Fluid Catalytic Cracking (FCC) Catalyst Optimization to Cope with High Rare Earth Oxide Price Environment

Introduction

Technical Note

The use of rare earths in FCC catalysts was driven by the need for more active and hydrothermally stable products with better yield performance. Rare earth oxides (REO) achieved these goals by enhancing catalytic activity and preventing loss of acid sites during normal unit operation. To address the specific needs of each FCC unit, catalyst manufacturers formulate catalysts with various rare earth levels that allow for optimal unit performance. The level of REO in a specific catalyst formulation is determined by operational severity and product objectives. As the need for increased amounts of gasoline grew over time, refiners tended to increase the level of rare earths in their catalyst

formulation to meet their profitability targets. Rare earth gradually increased over the years and at the end of 2010, the average was 3%, with several refineries running in excess of the average.

Figure 1 shows 2010 historical data for E-cat samples analyzed by BASF for rare earth oxide. These reflect all the samples that were received by BASF in the fourth quarter of 2010 before the REO price spike occurred. Sample count refers to the number of E-cat samples analyzed by the BASF laboratory. The blue trend line shows the cumulative percentage of samples at or below a specific REO content. Although operational demands have not changed in the industry; current rare earth market conditions have put pressure on catalyst manufacturers as well as refiners to reassess the role of RE in the FCC industry. When looking at the catalytic options, it is critical to look at the overall value and not just the cost of RE. BASF has actively helped its customers analyze their operations and determine when a drop in RE levels is beneficial. Nineteen out of sixty BASF customers that have looked at a low REO option have switched. BASFs products deliver the highest activity in the market and therefore are well suited for low REO operation. As will be discussed in this article, the cost benefits and possible performance deficits of this option need to be clearly understood before making a change.

REO Supply-Demand Balance

The supply-demand balance of the global rare earth market became disconnected when China, which produces 95% of the worlds supply of rare earths, severely cut its export quotas in July 2010. China is not expected to change its position, despite the World Trade Organizations warning that reluctance to share its rare earth supplies constitutes a violation of the global trade rules. Export quotas for the second half of 2011, recently released, indicate a significant increase over the 2010 numbers. On close examination, the new quotas reveal that nothing has changed as the new figures merely include ferrous alloys. These were not part of the quota in 2010. Market expectations are that price volatility will continue until new suppliers enter the market and re-establish the supplydemand balance. In a recent research note issued by Goldman Sachs1, prices are likely to rise in the short term, over the next 18 months, and then soften in the 2013 to 2015 period. This softening of rare earth prices will most likely be due to additional capacity coming online from non-Chinese sources that are expected to significantly shift the supply picture in the coming years.

45 Number of Sample Counts 40 35 30 25 20 15 10 5 0 0.5 1 1.5 2 2.5 REO wt%

Figure 1: Distribution of REO in FCC catalyst samples

100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% 3 3.5 4 5

Cumulative Percent of Samples at REO wt% Level

During the interim period, until rare earth prices once again normalize, the refining industry is looking for ways to address the increase in catalyst costs within its current budgetary constraints. Instinctively, the drive is to opt for lower rare earth catalyst formulations to offset the costs of the raw material. While this action can have an immediate and successful impact on the operating budget, it may not be the best decision for the refinery. Understanding the constraints of a specific FCC unit is critical to making the optimal economic decision. BASF has proactively worked with its customers to examine low rare earth catalytic options that fit the needs of the specific users.

The decision to change catalyst or reformulate catalyst is not a trivial one. Simply reducing rare earth levels of the catalyst without a comprehensive study can result in severe yield penalties and possibly force the refinery to cut feed rates to the unit. All such consequences are economically prohibitive. Helping customers evaluate the effect of rare earth level on key catalytic variables reduces the uncertainty of the change and facilitates the decision to move to a reformulation of their FCC catalyst, when appropriate. The specifics of this change in formulation and the impact of REO level on conversion, as well as the effect of fresh catalyst surface area and addition rate, will be examined in this paper.

Technological Differences
While all catalyst companies can offer catalyst products with lower levels of REO, BASF is the only company that can offer its customers an option of increasing activity, and thereby maintaining conversion at constant catalyst addition, due to an increase in zeolite content as represented by active and selective total surface area. BASF employs in-situ technology, which is particularly well suited for this application. The in-situ process begins with a catalyst-sized microsphere. The ensuing step consists of growing the zeolite crystal within the microsphere. The zeolite in-situ process serves two functions; it provides the active and selective area, as well as providing the strength imparted to the microsphere. This technology is distinct from the incorporated technology practiced by all other catalyst suppliers. With incorporated technology, a single particle is formed consisting of an admixture of clay, zeolite, and binder. As this technology is already optimized, addition of substantial amounts of zeolite will require reducing either the clay or binder. The incorporated catalyst technique is inherently limited to an upper level of zeolite content and cannot increase surface area without seriously compromising the strength to withstand breakage in the FCC unit.

How Rare Earth Affects FCC Catalyst Performance

When considering a move to reduce REO component in the catalyst, it is critical to grasp the performance shifts and economic impact of such a change. The economic impact comprises two aspects. It is a function of total catalyst cost and the value created from a given catalyst formulation. Reducing the rare earth level will have an immediate cost saving, but this calculation alone will not give the true profit generation picture if the margin benefits from the yield slate are not included. To illustrate the impact of such change on key catalytic performance indicators, a proprietary FCC simulation model was used to study the effects of REO level, catalyst addition rate, and fresh surface area for FCC units operating with the following feedstocks. Hydrotreated Vacuum Gas Oil (VGO) - Refinery A Standard VGO - Refinery B n Moderate Resid - Refinery C n Heavy Resid - Refinery D
n n

Our choice in selecting the above feed types is to provide an analysis that covers the whole range of feed diets (types) used in FCC operations. The base case for all cases was 3% REO in the catalyst. As seen from Figure 1, this was the average level of rare earths used in 155 FCC units. For each operation, the REO level was changed to model the following scenarios:
n

Refinery API Concarbon wt% Sulfur wt% Basic N2 wt% % 650 F % 1000 F + TSA m2/g Activity REO wt%

A 26.3 0.3 0.5 0.03 15 <10 180 75 3

B 22 0.3 0.7 0.05 Distillation 20 <10 E-cat Properties 152 73 3

C 22.1 0.9 0.5 0.04 7 10 116 72 3

D 20.1 4.5 0.4 0.04 4 20 130 72 3

Impact of REO level on conversion, at constant catalyst addition rates and unit conditions Impact of fresh catalyst addition rate, to restore base case conversion at constant unit conditions Effect of increasing fresh catalyst surface area, at constant catalyst addition rates and unit conditions

Table 1: Feed and Equilibrium Catalyst Properties for Base Cases

Refinery Mode of operation Rx Outlet Temperature Regen Bed Temp C/O Conversion Liquefied Petroleum Gas (LPG) Gasoline Light Cycle Oil (LCO) Bottoms vol % vol % F F

A Full Burn 996 1326 5.3 81.9 28.8

B Full Burn 997 1291 7.1 75.4 27.4

C Partial Burn 995 1287 7.7 70.3 29.1

D Partial Burn 977 1319 8.7 74.1 24.4

This approach was adopted due to the fact that the first negative impact of the REO reduction effect is a decrease in activity of the catalyst. The second and third bullet points were methods to recover the loss in activity through either increased catalyst additions or through choosing catalyst with a higher intrinsic activity that is achieved through increased surface area. The base case for the feed types and E-cat properties are given in Table 1. Operating conditions of the four scenarios are provided in Table 2.

vol % vol % vol %

65.3 11.5 6.7

58.9 17.1 7.5

53.6 20.9 8.7

60.7 15.7 10.2

Table 2: Operating Conditions and Yields

Impact on Units Performance (Conversion) as REO is Reduced

In the first instance, the FCC simulation model was run by holding all variables constant with the exception of the rare earth levels of the catalyst. The result is a fairly smooth logarithmic curve with increasing conversion and lower bottoms yields with increasing REO levels in the catalysts (Figure 2). Therefore, as the rare earth levels decrease, conversion of feed to higher valued products will also drop.

76 75 Conversion 74 73 72 71 70 0 0.5 1 1.5 2 2.5 3

10.0 9.5 9.0 8.5 8.0 7.5 7.0 3.5 FCC Bottoms

In the case of (a), it is quite possible and often economically viable to increase catalyst additions to restore the conversion to the base case level. Figure 3 shows graphs of the amount of catalyst required to restore the unit to the base case conversion. As can be seen from the trend, when the desired decrease in REO is low to moderate (for example from 3 to 2.5 or 2 wt% REO), the objective can be achieved fairly easily. For Refineries B, C, and D this will require ~ 10% more catalyst at a rare earth level of 2% compared to the base case of 3% REO, while refinery A will require a higher level of fresh catalyst as it is operating at higher severity. However, the product slate for the same conversion may be different, and the refiners will need to check whether there may be constraints which prevent the refinery from taking a particular action.
180% Percent Of Additional Required For Constant Conversion 170% 160% 150% 140% 130% 120% 110% 100% 0 0.5 1 1.5 2 2.5 3 3.5

REO wt%
Figure 2: Conversion and bottoms changes with changing REO levels in catalyst at constant catalyst additions and constant total surface area at constant operating conditions

Restoring Conversions using either a combination of increasing catalyst additions and/or increasing activity by increasing Total Surface Area (TSA)
There are two catalytic approaches to reduce rare earth levels in the fresh catalyst and at the same time restore the unit to conversion levels of the base case (old REO level), a. Either the refiner can increase catalyst additions at lower REO levels or, b. Increase the activity via higher zeolite content as represented by total surface area of the catalyst.

REO wt%
A B C D

Figure 3: Increasing catalyst addition rate can restore conversion to base case

In case (b) catalysts with higher surface area (providing higher activity) furnish the flexibility to lower rare earth content of the catalyst and maintain performance and conversion at equal catalyst addition rates. BASF is uniquely placed to provide this technology solution through a unique manufacturing technique. BASFs in-situ technology allows the increase of TSA to a much greater extent than any other FCC catalyst

supplier as discussed above. The application of this technology depends largely on the starting point of the total surface area currently being used by the refinery. If one looks at Table 3, it can be seen if the refiner operating lower surface area, such as Refinery D, has a larger range of opportunity to reduce rare earth content than that of refiner operating with blend like Refinery A. To further understand the two above mentioned options, let us look at following example: A refiner using a catalyst with 3% REO, 325 m2/g fresh total surface area, and a daily consumption of 2 tons per day of catalyst. The refinery would like to lower catalyst costs by reformulating the catalyst to a 1.5 wt% REO. Assuming that the refinery can handle higher levels of LPG in its wet gas compressor and gas concentration system, there are three possible routes a refinery can follow to reduce REO in catalyst while maintain existing levels of conversion: a. Increase catalyst additions containing lower REO (exchanged on the zeolite). If we look at Figure 3, then the quantity of catalyst for this simulation is 20% higher. Therefore, the refinery can maintain conversion by increasing catalyst usage from 2 to 2.4 tpd but at REO level which is 50% lower than the base case b. It is also possible to reformulate the catalyst by keeping the total cat addition rate the same but increasing fresh total surface area. In this case if we look Table 3, it can be achieved by increasing the total surface area from 325 m2/g to 406 m2/g c. The third general approach is to use a combination of (a) and (b) described above. The refinery could increase cat additions by 10%, 2.2 tpd and increase total surface area of the catalyst from 325 m2/g to 350 m2/g This idealized example is to illustrate a means for addressing the problem. Of course, individual needs may be different and have to be taken into account when making the decision. In either case it is possible to combine the technology options of case (a) and (b) to meet a specific refiners FCC requirement.

TSA m2/g Case A B C D 3% REO 350 325 312 265 2.5% REO 370 344 330 291 2% REO 410 380 365 318 406 390 358 399 1.5% REO 1% REO

Table 3: Increasing catalyst fresh surface area to reduce REO for equal unit conversion at constant addition rates

Constraints
As was discussed previously, this paper addresses generic options and it is important to talk to your supplier to achieve a quality decision based on intimate knowledge of your operation needs and timing. When conversion is restored to the base case at lower REO levels, the unit necessarily produces larger amounts of LPG and lower amounts of gasoline. This is fundamentally due to the chemistry of the process. Rare earth exchanged on the zeolite will increase hydrogen transfer reaction, which will push the increased conversion towards paraffins and aromatics at the cost of reducing cycle oil naphthenes and olefins. The source of the naphthenes, which supply the hydrogen for the hydrogen transfer to take place, is usually in the light cycle oil boiling range.
LCO Naphthenes + Gasoline Ole ns LCO Aromatics + Gasoline Paraf ns

The aromaticity of the gasoline is not changed much but most of the increase in aromaticity will occur in the LCO stream thus lowering its cetane number. By reducing rare earth in the catalyst, the resulting gasoline will have a higher level of olefins, some of which will over crack making more LPG. As regards, LCO quality, lowering of REO result in quality of the LCO improving and its cetane number will tend to increase albeit marginally from a low base. Increasing the paraffinicity of LCO will also marginally increase its API gravity.

59.0 58.8 Gasoline vol % 58.6 58.4 58.2 58.0 57.8 57.6

29.2 29 28.8 28.6 LPG vol % 28.4 28.2 28 27.8 27.6 27.4 27.2 0 0.5 1 1.5 2 REO wt% 2.5 3 3.5

Economics
To assist readers in contextualizing the impact of the (continuing) rise in the price of rare earth materials, an analysis was done to show the effects of lowering rare earths in catalyst formulation while holding catalyst addition and surface area constant. The analysis was done by considering two sets of economic values as shown below in Table 4.

Stream

Units

Olefin Maximization Mode $28.19 $94.90 $55.68 $102.49 $73.42 $62.09 $92.64 $107.32 $82.00 $98.55

Gasoline Maximization Mode $28.19 $62.09 $55.68 $82.78 $73.42 $62.09 $101.69 $107.32 $82.00 $98.55

C2+ltr C3= C3
95.5 Research Octane Number 95.4 95.3 95.2 95.1 95.0 94.9 94.8 94.7 94.6

$/BFOE $/bbl $/bbl $/bbl $/bbl $/bbl $/bbl $/bbl $/bbl $/bbl

Figure 4: Graph of gasoline in vol % (blue) and LPG in vol % (green) versus REO

59.0 58.8 Gasoline vol % 58.6 58.4 58.2 58.0 57.8 57.6 0 0.5 1 1.5 2 2.5 3 3.5

C4= iC4 nC4 Gasoline LCO HCO Feed Cost

REO wt%
Figure 5: Graph of gasoline in vol % (blue) and Research Octane Number (green) versus REO

Table 4: Economic Values

From Figure 4, it can be seen that when REO is reduced from 3 wt% to 1 wt%, then gasoline decreases monotonically from 58.85 vol % to 57.7 vol %. Concomitantly, the LPG make increases from 27.4 vol % at 3 wt% REO and goes up to 29.1 vol % at a REO level of 1 wt% in the catalyst. This may not be an issue for some refinery that can handle higher LFG loads in the wet gas compressor, but for others it may be an issue to consider. In addition, as can be seen in Figure 5, the reduction in REO also drives an increase in Research Octane Number.

For the olefin maximization, the objective is to increase light olefins such as propylene and butylenes. These can be seen by comparing the prices between the olefins and gasoline mode of operation. Using the prices in Table 4 above for each mode of operation, and using the equation shown below for calculating the value created, the following conclusion was reached. As expected, maximum olefins mode occurs at the lowest rare earth levels and maximum gasoline product occurs at the highest rare earth levels. These can be seen in Figures 6 and 7, respectively.

The equation used for the net contribution after total catalyst cost: {[ (Product Prices in $/bbl)i * (vol %)i } - (Feed costing $/ bbl)]*Feed rate bbl/day} - [Catalyst cost in $/ton]*tons per day
Contribution margin in $/bbl after total catalyst cost $7.05 $7.00 $6.95 $6.90 $6.85 $6.80 $6.75 $6.70 0.00 0.50 1.00 1.50 2.00 REO wt% 2.50 3.00 3.50

REO Catalyst consumption in %/per day Additional (%) catalyst used over base to maintain conversion Savings in $/bbl

wt% Base(3) 100

2.5 105

2 112

1.5 125

1 146

12

25

46

$0.08 $0.18 $0.30 $0.38

Table 5: Constant conversion achieved by lower REO with increased catalyst addition

Figure 6: Continuous increase in value created by operating at lower rare earth levels during olefins maximization mode

$7.00 Margin after total catalyst cost in $/bbl $6.90 $6.80 $6.70 $6.60 $6.50 $6.40 0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

In the example illustrated in Table 5, it can be seen that the savings realized by lowering the rare earth levels can be substantial. Should a refinery using 5 tons per day be able to meet its objective by reducing rare earth levels from 3% to 2%, the savings would be about $1.5 million per year based on the catalyst cost of $5,000 per ton. The savings would be even greater if the catalyst cost is lower than the assumed price and correspondingly, the savings would be lower if the catalyst cost is higher than $5,000 per ton. In a similar way, our analysis indicates that in addition to supplementing activity by increasing catalyst addition, an increase in activity can be achieved by increasing the total surface area of the catalyst. When these two options are applied, a greater range of flexibility is achieved. The benefits of increased total surface area can be seen in Table 6 below. In this case, the break even cost ranges from $224 to $155 m2/g. The actual cost of catalyst is a small fraction of this amount and therefore, the savings using this approach is even higher than supplemental catalyst addition rates.

REO wt%
Figure 7: Continuous increase in value created with increasing rare earth levels during maximum gasoline mode of operation

As an alternate cost saving measure, break-even calculations are shown below. Refiners have two levers that can be actuated to achieve lower cost options for meeting their catalyst needs. In the first case, a demonstration is shown where refiners are able to trim or even substantially reduce the level of rare earths in their catalyst depending on their needs and objectives.

REO TSA Catalyst consumption in %/per day Delta Surface Area Savings in $/bbl m2/g m /g
2

Base(3) 325 100

2.5 344 100

2 380 100

1.5 406 100

Catalyst in Use Case Description Riser/ Reactor Operation Feed Rate Feed Specific Gravity @ 60/60 Catalyst Circulation Rate Regen 1 Bed Temperature Fresh Cat Make-up Rate Conversion Fresh Feed Con- wt% version (as cut) Hydrogen Methane Ethane Ethylene Propane Propylene N-Butane Isobutane Total Butenes C5 to 221 C Gasoline Light Cycle Oil, 221 to 350 C Slurry, 350+ C Coke wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt%

NaphthaMax NaphthaMax (2.8% REO, (1.8% REO, 360 TSA) 360 TSA) Projected Tonnes/ Base hr Base Tonnes/ 18.8 min C 711 Actual Base Base 20.5

19 $/bbl 0.11

55 0.22

81 0.32

Table 6: Calculation based on constant conversion achieved by increased TSA

Regenerator Operation 697 2.20

Post Audit
As part of the comprehensive technical service provided to customers, BASF provides a post audit service. The objective of the post audit is to confirm the performance of the reformulation and to assess whether there is scope for further fine tuning. Of course, should the refineries objective have changed significantly, the post audit can also help develop new strategies for the refinery to target its new priorities. An example of a post audit is given below for a European refinery that changed its catalyst formulation from a rare earth of 2.8% to 1.8%, keeping its catalyst addition the same but using a reformulated higher total surface area catalyst. After the refinery assessed the performance and felt comfortable with this new reformulation, it is looking at other options to further cut its rare earth levels. As can be seen from Table 7, the post audit was carried out after a full inventory changeover. By comparing the projected and actual yield patterns from the unit, it can be seen that the accuracy of the BASF modeling tool kit is very good. This is testament to the understanding, expertise, and experience that resides in the global technical team of BASF.

Tonnes/ 2.15 day 73.8

73.4

Product Yields Weight Percent Basis 0.09 0.17 1.56 1.14 1.32 1.84 7.32 0.95 3.71 7.57 42.95 13.79 12.53 5.19 0.08 0.15 1.54 1.11 1.32 1.76 7.65 0.95 3.78 7.82 42.08 14.41 12.18 5.17 Hydrogen Sulfide wt%

Table 7: Post audit results

BASF Technical Service

As part of BASFs standard service, all catalyst offerings undergo a review from their product selection team that includes representatives from sales, service, manufacturing and marketing. Each catalyst offer is customized to meet the objectives of the refiner; taking into consideration the specific user constraints, whether they are operational or economic. This approach allows BASFs technical sales team to deliver the best value to their customers. As a technical support follow-up after sales, BASF has instituted a regular Technical Support Services (TSS) report that is made available to all of our customers. These reports provide the refinery management with an ongoing systematic evaluation of their FCC operating conditions together with the impact of the catalyst to support the strategic direction of the FCC management.

Conclusion
In the context of the high rare earth price environment, BASF makes available critical competencies that refiners can apply to reduce operating costs associated with fresh catalyst purchase and minimize the risk of a catalyst reformulation. The process of extracting maximum benefit comes into being by the interplay of information between customer and BASF through communication, understanding, tools, and products. BASF has managed this process at the front end with heavy investments in R&D, production process and equipment to bring about best-in-class products. The process begins with the account manager fully understanding the needs of customer to reduce operating costs, as well as being fully versed regarding the operating objectives and constraints of the unit. This information is presented to the product selection

Information Flow for TSS

Operating Data
Refinery provides BASF with operating data

Process Check
Accuracy of data Mass balance closure Heat balance H2 balance

Process Analysis
E-cat data Fines analysis Scrubber water analysis Feed analysis

Operation Optimization
Create models using state-of-the-art simulation programs Compare performance against refineries using proprietary benchmarking

Final Report
BASF publishes a quarterly report with findings to ensure refinery operating and profitability targets are met

Figure 8: Information flow to support refinery operations to create maximum value

The major objective of the after sales technical service is to ensure that the catalyst formulation fits into the refinery strategic decision of optimizing its profitability on an ongoing basis. This is done to support the refinery with optimum catalyst recipe to meet the changing needs of the refinery within its operating unit, market, and logistical constraints. A quick summary of information flow for the technical support system can be seen in the Figure 8.

team, comprised of members with global experience, to select one or more products for a given set of operation conditions. Once the catalyst is selected, the product is evaluated in a proprietary FCC simulations model against the customers operating capabilities and constraints. The information gathered from simulation programs are then compared against a benchmark database to ensure practical potential reality of the selection, which the account manager then fully discloses to the customer.

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Once a decision is made by the customer, the execution of the process moves into the next phase. A heightened level of technical support is initiated where real operational data from the refinery is analyzed for consistency and accuracy. Regular and timely meetings are held with the customer accompanied by detailed reports to keep the refiner fully apprised of the unit operation, economic impacts, and constraint positions. This is to minimize surprises for the FCC management. After the total inventory has been turned over, a post audit is carried out to assess and confirm the projections. The post audit also gives the refinery the opportunity to decide if there is still further scope for improvement. Through state-of-the-art technology and a partnering approach, BASF is able to combine the benefits of selecting the optimal product, expertise, and global experience to ensure continued value creation for its customers. For the customers, this approach helps them make highly informed, high quality decisions to support the refinerys plan by minimizing risk and surprises and increasing profitability. BASF has successfully partnered with a large percentage of its customers to evaluate the rare earth content in their catalyst formulations, which has resulted in several successful reductions in rare earth. This is done through a comprehensive technical evaluation that ensures the reformulation is optimized for the specific FCC unit being evaluated. BASFs highly specialized experts work closely with the refiner throughout the process to understand unit restraints and yield objectives in order to carefully engineer the right strategy that results in the cost savings the refiner desires without unacceptably compromising the performance. Following implementation of the lower rare earth catalyst, BASF provides a post audit service to confirm catalyst performance and to identify opportunities for further refinement.

References
1. Rare Earth Supply Peaking to Surplus by 2013 Goldman, published by Dow Jones (Sydney), 05-04-2011. 2. The table was based on CMAI estimates and then modified with internal documents for estimating the FCC economics. CMAI reports are supplied by Chemical Market Associates.

Author
Solly Ismail, FCC Modeling Specialist BASF Corporation 25 Middlesex/Essex Turnpike Iselin, NJ 08830

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About Us
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