatic reductions in the size (elevation, volume, catalyst inventory) and hence cost of a FCC unit required per barrel of feed charged and converted.

FCC Catalyst Developments

An important part of the process improvements were enabled by catalyst developments7, 8.

In the 1950s a big step was made when zeolites were and their potential recognized for application in catalysis9. In the 1960s Mobil10 introduced Rare Earth stabilized Faujasite zeolites into FCC catalysts leading to very substantial increases in conversion and Gasoline production as shown in the following table: Table 1 - Improvements by zeolite cracking catalysts10 Conversion (vol%) Silica-Alumina gel REHX REHY 56 68 75 Gasoline (vol%) 40 52 58

The high hydrogen transfer characteristics of these catalysts strongly reduced the light olefin yields. A typical example of this is given in the following table: Table 2 - Loss in light Olefins yield by zeolite cracking catalysts Conversion (vol%) Silica-Alumina gel REHY 75.5 85.5 Gasoline (vol%) 47.5 61.0 Propylene(vol%) 8.5 5.9

In the 1970s The FCC unit design and operation evolved to regain some of the lost octane and light olefin yields by higher reactor temperature operation and riser cracking, unfortunately usually at the cost of dry gas production. In the 1980s the advent of Short Contact Time (SCT) FCC by amongst others closed cyclones and the introduction of the small pore ZSM-5 zeolites resulted in improved octanes and light olefin yields while limiting the incremental dry gas production. Table 3 - Higher reactor temperatures and ZSM-5 addition Dry gas(wt%) Base Case Higher Temperature ZSM-5 additive 2.6 3.3 2.6 Gasoline (wt%) 45.0 44.2 42.7 Propylene (wt%) 4.2 6.3 5.2

The concept behind the application of shape selective small pore zeolites in FCC involves the reactant shape selectivity by which preferentially (linear) olefins and possibly also n-alkane molecules or side chains are preferentially removed by cracking to lighter Olefins. When ZSM-5 is added to the FCC unit it mainly cracks and isomerizes C5+ molecules. ZSM-5 is able to intercept and crack heavy olefin intermediates that would otherwise undergo hydrogen transfer over the Faujasite zeolite11. From the other side we can explain the mechanism of Faujasite cracking as one whereby, the Olefins are stabilized by hydrogen transfer into less reactive molecules like (iso) paraffins and Aromatics, leading to a higher Gasoline yield, but lower light olefin production12. As both raising the reactor temperature and the addition of ZSM-5 tend to increase the rate of cracking of Gasoline Olefins relative to the rate of hydrogen transfer, it has been observed that there is little synergy between the two methods for boosting light Olefins when using large amounts of ZSM-5 as most of the higher Olefins, the precursors for ZSM5 cracking, are already removed13.

Feed Aromatics

Gasoil, Gasoline Aromatics

Naphthenes

Paraffin's

Olefins & Paraffin's

Light Olefins

Figure 1 - FCC Reaction model: Aromatics versus Light Olefins A simplified reaction scheme based on the foregoing observations is given in Figure 1. This strongly suggests that mainly higher (linear) Olefins are the reactants which can be converted to lighter Olefins like Propylene in FCC, and that the supply of these molecules will set or limit the maximum Propylene yield. Furthermore it also implies that the maximization of light Olefins in the FCC is indeed congruent with the objective to reduce the quantity of Aromatics being produced in the FCC and going to the Gasoline and diesel pools.

Present State of the Art Stabilization of Small pore zeolite activity

Since the first commercial trial14 with a ZSM-5 FCC catalyst in 1984, several further improvements in the technology have occurred15. A very significant innovation has been the stabilization of ZSM-5 with Phosphorus. Phosphorus retards the dealumination of the zeolite and results in a zeolite which after hydrothermal deactivation retains a larger fraction of its acidity and hence activity. Phosphorus will reduce the initial acidity of the zeolite slightly. Table 4 - Phosphorus stabilization of ZSM-5 Relative Activity*) ZSM-5, fresh ZSM-5, steamed** ZSM-5, fresh stabilized with 1wt% P ZSM-5, steamed after stabilized with 1wt% P * n-hexane cracking at 811 K. **5 hours 1033K, 100% steam, atmospheric. In the industrial FCC applications the stabilization by phosphorus has resulted in roughly a doubling of the activity per wt% ZSM-5 crystal for producing Propylene when applying 2 to 3% crystal on FCC inventory. This increased effectiveness has led to a much wider use of ZSM-5 additives in FCC. 100 1 80 6

A direct and smooth correlation exists between the product yields and the total number of ZSM-5 acid sites as measured by ammonia temperature programmed desorption16. Phosphorus seems to stabilize these acid sites. The particle size of ZSM-5 also plays a role, the small particles favor the Gasoline loss (less stabilized Aromatics) and LPG increase. This effect is more pronounced with higher acidity ZSM-5 particles16. As may be expected the benefits of phosphorus stabilization also are valid for other (small pore alumino-silicate) zeolites, like for instance zeolite . Phosphorus stabilization has also been successfully applied to stabilize Faujasite (Y-type) and MCM-41 type zeolites17.

Optimization of the FCC Catalyst and ZSM-5 additive system

The interaction between the hydrogen transfer activity of the Faujasite Y based zeolite FCC catalyst and the ZSM-5 containing additives is critical18, 19. The effectiveness of ZSM-5 decreases when the hydrogen transfer activity of the host FCC catalyst increases, as for instance by increasing the Rare Earth content and hence hydrogen transfer activity of the zeolite.

Relative Propylene Yield

3 2.5 2 1.5 1 0.5 0 0.1 0.2 0.3 ZSM-5 / ZSM-5 + Y ratio Low Rare Earth on Y High Rare Earth on Y

Figure 2 - Propylene yield versus ZSM-5 to total zeolite ratio This phenomenon is illustrated in Figure 2 whereby catalysts with high and low Rare Earth (RE) on zeolite (Y) were tested in a short contact time Fluid bed test (FST) in various ratios with ZSM-5 additives. At constant conversion operation we observe that the Propylene yield will be maximized when a host catalyst is used with a minimum hydrogen transfer activity. Unfortunately this coincides with a higher dry gas make and a lower catalyst activity. Furthermore we can observe that there seems to be a limit to the Propylene yield that can be achieved with these catalyst systems.

Systems with very high ZSM-5 in catalyst inventory

Because of the limitation in supply of higher Olefins precursors there is a limited benefit to adding more ZSM-5 crystal to the FCC unit above a certain point18, 20. Also we can observe a loss in ZSM-5 effectiveness when the amount of crystal is too highly concentrated in only part of the catalyst system. This is illustrated in Figure 3, where the amount of ZSM-5 crystal required to obtain a constant production of propylene is given as a function of various ZSM-5 addition strategies.

120 100 Relative Activity 80 60 FCC with ZSM-5 40 20 0 1 5 % ZSM crystal in FCC Figure 3 - ZSM-5 crystal effectiveness at various Additive concentrations We propose that we are confronted with two distinct issues here: First of all at macro (catalyst system) as well as at micro scale (catalyst particle), the cracking rate of ZSM-5 will be limited by the (local) supply of linear Olefins. This implies that above a certain conversion the cracking rate per % crystal will deteriorate strongly. Secondly, one can observe that the effectiveness of zeolite crystal embedding and stabilization deteriorates when increasing the amount of crystal in the additive or catalyst. This second effect has been addressed (e.g. by Ziebarth et al21) in Figure 3 this improvement in stabilization has been designated as the new generation of additives. Unfortunately this approach does not solve the first problem, as the local depletion of linear Olefins (due to the very high local ZSM-5 crystal concentrations) will eventually cause a loss in cracking rate to lighter Olefins. Since we found that the phosphorus needed for ZSM5 stabilization interacted with other active components in FCC catalyst22, we stabilized the ZSM5 ex situ before incorporation in order to get high efficiency in Propylene make with a good bottoms cracking. The ex situ stabilization is achieved by treating the zeolite crystal with a phosphate source followed by a fixation step. Subsequently the stabilized zeolite is added to the catalyst composition, preferably just before (spray) drying. Table 5 - High light Olefins yields combined with bottoms cracking Catalyst system . FCC Catalyst FCC Catalyst + Additive c TP-1 d
a b

FCC + Additives Next generation

FCC + Additives

10

Yields (%wt) a, e C3= C4= + iC4= 4.8 7.4 6.2 8.1 10.1 10.2

NBC b 82.0 80.6 83.1

Yields at constant Cracking Severity (Cracking Temperature, Catalyst to Oil Ratio) NBC= Net Bottoms Conversion = 100 Bottoms Coke , %wt. c 10% of additive containing 25% ZSM-5 crystal, phosphorus activated. d Novel FCC catalyst system containing 5% ZSM-5 crystal, ex-situ phosphorus activated. e Catalysts tested in a very short contact time (~ 1 sec) test SCT-RT32 with Resid feedstock

The foregoing table indicates that it is indeed possible to combine high Propylene production with good bottoms conversion making use of a proprietary catalyst (designated TP-1) containing ex-situ stabilized ZSM-5 in combination with Y zeolite. We can also observe that in terms of Propylene make per % crystal, the route of using an additive is more effective. The exact reasons for this are not yet clear. We speculate though that the close presence of a high concentration of Y zeolites in the same catalyst particle containing ZSM-5 may have a negative effect due the loss of linear Olefins by hydrogen transfer.

Recent Process and Catalyst Innovations The ultimate in light Olefins yield in FCC?
As indicated by the foregoing with the optimization of the FCC base catalyst system and the application of small pore zeolites it is possible to at least double or maybe triple the Propylene yields. We must however also conclude (Figure 2 and Aitani et al20) that there is a limitation to the production of light Olefins that can be achieved in conventional FCC. Therefore a next step forward will require substantial changes in the FCC process and catalyst philosophy. Recently we can observe the emergence of several new process-catalyst combinations, all originating from the FCC process, but including specific innovations to enhance light Olefins production. These processes bridge the gap between traditional FCC and Steam Cracking. Table 6 - Light Olefin Yields of FCC and related Processes Process FCC New FCC Technology Including small pore zeolites Deep Catalytic Cracking, DCC23 Stand alone FCC for cracking light (naphtha) feed to Olefins Steam Cracking, SC Ethane feed Naphtha Yield ranges (%wt)8 = = C2 C3 1-2 2 10 5 - 10 8 30 2.5 - 10 8 25 ~ 20 25 40 Relative to 5% wt = C3 1-2 2-5 ~4 5 -8

70 - 80 20 - 50

10 20 10 - 20

2-4 24

As stated in our introduction it is our intention focus on the case that one wishes to combine the important function of the FCC as producer of transportation fuels from heavier fuels with the objective to maximize the light Olefins production. In the following a short description of a few salient innovations in this field are given:

Deep Catalytic Cracking (DCC)

The DCC process is a fluidized catalytic cracking (FCC) process modified to increase the production of light Olefins from heavy oil feedstock23. One commercial version, DCC Type I, maximizes selectivity to Propylene and substantially increases the yield of ethylene. In a second commercial version, DCC Type II, isobutylene and isoamylene selectivity is maximized. The DCC flow scheme is similar to a conventional FCC unit. The main fractionator and light ends recovery, use the same basic configuration with the necessary adjustments required by the different yield structures. DCC operation is similar to FCC or RFCC in the way the catalyst is handled and regenerated. Compared to FCC the operating conditions are similar but the reactor temperature is higher and the hydrocarbon partial pressure nominally lower.

A proprietary zeolite catalyst is used in the DCC process24. The invention applied is a very elegant one whereby Rare Earth is incorporated into the ZSM-5 structure by crystallizing the zeolite making use of Rare Earth-containing Faujasite seeds. This results in a significant improvement of the activity and stability of the zeolite. It is claimed that even further stabilization can be achieved by post treatment with phosphorus. Yoshimura et al , investigated the stabilization of ZSM-5 with a combination of Rare Earth and Phosphorus. They conclude that Rare Earth reduces the rate of formation of Aromatics on the external surface area of the zeolite, while Phosphorus reduces the loss in activity by dealumination. It should be noted that the zeolite was externally impregnated with Rare Earth (Lanthanum), while in the system of Xingtian et al24, the Rare Earth is actually incorporated into the internal zeolite structure.
25

Ultimate Catalytic Cracking (UCC)

Ultimate Catalytic Cracking (UCC) is a process developed by Indian Oil (IOCL) and described by Mandal et al26, for maximizing the production of LPG from VGO and resid. The major important features are the maintenance of a high space velocity (40-120 hr-1) and a high catalyst to oil ratio (15-25). A comparison of the main process conditions of the process with conventional FCC and the DCC process is given in the next table: Table 7 - Comparison of FCC, DCC and UCC process conditions Process: WHSV, hr-1 Catalyst / Oil ratio Riser exit temperature, oC Steam injection, wt% on feed FCC 150 200 48 490 540 0 10 DCC 0.2 20 2 12 540 625 5 50 UCC 50 - 80 18 - 22 530 - 600 20 - 35

The catalyst employed in the UCC process is claimed to be unique and predominantly consists of ZSM-5 type zeolites, but also includes a limited content of Ultra Stable Y (USY) zeolites and a bottoms cracking matrix.

High Severity (HS) FCC

High Severity (HS) FCC is designed to optimize both overall product yields and petrochemical feedstock production. Key features of the process include contact time less than one second, in a down-flow reactor that suppresses back-mixing and improves residence time distribution control, and a high catalyst-to-oil ratio to minimize thermal cracking, over-cracking and hydrogen transfer. The HS FCC process has been jointly developed by the Petroleum Energy Center (Tokyo) and the King Fahd University of Petroleum and Minerals 27, 28. The claims are that this process is able to produce up to 25%wt of Propylene and 5% of Ethylene.

FCC Down-flow reactor systems and catalyst design

In conventional FCC the catalyst particles move in an up-flow reactor or riser, against gravity. Back mixing of solids inside riser reactors results in a wide variation in residence times for the solids, as well as clustering and radial solids segregation. A distinguishing feature of all riser reactors is the slip factor, the ratio between catalyst and hydrocarbon residence times. In a riser reactor both catalyst and hydrocarbon move vertically upward, but the hydrocarbon moves faster. Most of the hydrocarbon vapor moves in the middle of the reactor, while the catalyst moves near the walls.

Typically the hydrocarbon vapor velocity is 2 to 3 times that of the catalyst. Thus, while the catalyst may take 4 to 8 seconds to pass up the full length of the riser, the hydrocarbon may take only 2 to 3 seconds. In contrast to what happens in a riser, particles in a down-flow reactor move with gravity. Particle flow in down-flow reactors is much more uniform radially than in up-flow reactors. The back mixing of solids is reduced, leading to shorter and more uniform solids residence times. Hydrocarbon and catalyst have an almost equal residence time of in a down-flow reactor. Characteristic improvements in LPG and light Olefins yield by FCC down-flow operation are given in the following table: Table 8 - FCC Down-flow versus FCC Riser comparison6 FCC Process Riser Down-flow
a

Catalyst / Oil 7.8 8.7

Yields in %wt at 8.8%wt Coke C3= LPG Bottoms 4.8 6.6 18.0 20.3 11.4 13.0

NBCa 79.8 78.2

NBC= Net Bottoms Conversion = 100 Bottoms Coke, %wt.

Note however the loss in (bottoms) conversion in the downer. Also this can be explained by the hydrodynamics of the downer: In a riser, almost all conversion occurs in the reactor entrance region, where catalyst comes in contact with the fresh feed. After the first few meters, the riser serves more as a conveyer than as a reactor since most of the catalyst is already deactivated. In a down-flow reactor, there is relatively little conversion in the entrance region since the 6 solids are not held up in the entrance region as much as they are in a riser . Thus conversion occurs throughout the whole down-flow reactor and gas will come in contact with fresh catalyst at any axial location. On the other hand, in risers conversion benefits from backmixing and higher catalyst holdup in the entrance region, and a large amount of conversion will be obtained by thermal cracking, when fresh hydrocarbon comes into contact with a large amount of Coked catalyst. The down-flow reactor provides significant selectivity advantages, in particular in terms of Coke and Olefins, due to its much more uniform gas-solids flow pattern. In down-flow reactors, catalyst residence time is lower at equal hydrocarbon residence time compared to a riser, and catalyst holdup is lower. Thus, to obtain adequate conversion levels, a higher catto-oil ratio, a higher reaction temperature, or more active catalyst will be necessary in a downflow reactor to compensate for lower catalyst holdup and a lower catalyst residence time. Fortunately developments in catalyst technology achieving high accessibility make it possible to run down-flow systems without penalties on conversion, under conventional FCC operating conditions6, 29, 30, in Table 9, an example is shown in which the limitation in cat-to-oil ratio is resolved by the use of a proprietary high accessibility catalyst: Table 9 - High Accessibility Catalysts in FCC downer operation29 Catalyst Accessibility Standard . High Catalyst / Oil 7 9 6 7 Yields in %wt Conversion 73.1 77.2 77.0 79.0 Coke 8.2 9.1 7.9 8.0 Bottoms 13.0 9.5 8.5 7.5 NBC 78.8 81.4 83.6 84.5

FCC Feed pre-vaporization

9

One point, which has not received much attention up to now6, is the heating of the feed up to vaporization, before contacting with catalyst. In the state-of-the-art FCC process, it is only when the feed contacts the regenerated hot catalyst that heat transfer occurs to attain the required temperatures to vaporize the feed and effect the cracking reactions. The initial contact of the catalyst with the feed thus has a decisive influence on the conversion and selectivity to desirable products. Improvements in the contact between catalyst and feed always aim at promoting a quick vaporization of the feed and an intimate contact with the catalyst in the short time available in the reaction zone. In order to favor the catalytic reactions, it is necessary that the vaporization of the in the mixing area occurs in few milliseconds, so that the molecules of vaporized hydrocarbons may contact the catalyst particles, permeate its pores and reach the sites of the catalyst which cause the desired catalytic cracking. If vaporization and catalyst contacting are not fast enough, thermal cracking of the liquid portions of the feed is observed. The thermal cracking leads to by-products such as Coke and fuel gas, especially with residue-containing feeds. Thermal cracking thus undesirably competes with the catalytic cracking kinetics we are aiming for in the FCC process. In the novel PREVAP31 process designed and developed by Petrobras, feed is to a large extent vaporized before it makes contact with the hot cracking catalyst from the regenerator vessel. Heat exchange with the catalyst is not necessary to vaporize the feed. Thus, Coke deposits on the catalyst surface are reduced, the Gasoline and light Olefins yields are improved and the unit may even operate under very low contact times (lower than 0.5 seconds). Table 10 - Pilot Riser testing of PREVAP concept 6 FCC Process Base with PREVAP Yields in %wt at 9.0%wt Coke C3= LPG Gasoline 4.5 5.2 16.3 16.2 40.3 43.3 Bottoms 15.7 13.8 NBC 75.3 77.2

One may visualize the concept as follows: The feed is introduced into the riser in a supercritical state and instantaneously flashes over the feed nozzle, which functions as a relief or restriction valve. PREVAP will be an important design innovation for maximum Light Olefins FCC technology aiming at extremely reduced contact times between catalyst and hydrocarbons.

Exploring novel FCC catalyst designs Maximizing Light Olefins while maintaining FCC Robustness
Diluting the host FCC catalyst with ZSM-5 additive will usually result in a loss in bottoms cracking and consequently an important challenge in catalyst design has been to enhance the capabilities for the production of light Olefins, while maintaining the robustness of the catalyst for resid conversion and distillate fuels production21, 26. Our initial efforts (Table 5) have not been completely successful, as while we were able to maintain an excellent bottoms cracking activity, the conversion to light Olefins (particularly Propylene) remains disappointing. We speculate that this may be caused by the relatively low ZSM-5 to Y zeolite ratios applied, meaning that the Y zeolite is still dominating the reactants pool converting a large part of the potential ZSM-5 feed stock to Aromatics. Above a certain percentage of ZSM-5 crystal added, Propylene yield does not increase very much. We propose this is due to the depletion of the higher (linear) olefins and that the supply

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of these molecules basically sets or limits the maximum achievable Propylene yield (Figure 1). Therefore we designed and evaluated a novel catalyst system (designated AFX, Advanced Fuels eXperimental) with the objective to reduce rate of Aromatics production in FCC. Our working hypothesis is that this will reduce the Aromatics from the FCC going to the Gasoline and diesel pools, and in parallel enable an increase in the maximum achievable light Olefins production from the FCC.
5 Relative Propylene Yield 4 3 2 1 0 0 0.2 0.4 0.6 0.8 1 ZSM-5 / ZSM-5 + Y Zeolite ratio High Rare Earth on Y + Additive Pure ZSM Additive Low Rare Earth on Y + Additive TP System AFX System

100% Additive

Figure 4 - Relative Propylene Yield for Advanced Fuels (AFX) Catalysts All the benchmark and experimental catalysts were tested in a very short (~ 1 second) 32, 33 contact time small scale test SCT-RT (Short Contact Time Resid Test) with an atmospheric Resid feedstock. This test shows a good correspondence with large scale pilot plant testing and industrial riser FCC operations. The results (Figure 4) confirm that with the AFX system it is indeed possible to increase the Propylene production (and total light olefin yield) further. This is not the case with conventional state-of-the-art ZSM-5 additives. The reason for this is that these additives are not capable of (pre) cracking the larger molecules into the range where they can be cracked by ZSM-5 or other small or medium pore type zeolites.

95 Net Bottoms Conversion, %wt 90 85 80 75 70 65 60 0.00 100% Additive Case High RE on Y Low RE on Y RFCC Champion AFX System

1.00

2.00

3.00

4.00

5.00

Relative Propylene Yield

Figure 5 - Net Bottoms Conversion (NBC) for AFX system This is demonstrated in Figure 5, indicating that contrary to the case with conventional ZSM-5 additives, with the AFX system we are able to increase the Propylene yield, while maintaining a good bottoms conversion. We should point out that the results with the AFX systems were

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obtained at a higher cracking severity than normally applied in conventional FCC. Because of the very low Y zeolite activity and hydrogen transfer, the catalyst will make less Coke and therefore equilibrate (Heat balance) at a higher catalyst to oil ratio (CTO). In Figure 6 the relative Propylene yield is plotted versus relative severity. With the present feedstock even running at a higher FCC severity, it does not seem possible to produce a higher Propylene yield than 2.8 (see Figure 2) times the base case. With the AFX system we reach 4.0. The next step forward is to combine this with innovations in FCC process design (Down-flow reactor, PREVAP, Higher CTO and Temperature), towards a Propylene yield which is in the range of DCC and stand alone FCC type unit to produce Propylene from FCC Gasoline or Naphtha.
5.00 Relative Propylene Yield 4.00 3.00 2.00 1.00 0.00 0.00 Max FCC + Additive High RE on Y Low RE on Y RFCC Champion AFX System Modified FCC + AFX (Target)

1.00

2.00

3.00

4.00

Relative Cracking Severity

Figure 6 - NBC for Advanced Fuels (AFX) Catalysts The next question is if the increase of the production of light Olefins goes hand in hand with the reduction of Aromatics from the FCC going to the fuel (Gasoline and diesel) pool.

Maximizing Light Olefins and minimizing Aromatics

We evaluated this for the Gasoline pool in refinery. Although the Aromatics content of the FCC Gasoline does not change a lot the Aromatics stream to the Gasoline pool does drop strongly, because of the shift from Gasoline to Olefins. If the loss in FCC Gasoline is (partly) compensated by the conversion of LPG to Gasoline, the net effect is positive (Table 11): Table 11 - Light Olefins and Low Aromatics Gasoline Catalyst system . FCC Catalyst FCC Catalyst + Additive High CTO FCC with AFX
a b

Yields (%wt) a C3= C4= + iC4= 5.5 7.4 21.1 7.9 10.1 14.7

iC4 2.5 1.8 1.5

Gsln 50.9 46.4 20.6

Aroa PGb 100 98 39 100 95 60

Aro = % Aromatics from FCC to Gasoline pool (%wt on feed) PG = % Potential Gasoline (including Alkylate, Isomerate, MTBE etc).

Although we have not evaluated this yet in detail in the context of this study, we expect also to see a drop in the Aromatics produced in the light cycle oil range. Table.12 illustrates how

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the operation with AFX at a high FCC severity (CTO) allows the trade-off of Gasoline for light Olefins. Table 12 - Total Light Olefins versus Gasoline production Catalyst system . FCC Catalyst High CTO FCC with AFX
a b

Yields (%wt) a C2= C3= 1.1 5.0 5.5 21.1

C4= + iC4= 7.9 14.7

iC4 2.5 1.5

TLO a 14.5 40.8

Gsln TLO 50.9 20.6 100 280

TLO = Total light Olefins, %wt on feed. TLO = % Total light Olefins production.

Conclusions and Future Challenges

Innovations in FCC Process and FCC Catalysis and synergistic combinations thereof are emerging which enhance the capabilities for the production of light Olefins, while maintaining the robustness of the FCC process for resid conversion and/or distillate fuels production. The FCC process can compete with processes like DCC and stand alone (Gasoline/Naphtha) FCC operation, maximizing light Olefins while maintaining FCC robustness. The maximization of light Olefins is consistent and congruent with the trend in future specifications towards lower Aromatics in transportation fuels. Developments in FCC catalyst research and FCC process design are highlighted, indicating that improvements in catalyst design (Like for instance High accessibility catalysts, TP and AFX systems) and the synergy with process design will continue to have a big impact on the success of this endeavor.

References
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