fluid catalytic cracking (fcc)

7/30/2019 Fluid Catalytic Cracking (FCC)

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Introduction

The use o rare earths in FCC catalystswas driven by the need or more activeand hydrothermally stable products withbetter yield perormance. Rare earthoxides (REO) achieved these goals byenhancing catalytic activity andpreventing loss o acid sites during

normal unit operation. To address thespecic needs o each FCC unit, catalystmanuacturers ormulate catalysts withvarious rare earth levels that allow oroptimal unit perormance. The level oREO in a specic catalyst ormulation isdetermined by operational severity andproduct objectives. As the need orincreased amounts o gasoline grewover time, reners tended to increase thelevel o rare earths in their catalyst

TechnicalNote

Fluid Catalytic Cracking (FCC)Catalyst Optimization to Copewith High Rare Earth OxidePrice Environment

ormulation to meet their protabilitytargets. Rare earth gradually increasedover the years and at the end o 2010,the average was 3%, with severalreneries running in excess o theaverage.


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2

0

5

10

15

20

25

30

35

40

45

0.5 1 1.5 2 2.5 3 3.5 4 5

NumberofSample

Counts

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

CumulativePercentof

SamplesatREOwt%

Level

REO wt%

Figure 1 shows 2010 historical data or E-cat samplesanalyzed by BASF or rare earth oxide. These refect all thesamples that were received by BASF in the ourth quarter o2010 beore the REO price spike occurred. Sample countreers to the number o E-cat samples analyzed by the BASFlaboratory. The blue trend line shows the cumulativepercentage o samples at or below a specic REO content.

Although operational demands have not changed in theindustry; current rare earth market conditions have put

pressure on catalyst manuacturers as well as reners toreassess the role o RE in the FCC industry. When looking atthe catalytic options, it is critical to look at the overall value andnot just the cost o RE. BASF has actively helped itscustomers analyze their operations and determine when adrop in RE levels is benecial. Nineteen out o sixty BASFcustomers that have looked at a low REO option haveswitched. BASFs products deliver the highest activity in themarket and thereore are well suited or low REO operation. Aswill be discussed in this article, the cost benets and possibleperormance decits o this option need to be clearlyunderstood beore making a change.

REO Supply-Demand Balance

The supply-demand balance o the global rare earth marketbecame disconnected when China, which produces 95% othe worlds supply o rare earths, severely cut its export quotain July 2010. China is not expected to change its position,despite the World Trade Organizations warning that reluctancto share its rare earth supplies constitutes a violation o theglobal trade rules. Export quotas or the second hal o 2011,recently released, indicate a signicant increase over the 2010

numbers. On close examination, the new quotas reveal thatnothing has changed as the new gures merely include erroualloys. These were not part o the quota in 2010. Marketexpectations are that price volatility will continue until newsuppliers enter the market and re-establish the supply-demand balance. In a recent research note issued byGoldman Sachs1, prices are likely to rise in the short term,over the next 18 months, and then soten in the 2013 to 2015period. This sotening o rare earth prices will most likely bedue to additional capacity coming online rom non-Chinesesources that are expected to signicantly shit the supplypicture in the coming years.

Figure 1: Distribution o REO in FCC catalyst samples


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During the interim period, until rare earth prices once againnormalize, the rening industry is looking or ways to addressthe increase in catalyst costs within its current budgetaryconstraints. Instinctively, the drive is to opt or lower rare earthcatalyst ormulations to oset the costs o the raw material.While this action can have an immediate and successulimpact on the operating budget, it may not be the bestdecision or the renery. Understanding the constraints o aspecic FCC unit is critical to making the optimal economic

decision. BASF has proactively worked with its customers toexamine low rare earth catalytic options that t the needs othe specic users.

Technological Dierences

While all catalyst companies can oer catalyst products withlower levels o REO, BASF is the only company that can oerits customers an option o increasing activity, and therebymaintaining conversion at constant catalyst addition, due to anincrease in zeolite content as represented by active andselective total surace area. BASF employs in-situ technology,which is particularly well suited or this application. The in-situprocess begins with a catalyst-sized microsphere. The ensuingstep consists o growing the zeolite crystal within themicrosphere. The zeolite in-situ process serves two unctions;it provides the active and selective area, as well as providingthe strength imparted to the microsphere.

This technology is distinct rom the incorporated technologypracticed by all other catalyst suppliers. With incorporatedtechnology, a single particle is ormed consisting o anadmixture o clay, zeolite, and binder. As this technology isalready optimized, addition o substantial amounts o zeolitewill require reducing either the clay or binder. The incorporatedcatalyst technique is inherently limited to an upper level ozeolite content and cannot increase surace area without

seriously compromising the strength to withstand breakage inthe FCC unit.

The decision to change catalyst or reormulate catalyst is not trivial one. Simply reducing rare earth levels o the catalystwithout a comprehensive study can result in severe yieldpenalties and possibly orce the renery to cut eed rates tothe unit. All such consequences are economically prohibitive.Helping customers evaluate the eect o rare earth level on kecatalytic variables reduces the uncertainty o the change andacilitates the decision to move to a reormulation o their FCCcatalyst, when appropriate. The specics o this change in

ormulation and the impact o REO level on conversion, as weas the eect o resh catalyst surace area and addition rate,will be examined in this paper.

How Rare Earth AectsFCC Catalyst Perormance

When considering a move to reduce REO component in thecatalyst, it is critical to grasp the perormance shits andeconomic impact o such a change. The economic impactcomprises two aspects. It is a unction o total catalyst costand the value created rom a given catalyst ormulation.Reducing the rare earth level will have an immediate cost

saving, but this calculation alone will not give the true protgeneration picture i the margin benets rom the yield slate anot included. To illustrate the impact o such change on keycatalytic perormance indicators, a proprietary FCC simulationmodel was used to study the eects o REO level, catalystaddition rate, and resh surace area or FCC units operatingwith the ollowing eedstocks.

nHydrotreated Vacuum Gas Oil (VGO) - Renery AnStandard VGO - Renery Bn Moderate Resid - Renery Cn Heavy Resid - Renery D


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Our choice in selecting the above eedtypes is to provide an analysis thatcovers the whole range o eed diets(types) used in FCC operations. Thebase case or all cases was 3% REO inthe catalyst. As seen rom Figure 1, thiswas the average level o rare earths usedin 155 FCC units. For each operation,the REO level was changed to model the

ollowing scenarios:

n Impact o REO level on conversion, atconstant catalyst addition rates andunit conditions

n Impact o resh catalyst addition rate,to restore base case conversion atconstant unit conditions

n Eect o increasing resh catalystsurace area, at constant catalystaddition rates and unit conditions

This approach was adopted due to theact that the rst negative impact o theREO reduction eect is a decrease inactivity o the catalyst. The second andthird bullet points were methods torecover the loss in activity through eitherincreased catalyst additions or throughchoosing catalyst with a higher intrinsicactivity that is achieved throughincreased surace area.

The base case or the eed types andE-cat properties are given in Table 1.

Operating conditions o the ourscenarios are provided in Table 2.

Table 1: Feed and Equilibrium Catalyst Properties or Base Cases

Table 2: Operating Conditions and Yields

Refnery A B C D

API 26.3 22 22.1 20.1

Concarbon wt% 0.3 0.3 0.9 4.5

Sulur wt% 0.5 0.7 0.5 0.4

Basic N2 wt% 0.03 0.05 0.04 0.04

Distillation

% 650 F - 15 20 7 4

% 1000 F +


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Impact on Units Perormance (Conversion)as REO is Reduced

In the rst instance, the FCC simulation model was run byholding all variables constant with the exception o the rareearth levels o the catalyst. The result is a airly smoothlogarithmic curve with increasing conversion and lowerbottoms yields with increasing REO levels in the catalysts(Figure 2). Thereore, as the rare earth levels decrease,conversion o eed to higher valued products will also drop.

Restoring Conversions using either acombination o increasing catalyst additionsand/or increasing activity by increasing Total

Surace Area (TSA)There are two catalytic approaches to reduce rare earth levelsin the resh catalyst and at the same time restore the unit toconversion levels o the base case (old REO level),

a. Either the rener can increase catalyst additions at lowerREO levels or,

b. Increase the activity via higher zeolite content asrepresented by total surace area o the catalyst.

In the case o (a), it is quite possible and oten economicallyviable to increase catalyst additions to restore the conversionto the base case level. Figure 3 shows graphs o the amounto catalyst required to restore the unit to the base caseconversion. As can be seen rom the trend, when the desireddecrease in REO is low to moderate (or example rom 3 to 2or 2 wt% REO), the objective can be achieved airly easily. FoReneries B, C, and D this will require ~ 10% more catalyst ata rare earth level o 2% compared to the base case o 3%

REO, while renery A will require a higher level o resh catalysas it is operating at higher severity. However, the product slateor the same conversion may be dierent, and the reners wilneed to check whether there may be constraints whichprevent the renery rom taking a particular action.

In case (b) catalysts with higher surace area (providing higheractivity) urnish the fexibility to lower rare earth content o thecatalyst and maintain perormance and conversion at equalcatalyst addition rates. BASF is uniquely placed to providethis technology solution through a unique manuacturingtechnique. BASFs in-situ technology allows the increase o

TSA to a much greater extent than any other FCC catalyst

Figure 2: Conversion and bottoms changes with changing REO levels

in catalyst at constant catalyst additions and constant total surace

area at constant operating conditions

Figure 3: Increasing catalyst addition rate can restore conversion to

base case

100%

110%

120%

130%

140%

150%

160%

170%

180%

0 0.5 1 1.5 2 2.5 3 3.5

REO wt%

PercentOfAddi

tionalRequired

ForConstant

Conversion

A B C D

76

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74

73

72

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70

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7.0

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Conversion

FCC

Bottoms

REO wt%


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supplier as discussed above. The application o thistechnology depends largely on the starting point o the totalsurace area currently being used by the renery. I one looksat Table 3, it can be seen i the rener operating lower suracearea, such as Renery D, has a larger range o opportunity toreduce rare earth content than that o rener operating withblend like Renery A.

To urther understand the two above mentioned options, let us

look at ollowing example: A rener using a catalyst with 3%REO, 325 m2/g resh total surace area, and a dailyconsumption o 2 tons per day o catalyst. The renery wouldlike to lower catalyst costs by reormulating the catalyst to a1.5 wt% REO. Assuming that the renery can handle higherlevels o LPG in its wet gas compressor and gas concentrationsystem, there are three possible routes a renery can ollow toreduce REO in catalyst while maintain existing levels oconversion:

a. Increase catalyst additions containing lower REO(exchanged on the zeolite). I we look at Figure 3, then thequantity o catalyst or this simulation is 20% higher.

Thereore, the renery can maintain conversion byincreasing catalyst usage rom 2 to 2.4 tpd but at REO levelwhich is 50% lower than the base case

b. It is also possible to reormulate the catalyst by keeping thetotal cat addition rate the same but increasing resh totalsurace area. In this case i we look Table 3, it can beachieved by increasing the total surace area rom 325 m2/gto 406 m2/g

c. The third general approach is to use a combination o (a)and (b) described above. The renery could increase catadditions by 10%, 2.2 tpd and increase total surace area othe catalyst rom 325 m2/g to 350 m2/g

This idealized example is to illustrate a means or addressingthe problem. O course, individual needs may be dierent andhave to be taken into account when making the decision. Ineither case it is possible to combine the technology options ocase (a) and (b) to meet a specic reners FCC requirement.

Constraints

As was discussed previously, this paper addresses genericoptions and it is important to talk to your supplier to achieve aquality decision based on intimate knowledge o youroperation needs and timing.

When conversion is restored to the base case at lower REOlevels, the unit necessarily produces larger amounts o LPG

and lower amounts o gasoline. This is undamentally due tothe chemistry o the process. Rare earth exchanged on thezeolite will increase hydrogen transer reaction, which will pusthe increased conversion towards parans and aromatics atthe cost o reducing cycle oil naphthenes and olens. Thesource o the naphthenes, which supply the hydrogen or thehydrogen transer to take place, is usually in the light cycle oilboiling range.

The aromaticity o the gasoline is not changed much but mos

o the increase in aromaticity will occur in the LCO stream thulowering its cetane number. By reducing rare earth in thecatalyst, the resulting gasoline will have a higher level oolens, some o which will over crack making more LPG. Asregards, LCO quality, lowering o REO result in quality o theLCO improving and its cetane number will tend to increasealbeit marginally rom a low base. Increasing the paranicity oLCO will also marginally increase its API gravity.

TSA m2/g

Case 3%REO

2.5%REO

2%REO

1.5%REO

1%REO

A 350 370 410

B 325 344 380 406

C 312 330 365 390

D 265 291 318 358 399

Table 3: Increasing catalyst resh surace area to reduce REO or

equal unit conversion at constant addition rates

LCO Naphthenes +

Gasoline Olens

LCO Aromatics +

Gasoline Parafn


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From Figure 4, it can be seen that when REO is reduced rom

3 wt% to 1 wt%, then gasoline decreases monotonically rom58.85 vol % to 57.7 vol %. Concomitantly, the LPG makeincreases rom 27.4 vol % at 3 wt% REO and goes up to29.1 vol % at a REO level o 1 wt% in the catalyst. This maynot be an issue or some renery that can handle higher LFGloads in the wet gas compressor, but or others it may bean issue to consider. In addition, as can be seen in Figure 5,the reduction in REO also drives an increase in ResearchOctane Number.

Economics

To assist readers in contextualizing the impact o the(continuing) rise in the price o rare earth materials, an analysiswas done to show the eects o lowering rare earths incatalyst ormulation while holding catalyst addition and suracearea constant.

The analysis was done by considering two sets o economicvalues as shown below in Table 4.

Figure 4: Graph o gasoline in vol % (blue) and LPG

in vol % (green) versus REO

Figure 5: Graph o gasoline in vol % (blue) and Research Octane

Number (green) versus REO

Table 4: Economic Values

Stream Units OlefnMaximization

Mode

GasolineMaximization

Mode

C2+ltr $/BFOE $28.19 $28.19

C3= $/bbl $94.90 $62.09

C3 $/bbl $55.68 $55.68

C4= $/bbl $102.49 $82.78

iC4 $/bbl $73.42 $73.42

nC4 $/bbl $62.09 $62.09

Gasoline $/bbl $92.64 $101.69

LCO $/bbl $107.32 $107.32

HCO $/bbl $82.00 $82.00

Feed Cost $/bbl $98.55 $98.55

For the olen maximization, the objective is to increase lightolens such as propylene and butylenes. These can be seenby comparing the prices between the olens and gasolinemode o operation. Using the prices in Table 4 above or eachmode o operation, and using the equation shown below orcalculating the value created, the ollowing conclusion wasreached. As expected, maximum olens mode occurs at thelowest rare earth levels and maximum gasoline product occurat the highest rare earth levels. These can be seen in Figures and 7, respectively.

57.6

57.8

58.0

58.2

58.4

58.6

58.8

59.0

0 0.5 1 1.5 2 2.5 3 3.5

27.2

27.4

27.6

27.8

28

28.2

28.4

28.6

28.8

29

29.2

Gasolinevol% L

PGvol%

REO wt%

57.6

57.8

58.0

58.2

58.4

58.6

58.8

59.0

0 0.5 1 1.5 2 2.5 3 3.5

94.6

94.7

94.8

94.9

95.0

95.195.2

95.3

95.4

95.5 ResearchOctaneNumber

Gasolinevol%

REO wt%


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The equation used or the net contribution atertotal catalyst cost:

{[ (Product Prices in $/bbl)i* (vol %)

i} - (Feed costing $/

bbl)]*Feed rate bbl/day} - [Catalyst cost in $/ton]*tons per day

As an alternate cost saving measure, break-even calculationsare shown below. Reners have two levers that can beactuated to achieve lower cost options or meeting theircatalyst needs. In the rst case, a demonstration is shownwhere reners are able to trim or even substantially reduce thelevel o rare earths in their catalyst depending on their needsand objectives.

In the example illustrated in Table 5, it can be seen that thesavings realized by lowering the rare earth levels can besubstantial. Should a renery using 5 tons per day be able to

meet its objective by reducing rare earth levels rom 3% to 2%the savings would be about $1.5 million per year based on thcatalyst cost o $5,000 per ton. The savings would be evengreater i the catalyst cost is lower than the assumed price ancorrespondingly, the savings would be lower i the catalystcost is higher than $5,000 per ton.

In a similar way, our analysis indicates that in addition tosupplementing activity by increasing catalyst addition, anincrease in activity can be achieved by increasing the totalsurace area o the catalyst. When these two options areapplied, a greater range o fexibility is achieved. The benetso increased total surace area can be seen in Table 6 below.

In this case, the break even cost ranges rom $224 to $155m2/g. The actual cost o catalyst is a small raction o thisamount and thereore, the savings using this approach is evehigher than supplemental catalyst addition rates.

$6.70

$6.75

$6.80

$6.85

$6.90

$6.95

$7.00

$7.05

0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Contributionmarginin$/bbl

aftertotalcatalystcost

REO wt%

Figure 6: Continuous increase in value created by operating at lower

rare earth levels during olefns maximization mode

Table 5: Constant conversion achieved by lower REO with increased

catalyst addition

REO wt% Base(3) 2.5 2 1.5 1

Catalystconsumptionin %/per day

100 105 112 125 146

Additional(%) catalystused over

base tomaintainconversion

% 5 12 25 46

Savings in$/bbl

$0.08 $0.18 $0.30 $0.3

$6.40

$6.50

$6.60

$6.70

$6.80

$6.90

$7.00

0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Marginaftertotal

catalystcostin$/bbl

REO wt%

Figure 7: Continuous increase in value created with increasing rare

earth levels during maximum gasoline mode of operation


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Post Audit

As part o the comprehensive technical service provided tocustomers, BASF provides a post audit service. The objectiveo the post audit is to conrm the perormance o thereormulation and to assess whether there is scope or urther

ne tuning. O course, should the reneries objective havechanged signicantly, the post audit can also help developnew strategies or the renery to target its new priorities.

An example o a post audit is given below or a Europeanrenery that changed its catalyst ormulation rom a rare eartho 2.8% to 1.8%, keeping its catalyst addition the same butusing a reormulated higher total surace area catalyst. Aterthe renery assessed the perormance and elt comortablewith this new reormulation, it is looking at other options tourther cut its rare earth levels.

As can be seen rom Table 7, the post audit was carried out

ater a ull inventory changeover. By comparing the projectedand actual yield patterns rom the unit, it can be seen that theaccuracy o the BASF modeling tool kit is very good. This istestament to the understanding, expertise, and experiencethat resides in the global technical team o BASF.

REO Base(3) 2.5 2 1.5

TSA m2/g 325 344 380 406

Catalystconsumption in%/per day

100 100 100 100

Delta SuraceArea

m2/g 19 55 81

Savings in$/bbl

$/bbl 0.11 0.22 0.32

Riser/ Reactor Operation

Feed Rate Tonnes/hr

Base Base

Feed SpecicGravity @ 60/60

Base Base

CatalystCirculation Rate

Tonnes/

min18.8 20.5

Regenerator Operation

Regen 1 BedTemperature

C 711 697

Fresh CatMake-up Rate

Tonnes/

day2.15 2.20

Conversion

Fresh Feed Con-version (as cut)

wt% 73.8 73.4

Product Yields Weight Percent Basis

Hydrogen wt% 0.09 0.08

Hydrogen Sulde wt% 0.17 0.15

Methane wt% 1.56 1.54

Ethane wt% 1.14 1.11

Ethylene wt% 1.32 1.32

Propane wt% 1.84 1.76

Propylene wt% 7.32 7.65

N-Butane wt% 0.95 0.95

Isobutane wt% 3.71 3.78

Total Butenes wt% 7.57 7.82

C5 to 221 CGasoline

wt% 42.95 42.08

Light Cycle Oil,221 to 350 C

wt% 13.79 14.41

Slurry, 350+ C wt% 12.53 12.18

Coke wt% 5.19 5.17

Table 6: Calculation based on constant conversion achieved by

increased TSA

Table 7: Post audit results

Catalyst in Use

NaphthaMax

(2.8% REO,360 TSA)

NaphthaMax

(1.8% REO,360 TSA)

Case Description Projected Actual


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BASF Technical Service

As part o BASFs standard service, all catalyst oeringsundergo a review rom their product selection team thatincludes representatives rom sales, service, manuacturingand marketing. Each catalyst oer is customized to meet theobjectives o the rener; taking into consideration the specicuser constraints, whether they are operational or economic.

This approach allows BASFs technical sales team to deliverthe best value to their customers.

As a technical support ollow-up ater sales, BASF hasinstituted a regular Technical Support Services (TSS) reportthat is made available to all o our customers. These reportsprovide the renery management with an ongoing systematicevaluation o their FCC operating conditions together with theimpact o the catalyst to support the strategic direction o theFCC management.

Conclusion

In the context o the high rare earth price environment, BASFmakes available critical competencies that reners can applyto reduce operating costs associated with resh catalystpurchase and minimize the risk o a catalyst reormulation. Thprocess o extracting maximum benet comes into being bythe interplay o inormation between customer and BASFthrough communication, understanding, tools, and products.

BASF has managed this process at the ront end with heavyinvestments in R&D, production process and equipment tobring about best-in-class products. The process begins withthe account manager ully understanding the needs ocustomer to reduce operating costs, as well as being ullyversed regarding the operating objectives and constraints othe unit. This inormation is presented to the product selection

Inormation Flow or TSS

Operating DataRefnery provides

BASF with operating

data

Process CheckAccuracy o data

Mass balance closure

Heat balance

H2 balance

Process AnalysisE-cat data

Fines analysis

Scrubber water analysis

Feed analysis

Operation OptimizationCreate models using

state-o-the-art

simulation programs

Compare perormance

against refneries using

proprietary benchmarking

Final ReportBASF publishes a

quarterly report with

fndings to ensure

refnery operating and

proftability targets

are met

The major objective o the ater sales technical service is to

ensure that the catalyst ormulation ts into the renerystrategic decision o optimizing its protability on an ongoingbasis. This is done to support the renery with optimumcatalyst recipe to meet the changing needs o the renerywithin its operating unit, market, and logistical constraints.

A quick summary o inormation fow or the technical supportsystem can be seen in the Figure 8.

team, comprised o members with global experience, to selec

one or more products or a given set o operation conditions.Once the catalyst is selected, the product is evaluated in aproprietary FCC simulations model against the customersoperating capabilities and constraints. The inormationgathered rom simulation programs are then compared againsa benchmark database to ensure practical potential reality othe selection, which the account manager then ully disclosesto the customer.

Figure 8: Information ow to support renery operations to create maximum value


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Once a decision is made by the customer, the execution o theprocess moves into the next phase. A heightened level otechnical support is initiated where real operational data romthe renery is analyzed or consistency and accuracy. Regularand timely meetings are held with the customer accompaniedby detailed reports to keep the rener ully apprised o the unitoperation, economic impacts, and constraint positions. This isto minimize surprises or the FCC management.

Ater the total inventory has been turned over, a post audit iscarried out to assess and conrm the projections. The postaudit also gives the renery the opportunity to decide i there isstill urther scope or improvement. Through state-o-the-arttechnology and a partnering approach, BASF is able tocombine the benets o selecting the optimal product,expertise, and global experience to ensure continued valuecreation or its customers. For the customers, this approachhelps them make highly inormed, high quality decisions tosupport the renerys plan by minimizing risk and surprises andincreasing protability.

BASF has successully partnered with a large percentage o its

customers to evaluate the rare earth content in their catalystormulations, which has resulted in several successulreductions in rare earth. This is done through a comprehensivetechnical evaluation that ensures the reormulation is optimizedor the specic FCC unit being evaluated. BASFs highlyspecialized experts work closely with the rener throughoutthe process to understand unit restraints and yield objectivesin order to careully engineer the right strategy that results inthe cost savings the rener desires without unacceptablycompromising the perormance. Following implementation othe lower rare earth catalyst, BASF provides a post auditservice to conrm catalyst perormance and to identiyopportunities or urther renement.

Reerences

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 modiedwith internal documents or estimating the FCC economicsCMAI reports are supplied by Chemical Market Associates

Author

Solly Ismail, FCC Modeling SpecialistBASF Corporation25 Middlesex/Essex TurnpikeIselin, NJ 08830


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fluid catalytic cracking (fcc)

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