catalagram no. 111 / spring 2012/ww w.grace · 2014. 4. 3. · 1000/2000 2000/3000 z-21 reusy...

No. 111 / Spring 2012 / www.grace.com

A Catalysts Technologies Publication

®Catalagram

Rare-earth price inflation is a serious issue facing the global refining industry.

Grace, with our long history of innovation and strong R&D, leads the industry

with the first line of commercially successful zero/low rare-earth FCC catalysts:

the REpLaCeR® family.

Launched in the first quarter of 2011, the REpLaCeR® family includes five new

catalysts for both hydrotreated and resid feed processing with zero and low

rare-earth content. The REpLaCeR® family of catalysts utilizes proprietary

zeolites and state-of-the-art stabilization methods to deliver performance similar

to current rare-earth-based FCC technologies.

We’re also investing in our plants to bring these products to the refining industry

quickly and globally.

So if you’re concerned about rare-earth pricing and availability, but need optimal

FCC performance, call the technical experts at Grace. We’ll customize a solution

using one of our new zero/low rare-earth catalysts that delivers the yields you expect.

REp R®

Worried about the cost of rare earth?Grace has the solution:

Grace Catalysts Technologies7500 Grace DriveColumbia, MD USA 21044+1.410.531.4000

www.grace.comwww.e-catalysts.com

Catalagram 111ISSUE 2012

Managing Editor:Joanne Deady

Technical Editor:Rosann Schiller

Contributors:Colin Baillie

Eric Griesinger

David Hunt

Sudhakar Jale

Rosann Schiller

Stuart Kipnis

Greg Rosinski

Chuck Olsen

Brian Watkins

Guest Contributors:Ron Colwell

Doug Jergenson

Montana Refining Company

Please address your comments to:[email protected]

Grace CatalystsTechnologies7500 Grace DriveColumbia, MD 21044410.531.4000

Our main color illustration on the front is an

original watercolor of Montana Refining,

done by Frederick, MD artist Mick Williams.

© 2012 W. R. Grace & Co.-Conn.

No. 111 / Spring 2012 / www.grace.com

A Catalysts Technologies Publication

®Catalagram2 Alternatives to Rare Earth - Commercial Evaluation ofREpLaCeR® FCC Catalysts at Montana Refining Company

12 Maximize Distillate Yield to Meet Growing Market Demand

15Improve Wet Gas Scrubber Economics with Super DESOX®Additives

18

People on the Move

19

Grace Upgrades Ecat Test Laboratory in North America

EditorialA new year is upon us and the refining industry is again faced with significant challenges in 2012.

Last year all of us were consumed by the rapid inflation in rare-earth price and the impact on our

businesses. This year, capacity rationalization is occurring at a similar rapid pace. Growth in

transportation fuels demand is shifting the base to the emerging regions, where new mega-refining

projects have recently started up or are under construction. Refiners in mature markets, particularly

those around the Atlantic basin will be at an economic disadvantage relative to the new players;

already we have seen several large facilities along the East Coast shutdown due to poor margins.

And for the first time, the US became a net exporter of gasoline in 2011 due to declining demand

domestically.

So what does it mean? It means that we are operating in a truly global marketplace, where to

compete and maintain profit margin, you need the right catalyst at the right time to make the right

products. This issue of the Catalagram® highlights various ways that we can help you stay

competitive by either reducing your exposure to rare-earth price, using our products to reduce your

commodity chemical spend or maximizing the yield of diesel in your refinery.

This isn’t our first challenge and it won’t be the last but the team at Grace is dedicated to helping you

achieve success with innovative catalytic solutions from our broad catalyst portfolio. Our new

organization, which is described in the “People on the Move” article in this issue, is as focused as

ever at working towards a total Grace solution for your refinery, leveraging our expertise in FCC and

HPC to drive your profitability in the right direction.

Sincerely,

Rosann K. Schiller

Senior Marketing Manager

Grace Catalysts Technologies

17

Maximize Yields of High Quality Diesel

Improve Contaminant Metals Flushing with TITAN™

16

Alternatives to Rare Earth

Ron ColwellEngineering Manager

Doug JergensonOperations Manager

Montana RefiningCompanyGreat Falls, MT, USA

David HuntFCC TechnicalManager

GraceHouston, TX, USA

Sudhakar JaleFCC MarketingManager

GraceColumbia, MD, USA

Emery UdvariNational TechnicalSales Manager

GraceAurora, CO, USA

AbstractAfter the sweeping reduction of Chinese export quotas, rare-earth metals experienced price hyperinflation in

the range of 2700% between August 2010 and July 2011. FCC catalyst has experienced unprecedented in-

flation as a result. Rare earth is used to stabilize FCC catalyst zeolite in order to provide high FCC catalyst

activity, liquid selectivities and superior coke selectivity. Removing rare earth from FCC catalyst will provide

relief in catalyst expenses; however, it is not an economical solution in most FCC operations due to a lower

activity and product value.

Alternate materials and processing must be used to stabilize the FCC zeolite to ensure a profitable yield

slate without rare earth. Grace has recently developed and commercialized its new REpLaCeR® family of

catalysts, a portfolio of low and zero rare-earth catalysts applicable to a broad range of FCC applications.

Presently, over 50 units worldwide use REpLaCeR® FCC technology.

Montana Refining Company (MRC) partnered with Grace to commercialize a rare-earth-free REMEDY™

catalyst from Grace’s new REpLaCeR® family of catalysts. MRC has successfully applied a zero rare-earth

REMEDY™ over a moderate rare earth GENESIS® FCC catalyst. Commercial results demonstrate similar

unit conversion at similar catalyst additions. Coke selectivity and slurry cracking were maintained with REM-

EDY™ while gasoline selectivity increased.

MRC is an independent refiner located in Great Falls, MT. Sour heavy crudes are processed in their com-

plex refinery producing low sulfur gasoline, ultra-low sulfur diesel, jet and a full slate of asphalt products.

W.R. Grace & Co. is the world’s leading supplier of FCC catalysts and additives with headquarters in

Columbia, MD.

2 Issue No. 111 / 2012

Commercial Evaluation of REpLaCeR® FCC Catalystsat Montana Refining Company

Grace Catalysts Technologies Catalagram® 3

REpLaCeR® TechnologyGrace’s zero and low rare-earth REpLaCeR® catalyst portfolio

quickly gained momentum in 2011. The explosive growth of the tech-

nology was sparked by rare-earth hyperinflation stemming from Chi-

nese export quota restrictions in 2010.1

Grace’s REpLaCeR® technologies include zero and low rare-earth

catalysts for all FCC applications.2 Today there are over 50 applica-

tions of REpLaCeR® technologies ranging from low to moderate

metal vacuum gas oil (VGO) applications to operations with high

metals residual feedstocks. Those REpLaCeR® applications are de-

TABLE 1: REpLaCeR® Catalyst Commercial Successes

scribed in Table 1. In over 20 current REpLaCeR® applications, all of

the rare earth has been removed from the FCC catalyst. These ap-

plications range from low metals to as high as 4700 ppm Ni plus V.

For higher metals operations, 20 to 80% of the rare earth can be

eliminated with REpLaCeR® catalyst. Some current resid applica-

tions are operating with Ecat Ni plus V levels greater than 10,000

ppm and V plus Na levels higher than 9,000 ppm.

The purpose of zeolite stabilization is to preserve acid site density

and control catalyst activity and product selectivities. Rare earth has

been traditionally used to stabilize the zeolite by controlling de-alu-

mination, which increases hydrogen transfer and activity.3

Unit cell size (UCS), as measured by x-ray diffraction, is a common

benchmark to judge zeolite stabilization and acid site density. Until

recently, rare earth was the most cost effective material to stabilize

the zeolite. Now Grace is using alternative materials and processing

to stabilize the zeolite to achieve desired catalyst activity, stability

and selectivity without rare earth.

Grace’s current catalyst portfolio is described in Figure 1. The RE-

pLaCeR® catalysts are the grades listed in blue. Catalysts listed on

the far left are high zeolite to matrix catalysts while the low zeolite to

matrix catalysts are shown on the right. Catalysts listed in the mid-

dle, such as GENESIS®, incorporate a combination of technologies

and provide excellent coke selectivity and slurry cracking.

ApplicationNo.

% REReduction Ni + V, ppm V + Na, ppm

1 100 56 2,700

4 100 250 3,500

22 100 2373 5,276

23 100 4743 5,466

24 80 1798 4,714

25 80 8263 9,478

47 30 8229 7,759

52 20 11195 5,810

Figure 1: Grace Has the Broadest Catalyst Portfolio in the Industry – [REpLaCeR® Technologies Shown in Blue]

ALCYON®

Ultra High Activity

GENESIS®XTNext GenerationFlexibilty for Resid Feeds

GENESIS®LXFormulation Flexibilty forOptimum Activity and Coke

MIDAS®

Max Bottoms Reduction

ALCYON® MHigh Activity High MSA

IMPACT®

Metals Trap Technologyfor Resid Feeds

GENESIS®

Ultimate FormulationFlexibility

RESID MXMax Metals Tolerance

REACTORTM

Z-22 Technology forHigher Olefins

REDUCERTM

Low RE Technologyfor Resid Feeds

REBELTM

Z-21 Technology forBottoms Reduction

REMEDYTM

Low RE Technologyfor VGO Feeds

REp R®

Resid

HeavyFeeds

VGO/HT

LightFeeds

High Zeolite Activity Low Zeolite Activity

Family in BLUE

AURORA®

Low Coke and GasVGO Feeds

ResidUltraTM

Next Generation MetalsTrap Technology

4 Issue No. 111 / 2012

catalysts. Zeolites, especially, possess heterogeneous acid sites of

discrete strengths which can be identified by measuring ammonia

desorption.

Z-21 provides higher total acidity than the RE USY zeolite catalyst.

Z-22 zeolite has less total acidity than Z-21, but similar acidity as

the RE USY with 3% RE/Z. The relative acidity of the catalyst

shown in Figure 3 is consistent with the iC4= selectivity ranking

shown in Figure 2.

Figures 2 and 3 suggest that the proprietary materials and process-

ing used for Z-21 and Z-22 zeolite provide similar hydrogen transfer

activity as a traditional rare-earth system.

Rare earth has also been used to control zeolite surface area sta-

bility especially in high metals applications. Zeolite stability is

commonly judged by zeolite surface area retention, the ratio of de-

REMEDY™ technology is zero or low rare-earth catalyst designed

for VGO applications. REDUCER® catalysts incorporate low levels

of rare earth for FCC units that process high metals residual FCC

feedstocks.

Two principal zero rare-earth catalysts that can be used in Grace’s

REMEDY™ technology are REACTOR® and REBEL™ catalysts.

REACTOR® is a zero rare-earth catalyst which incorporates Grace’s

Z-22 zeolite. Relative to rare earth ultra stable Y zeolite (RE USY),

Z-22 provides equivalent activity, higher LPG olefins and gasoline

octane as a moderately exchanged rare earth zeolite. A proprietary

stabilization process is used to provide zeolite acidity and preserve

activity similar to what has traditionally been accomplished by rare

earth.2

REACTOR® catalyst is high zeolite to matrix catalyst from Grace’s

Alumina-Sol catalyst platform. As a Grace Alumina-Sol catalyst, RE-

ACTOR® will provide excellent yield selectivities, low attrition index

and flue gas stack particulates similar to other Grace Alumina-Sol

catalysts such as AURORA® and IMPACT®.4

REBEL™ is a zero rare-earth, low zeolite to matrix catalyst formu-

lated with Z-21 zeolite. REBEL™ is an extension of Grace’s indus-

try leading bottoms cracking MIDAS® catalysts. Z-21 also uses a

distinctive proprietary zeolite stabilization process to provide neces-

sary activity and yield selectivities without rare earth.2

Isobutylene, iC4=, selectivity is a common benchmark to judge hy-

drogen transfer activity. Figure 2 shows the relative iC4= selectivity of

two catalysts with RE USY zeolites together with rare-earth free cat-

alysts, one using Z-21 and the other Z-22 zeolite. This data was

generated in an Advanced Cracking Evaluation Unit (ACE) using

metals free deactivated catalysts.5

The catalyst with an 8% rare earth on zeolite RE USY (8% RE/Z

corresponding to a UCS of ~24.31Å) produces the lowest iC4= selec-

tivity and hence the highest hydrogen transfer activity. Isobutylene

selectivity was the highest from the 3% rare earth on zeolite catalyst

(3% RE/Z corresponding to a ~UCS of ~24.27Å).

The catalyst using Z-21 provided similar iC4= selectivity as the cata-

lyst with 8% RE/Z. The high hydrogen transfer activity exhibited by

the Z-21 zeolite suggests similar acid site density and zeolite stabi-

lization as the 8% RE/Z base catalyst. Z-22 zeolite, which is used in

the REACTOR® catalyst, provided slightly less iC4= selectivity than

the 3% rare earth on zeolite catalyst, confirming slightly higher acid

site density for the Z-22 system.

Figure 3 shows total acidity for catalysts with a 3% RE/Z USY zeo-

lite, Z-21 and Z-22 zeolites. Total acidity was measured by a NH3-

STPD technique. STPD method (Stepwise Temperature

Programmed Desorption) can be used to differentiate acid site

density in aluminas, clay, zeolites, fresh catalysts, and deactivated

Conversion, wt.%

Z-22 REUSY- 8 wt.% RE/Z

REUSY- 3 wt.% RE/Z Z-21

iC4=

,wt.

%

3

2.8

2.6

2.4

2.2

275 76 77 78 79 80 81

FIGURE 2: Alternative Zeolite Stabilization MethodsDeliver Similar Hydrogen Transfer Activity asRare-Earth Based Systems

9.0E-06

8.0E-06

7.0E-06

6.0E-06

5.0E-06

4.0E-06

3.0E-06

2.0E-06

1.0E-06

0.0E+00REUSY, 3% RE/Z Z-21 Z-22

Zeolite Type

Tota

lAci

dity

,(m

ol/g

)

FIGURE 3: Total Acidity is Comparable for FCCCatalysts with RE USY, Z-21 and Z-22 Zeolites


Deactivation Metal Levels (Ni/V ppm)

0 50/1000

ZS

AR

eten

tio

n

50%

45%

40%

35%

30%1000/2000 2000/3000

RE USYZ-21

FIGURE 4: Z-21 Provides Similar Zeolite Retention asRE USY

Deactivation Metal Levels (Ni/V ppm)

RE USYZ-22

0 1000/2000 2000/4000

ZS

AR

eten

tio

n

65%

60%

55%

50%

70%

FIGURE 5: Z-22 Delivers Greater Zeolite Stabilitythan a RE USY Formulation

activated zeolite surface area to fresh zeolite surface area, as a

function of deactivation temperature and contaminant metals. Fig-

ure 4 shows zeolite surface area retention for REBEL™ with Z-21

compared with a MIDAS® catalyst with 8% RE/Z as a function of

contaminant metals. Rare-earth free REBEL™ with Z-21 zeolite

provides similar zeolite surface area retention as MIDAS® with a

RE USY zeolite.

In Figure 5, a similar comparison of zeolite surface area retention is

made between rare-earth free REACTOR® with Z-22 zeolite vs. an

AURORA® catalyst with approximately 4% RE/Z. In this Figure, Z-22

provides a slight improvement in zeolite stability compared to a RE

USY AURORA® catalyst.

Figures 4 and 5 confirm the proprietary stabilization compounds

used for Z-21 and Z-22 can maintain zeolite surface area like a tradi-

tional RE USY catalyst.

Montana Refining CompanyMRC is an independent energy company engaged in crude oil refin-

ing and the wholesale marketing of refined petroleum products. They

operate one of the last small, independent full production refineries

in the USA, producing approximately 10,000 barrels per day of vari-

ous petroleum products.

The refinery is a complex refinery (Nelson Complexity Factor of 9.3)

able to process heavy sour crude oil that is received via pipeline and

railcar. A basic process flow for the MRC facility is shown in Figure 6.

MRC produces a wide range of high quality products ranging from

multiple grades of low sulfur gasoline (including ethanol blended

gasoline) to ultra-low sulfur diesel, jet fuels, LPG’s and asphalt prod-

ucts. The finished gasoline and distillate products are distributed

through MRC’s terminal in Great Falls and the asphalt products are

marketed over racks at the refinery.6

MRC, with nearly ninety years in the Great Falls community as a pe-

troleum refiner with stringent quality control standards, has earned a

reputation as a dependable supplier of high-quality fuel and road

paving products. MRC is a wholly owned subsidiary of Connacher

Oil and Gas Limited, a Calgary-based Canadian crude oil and natu-

ral gas company.6

The FCC at MRC processes a hydrotreated VGO at a nominal rate

of ~3,000 barrels per day. During the summer months the unit is

constrained by the air blower and main column overhead con-

densers hydraulics. Reactor temperature is controlled to a relatively

low value of ~940°F as the unit generally operates in a maximum

Light Cycle Oil mode.

6 Issue No. 111 / 2012

Grace’s Super DESOX® OCI is used to control SOx to less than 25

ppm. NOx is controlled by minimizing excess O2 levels and the use

of Grace’s low NOx CP®P combustion promoter.

FCC gasoline is not hydrotreated at the facility. As a result gasoline

sulfur specifications are met by controlling the end point and FCC

feedstock sulfur. Grace’s SuRCA® gasoline sulfur reduction technol-

ogy is used to extend the VGO hydrotreater run length by providing

~30% gasoline sulfur reduction, allowing lower FCC feed hydro-

treater temperature for a target FCC gasoline sulfur.

MRC meets its FCC flue gas particulate limits without any external

particulate recovery device such as tertiary separator or electrostatic

precipitator (ESP). As a result, FCC catalyst attrition and retention

qualities are critical.

Grace is a long-term supplier of FCC catalysts and additives to

MRC. During that time several Grace products have been commer-

cialized at MRC including:

1. D-PrisM® and SATURN® Gasoline Sulfur Reduction

technologies

2. XP® and LIBRA® FCC catalysts

3. Super DESOX® OCI – reduced rare-earth SOx reduction

additive

4. CP®P – Non Platinum Low NOx Combustion Promoter

Reformulations Ahead of theSurchargeIn 2011, Grace offered MRC FCC catalyst technology from its new

REpLaCeR® portfolio to avoid pending rare-earth surcharges.

MRC reformulated their fresh FCC catalyst in two steps. REM-

EDY™ 1 GSR® reduced rare earth by a third, while REMEDY™ 2

GSR® completely removed rare earth from the catalyst. Fresh cata-

lyst properties are shown in Table 2. The objective of each reformu-

lation was to maintain the current yields, gasoline sulfur and

gasoline octane as the base rare-earth containing GENESIS® grade.

REMEDY™ 1 GSR® incorporates Grace’s REACTOR® technology

together with MIDAS®. MIDAS® is low zeolite to matrix, industry-

leading bottom cracking catalyst.7 REMEDY™ 2 GSR® uses both

REACTOR® and REBEL™ technologies and is a rare-earth free cat-

alyst. The original GENESIS® GSR® incorporated Aurora® and

MIDAS® technology. All FCC catalyst technologies incorporate

Grace’s gasoline sulfur reduction SuRCA® technology which pro-

vides ~30% gasoline sulfur reduction.

MRC reformulated to REMEDY™ 1 GSR® in January 2011 minimiz-

ing the first quarter 2011 rare-earth surcharge by one third. When

REBEL technology was available in August 2011, MRC reformulated

to REMEDY™ 2 GSR®and avoided the large third and fourth quar-

ter rare-earth surcharges entirely, as shown in Figure 8.

Crude

Asphalt Slurry Oil

Gasoline

Gasoline

Jet Diesel

LPGCRUDE

DISTILLATION

HYDROTREATING

OCTANEIMPROVEMENT

CrudeTower

VacuumTower

NaphthaHydrotreater

KeroHydrotreater

ULSD/GOHydrotreater

Isomerization

Catalytic Reformer

Alkylation

FCC

UPGRADINGLCO

Hydrogen

FIGURE 6: Basic Process Flow – Montana Refining Company


GENESIS® GSR® REMEDYTM 1 GSR® REMEDYTM 2 GSR®

Activity, wt.% 80 80 80

RE2O3, wt.% 1.5 1.0 Trace

Al2O3, wt.% 51 51 47

Zeolite Surface Area, m2/gm 200 200 220

Matrix Surface Area, m2/gm 90 90 75

0 to 40�, % 13 13 13

TABLE 2: Montana Refining Company Fresh Catalyst Properties

ResultsThe following REMEDY™ 2 GSR® data reflects operating data after

over 50% of the La2O3 had been purged from the inventory. GENE-

SIS® GSR® data represents weekly test run data from March 2010 to

July 2010, while REMEDY™ 2 GSR® data is from November

through December 2011 operations. During the GENESIS® GSR®

operation ~7.5% OlefinsMax® (ZSM-5) was used, while the REM-

EDY™ 2 GSR® operation employed just 2.5% OlefinsMax®.

AURORA®

MIDAS®

SuRCA®

REACTOR®

REBELTM

SuRCA®

GENESIS® GSR®

REMEDY® 2 GSR®

FIGURE 7: REMEDY™ 2 GSR® and GENESIS® GSR®Technology

0

REMEDYTM 2-GSR®

August 2011 eliminatedthe RE Surcharge

4th QTR2010

99%

LaO

,FO

B,C

hina

,$/M

etric

Ton

1st QTR2011

2nd QTR2011

3rd QTR2011

4th QTR2011

1st QTR2012

140,000

120,000

100,000

80,000

60,000

40,000

20,000

REMEDYTM 1-GSR®

January 2011 reducedthe RE Surcharge byone third

FIGURE 8: Each Reformulation Occurred Prior to an Increase in Rare-Earth Price

8 Issue No. 111 / 2012

Much of the MRC operating

data is represented in box

plots. An example of a box

plot is shown in Figure 9. A

box plot is a graphical sum-

mary of the distribution of a

data set that shows its

shape, central tendency, and

variability.

Figure 9 shows the key parts

of the box plot. Box plots

can be used to quickly un-

derstand a data distribution

and are particularly useful

for comparing different data

sets. The following box plots

compare the data distribu-

tion between GENESIS®

GSR® and REMEDY™ 2

GSR® at MRC.

Figure 10 shows that mean

catalyst additions on a pound

of catalyst per barrel of feed

basis were maintained at

~0.14 lb/b for both

GENESIS® GSR® and REM-

EDY™2 GSR® operations.

Conversion corrected for

430°F for the REMEDY™ 2

GSR® operation was within

the conversion range with

GENESIS® GSR®. The me-

dian value conversion was

77.5 vol.% during the REM-

EDY™ 2 GSR® operation

compared to 76 vol.% for the

GENESIS® GSR® period.

General operating conditions

and feed properties are

shown in Figure 11. Feed-

stock API was lower with

REMEDY™ 2 GSR® with a

median value of ~26.5°API

compared to 27.3°API with

GENESIS®. Reactor temper-

ature increased to 940°F

while using REMEDY™ 2

GSR® and feed rates were

~150 bpd lower. Differences

in key independent operating

74

72

70

68

73

71

69A

ctiv

ity,%

Catalyst

GENESIS® GSR® REMEDYTM 2 GSR®

3rd Quartile

95% Point

5% Point

2nd Quartile

Median Mean

FIGURE 9: Example Box Plot MRC Ecat Activity

430˚F Conversion, vol.% Catalyst Additions, lb/b


84%

80%

82%

78%

76%

72%

74%

70%

0.150

0.145

0.140

0.135

0.130

FIGURE 10: EMRC Conversion was Maintained at Similar Catalyst Additions


variables including reactor

temperature, feedstock

properties and feedstock

temperature were modeled

and the conversion differ-

ences between both periods

were <0.25 vol.%. As a re-

sult, the conversion shifts

shown in Figure 10 are not

influenced by differences in

operating temperatures and

feedstock properties.

Coke selectivity was main-

tained with REMEDY™ 2

GSR® as Figure 12 shows

similar coke yield versus

corrected conversion be-

tween the two catalysts.

Slurry cracking is a critical

attribute for all catalyst sys-

tems and Figure 12 confirms

that the operation with REM-

EDY™ 2 GSR® provided

similar or lower slurry as a

function of conversion.

Gasoline selectivities in-

creased during the operation

with REMEDY™ 2 GSR® as

shown in Figure 12. Gaso-

line and LPG yields are cor-

rected for ZSM-5 in Figure

12. Higher gasoline selectiv-

ity from rare-earth free REM-

EDY™ 2 GSR® confirms that

the zeolite is stabilized simi-

larly to a traditional rare-

earth catalyst. Gasoline

octane was maintained with

REMEDY™ 2 GSR®.

Zero rare-earth catalyst

often produces higher dry

gas rates. However, similar

dry gas rates as a function

of reactor temperature were

observed between REM-

EDY™ 2 GSR® and GENE-

SIS® GSR® as noted in

Figure 13. Dry Gas rates are

very low at MRC, consistent

with the low reactor temper-


Feed, BPD Feed, API

3000

2800

2900

2700

945

955

925

940

930

1310

1290

1270

1300

1280

28.0

27.0

26.0

27.5

26.5

Reactor T, ˚F Reg Dense, T

FIGURE 11: MRC Operating Condition Changes Contributed to Less than 0.25 vol.%Conversion


LPG (no ZSM-5), vol.%32%

30%

28%

24%

6%

26%

8%

10%

4%

70% 75% 80%

5.75

5.25

5.50

6.00

5.00

69%

66%

63%

60%

70% 75% 80%

Gasoline, vol.% (no ZSM-5)

Coke, wt.%Slurry 650˚F, vol.%

430˚F Conversion, vol.%

FIGURE 12: REMEDY™ Demonstrated Excellent Product Selectivities at MRC

10 Issue No. 111 / 2012

ature. Corrected conversion

values for a given catalyst-

to-oil ratio are similar for

both operations, suggesting

similar in-unit activity from

both catalysts.

Equilibrium catalyst (Ecat)

activity was maintained with

REMEDY™ 2 GSR®. Figure

14 shows the median Ecat

activity value of both REM-

EDY™ 2 GSR® and GENE-

SIS® GSR® is identical at 71

wt.%. Zeolite surface area

increased to a median value

of 115 m2/gm with REM-

EDY™ 2 GSR® consistent

with higher fresh catalyst ze-

olite surface area. Zeolite

surface retention, the ratio of

Ecat ZSA to fresh ZSA, is

54% for both catalyst sys-

tems, despite the lack of

rare-earth stabilization in

REMEDY™ 2 GSR®. Unit

cell size median values

dropped from 24.29Å to

24.27Å. A 24.27Å UCS con-

firms that the proprietary ma-

terial in REMEDY™ 2 GSR®

has successfully stabilized

the zeolite. The traditional

zero RE catalysts typically

equilibriate to a zeolite UCS

in the range of 24.21 to

24.24Å, depending on the

severity of the unit. Con-

stant activity and zeolite

surface area retention were

observed, despite a ~750

ppm increase of median

values of vanadium plus

sodium levels on Ecat.


84%

82%

80%

76%

70%

78%

72%

74%130

110

120

160

140

170

150

Cat/Oil Reactor T, ˚F6.5 7.0 7.5 8.0 8.5 925 930 935 940

430˚

FC

onve

rsio

n,Vo

l.%

Dry

Gas

,SC

FB

FIGURE 13: MRC Achieved Similar In-Unit Activity and Conversion with RE FreeREMEDY™ without an Increase in Dry Gas Yield


ConclusionsCommercial data at MRC confirms that rare-earth free REMEDY™

performance is comparable to the base rare-earth GENESIS® cata-

lyst providing a significant economic benefit. Specifically REM-

EDY™ showed the following at similar catalyst additions at MRC

compared to GENESIS® :

• Similar unit conversion

• Similar coke and slurry selectivities

• Higher gasoline selectivity

• Similar Ecat activity

Grace offers a family of REpLaCeR® catalysts with zero to low rare-

earth that has comparable hydrothermal stability and acidity as a tra-

ditional rare-earth catalyst.

The REpLaCeR® family of catalysts is currently used in 52 refineries

globally processing both VGO and resid. REpLaCeR® technology is

a great alternative to rare-earth containing catalysts, mitigating the

risk associated with the uncertainty in price and supply of rare earth.

AcknowledgementsThe authors thank MRC management for permission to publish this

data and Rosann Schiller of Grace for her valuable assistance.

74

72

70

3500

3000

2500

3250

2750

56.0%

52.0%

54.0%

50.0%

120

115

110

105

100

24.29

24.28

24.27

24.26

Activity, % Zeolite SA, m2/gm Unit Cell Size, Å

GENESIS® GSR®

REMEDYTM 2 GSR®

V + Na, ppm ZSA Retention, %

FIGURE 14: Ecat Properties Demonstrate Excellent Stability of the RE-Free REMEDYTM Catalyst

References1. O. Topete, et al “Optimizing FCC Operations in a High Rare-

Earth Cost World: Commercial Update on Grace Davison’s Low and

Zero Rare-Earth FCC Catalysts”, Catalagram®, 110 (2011) 2.

2. C. Baillie, R.Schiller, “The Development of Rare-Earth Free

FCC Catalysts”, Catalagram®, 109 (2011) 17.

3. R. Wormsbecher, W. Cheng, D. Wallenstein, “Role of the Rare-

Earth Elements in Fluid Catalytic Cracking”, Catalagram®, 108

(2010) 19.

4. N. Petti, et al, “Recent Commercial Experience in Improving

Refinery Profitability with Grace Davison Alumina-Sol Catalysts”,

Catalagram®, 99 (2006) 2.

5. J.C. Kayser, Versatile Fluidized Bed Reactor, U.S. Patent

6,069,012.

6. www.montanarefining.com

7. R. Schiller, “Grace Davison’s GENESIS® Catalysts System Pro-

vide Refiners Economic Opportunities”, Catalagram®, 107 (2010) 4.

12 Issue No. 111 / 2012

Maximize Distillate Yield toMeet Growing Market Demand

Rosann SchillerSenior MarketingManager


Despite a mild winter thus far, industry analysts forecast ULSD demand growth in the second half of 2012.

This is in part due to global demand growth for middle distillates1 and in part due to new sulfur regulations

set to take effect later this year. In 2012, the State of New York will become the first state to require that all

oil used for heating meet ULSD standards, which means that No. 2 heating oil sulfur levels will have to be

reduced to 15 ppm. Other Northeast states have announced dates to phase-in ULSD for heating oil.2 The

pending regulations could raise regional ULSD demand by 20%. Over the last 6 months, over 50% North-

east refining capacity has been idled as well as the HOVENSA refinery in the Virgin Islands, which was a

major importer of transportation fuels into the Northeast. The loss of refining volume serving the Northeast

coupled with bottlenecks in the transportation network from the Gulf Coast could potentially result in high

prices and potential shortages of ULSD in New York, Pennsylvania, and New England.

FCC and ART SynergyRefiners with additional sulfur removal capacity can increase profitability by maximizing the refinery yield of

ULSD. If you have room to process additional FCC LCO in your diesel hydrotreaters, Grace® and Advanced

Refining Technologies® technical service can work with you to help maximize your refinery profitability by en-

hancing both the yield and quality of your diesel and heating oil blending streams. We’ve published numer-

ous articles on the topic, which illustrate that the greatest challenge in a max LCO operation is managing the

incremental bottoms yield that accompanies a reduction in unit operating severity. Positive yield impact can

be achieved via an optimization of key operating variables discussed below.

CompetitiveCatalyst

GENESIS® 1(Max Gasoline)relative to base

GENESIS® 2(Max LCO)

relative to base

Gasoline, lv.% Base +3.0 +1.0

LCO, lv.% Base +1.5 +5.0

Bottoms, lv.% Base -1.5 -2.2

TABLE 1: GENESIS® Catalyst Delivers Flexibility to Shift Between Gasoline and LCOOperating Modes


Maximizing LCO from the FCCUIn general the following process changes should be made as a refin-

ery moves from a maximum gasoline/conversion operation to a max-

imum LCO operation3:

• Remove diesel range material from the FCC feedstock

• Reduce gasoline endpoint

• Reduce FCC conversion by

• Reducing riser outlet temperature;

• Raising feed temperature and;

• Lowering Ecat activity

• Initiate HCO or slurry recycle

• Optimize catalyst formulation

Increased slurry cracking and maintaining both the C3+ liquid yield

and gasoline octane are key requirements of a maximum LCO cata-

lyst system. In general, a maximum LCO catalyst is a low

zeolite/matrix surface area catalyst with low to moderate activity and

excellent slurry cracking qualities.

2003 2004 2005 2006 2007 2008 2009 2010 2011

Grace has several low Z/M catalyst options to help you increase

LCO yield. The workhorse high MSA catalyst in our portfolio is

MIDAS®, which is well suited for any refiner seeking deep bottoms

conversion. MIDAS® has been applied in over 100 refineries (Fig-

ure 1), alone or as part of a GENESIS® catalyst system. MIDAS®

can increase FCC LCO yield and profitability by as much as

$1.50/bbl3.

Any refiner can take advantage of short term economic opportunities

with a GENESIS® catalyst system. By simply adjusting the blend

ratio of two complete FCC catalysts, we can shift the Z/M ratio of the

total blend and deliver a significant selectivity shift in a short period

of time. The refinery in Table 1 was able to improve profitability by

shifting the catalyst formulation as well as operating conditions to

match current market demand.4

New Additions to the PortfolioWe are also pleased to offer two new choices for maximizing LCO

and bottoms conversion the FCC. REBEL™ is the only 100% rare-

earth-free high matrix FCC catalyst solution available in the market-

place. Introduced in the wake of the rare-earth crisis of 2011,

REBEL™ utilizes Z-21 zeolite technology and is in nine commercial

applications at press time. In testing, REBEL™ has been shown to

have equivalent activity relative to MIDAS® in low to moderate met-

als environments. These yield shifts have been confirmed by sev-

eral third party laboratories. Figure 2 demonstrates how without

rare earth, REBEL™ achieves the similar activity (cat-to-oil ratio) as

the rare-earth exchanged MIDAS® catalyst. In commercial testing,

REBEL™ retained bottoms conversion and helped to maintain cata-

lyst addition levels at baseline.

Another challenge of a max LCO operation is maintaining total liquid

volume. LPG and gasoline may still be important products from the

FCC even when diesel pricing is at a premium. In order to maximize

total yield (and dollars) it is important to appropriately balance zeo-

lite, matrix and activity. For those units that want to drive to maxi-

FIGURE 1: MIDAS® Sales Growth

FIGURE 2: REBEL™ Maintains Similar Activity and Bottoms Conversion as Midas® without Rare Earth

Conversion, wt.%

67 69 71 73 75 77 7965

C/O

Rat

io

9.5

8.5

7.5

6.5

5.5

4.5

3.5

REBELTM MIDAS®

Bo

tto

ms,

wt.

%

Conversion, wt.%

67 69 71 73 75 77 7965

10

9

8

7

6

5

4

REBELTM MIDAS®

14 Issue No. 111 / 2012

mum total fuels (gasoline + distillate) yield, but still require activity to

stay within unit constraints, we recommend ALCYON® M technology.

ALCYON® M combines the high activity zeolite of ALCYON® with the

proprietary matrix architecture of MIDAS® in a single FCC catalyst

that is primed to deliver deep selective bottoms conversion while

maintaining total liquid yield. High hydrogen transfer activity in

ALCYON® M facilitates conversion of the bottom of the barrel of

aromatic feedstocks, such as those derived from coker gasoils and

Canadian heavy crudes. If you still require more LPG, Grace’s light

olefins additives such as OlefinsUltra® and OlefinsUltra® HZ can be

pre-blended with your fresh catalyst to maintain LPG olefinicity de-

spite reduced FCC severity.

In summary, Grace has multiple catalyst solutions in order to maxi-

mize LCO yield in your FCC. MIDAS® is our benchmark bottoms

conversion catalyst, with commercial success well documented in

over 100 refineries around the world. The same conversion capabil-

ity can now be achieved without rare earth, which is available in the

new Grace REBEL™ catalyst technology. Now in nine applications

and growing, REBEL™ delivers similar activity and bottoms cracking

conversion as MIDAS®. Lastly, for those units desiring deep bottoms

conversion, but without sacrificing in-unit activity to get there, we can

offer ALCYON® M catalyst. Designed for short contact time units de-

siring deep bottoms conversion, ALCYON® M will crack the bottom

of the barrel without giving up activity or violating unit constraints

such as circulation rate.

Contact your ART and Grace technical service reps to understand

just how much more LCO you can produce and treat to maximize

ULSD yield and profitability in 2012.

References1. IEA, “Oil Market Report,“ February 10, 2012.

2. Energy Information Agency, ”Potential Impacts of Reductions in

Refinery Activity in the Northeast Petroleum Product Markets,“ Feb-

ruary 2012.

3. Hunt, et al,”Maximizing FCC Light Cycle Oil Operating Strate-

gies“, Catalagram® No. 104, 2008.

4. Schiller, R.,”GENESIS® Catalyst Systems Provide Refiners the

Flexibility to Capture Economic Opportunities“, Catalagram® No.

107, 2010.


People on the Move

Reporting to Grace’s President and Chief Op-

erating Officer Gregory Poling will be Shawn

Abrams, President of Grace Catalysts Tech-

nologies. Abrams most recently served as

Vice President, Refining Technologies within

the former Grace Davison operating segment.

The new Grace Catalysts Technologies seg-

ment includes catalysts and related technolo-

gies used in refining, petrochemical and other

chemical manufacturing applications. 2011 revenues for this seg-

ment were approximately $1.4 billion. Grace’s Advanced Refining

Technologies joint venture is managed in this segment.

Andre Lanning has been named General

Manager- EMEA,Refining Technologies (RT).

In his new role, Andre will have overall re-

sponsibility for all EMEA (Europe, Middle

East, Africa) commercial and research busi-

ness activities in support of the global RT

strategy. He will be a member of the RT global

leadership team, reporting directly to Shawn

Abrams.

Li Yong has accepted the position of Manag-

ing Director, Refining Technologies (RT)

China. In this newly created role demonstrat-

ing our long term commitment to the China

market, Li will develop and lead commercial

growth opportunities throughout China. Li has

the unique set of experience, knowledge and

relationships with government officials, cus-

tomers and vendors, needed to accelerate

our significant investments and growth in China. He will report to Jim

Nee for all commercial activities and to Shawn Abrams for business

development activities. His office will remain in Shanghai.

Dan McQueen has accepted the position of

Director, Marketing & Business Development,

Refining Technologies EMEA, reporting di-

rectly to Andre Lanning. In his new role, Dan

will focus on improving our strategic position

and portfolio within the EMEA region by

bringing together the market requirements

and trends, the R&D focus for technology

development as well as ensuring our asset

base meets current and future requirements.

Bob Riley has rejoined the North American

Refining Technologies organization as a Tech-

nical Sales Representative. For the past two

years as Commercial Development Manager,

Bob has been successful in leading global

sales and strategic partnership activities in

the emerging biofuels market, enhancing the

growth of the Renewable Technologies/Incu-

bator business. In his new role, Bob will con-

tinue to support several of these start-up initiatives, while resuming

responsibility for providing sales and technical service expertise to

our Refining Technologies customers. Bob will assume account

management responsibilities for several customers on the West and

Gulf Coasts, reporting to Shahab Parva.

Grace has announced a realignment of its business into three operating segments:Grace Catalysts Technologies, Grace Materials Technologies and Grace Construction Products.“This new business segment structure allows us to align our segments more closely with our mar-kets and to pursue operational efficiencies and reduce overhead costs,” said Chairman and ChiefExecutive Officer Fred Festa. “We are excited about the opportunities that lie ahead, and are ascommitted as ever to supporting and anticipating the needs of our customers.”

16 Issue No. 111 / 2012

Improve Wet Gas ScrubberEconomics with Super DESOX®Additives

Grace’s Super DESOX® product line of SOx reduction additives provides an effective way to reduce wet gas

scrubber caustic consumption, and improves the overall economics of SOx removal.

Sodium hydroxide, or caustic soda, is one of the most widely used commodity chemicals. Refiners utilize it in

FCCU wet gas scrubbers (WGS) to remove SO2 from regenerator flue gas stack emissions. Caustic pricing

tends to be cyclical, depending not only on the demand for caustic, but also on the demand for the co-pro-

duced chlorine. The continued slow down in the housing market has reduced the demand for chlorine deriva-

tives, thus limiting caustic production, and has been a contributing cause in caustic soda price increases.

Currently, caustic soda price is forecasted to exceed $600 per dry short ton through the third quarter of 2012

– a price threshold where use of SOx reduction additives can be cost effective. This situation has prompted

some refiners to consider use of Super DESOX® additives to reduce the SO2 loading on their WGS.

The high efficiency of Super DESOX® additives, at modest SOx reduction levels, makes them an economi-

cally attractive option to reduce WGS caustic consumption. Using Super DESOX® MCD, Grace’s most cost-

effective additive to reduce the amount of SOx going to the WGS, provides refiners an opportunity to lower

caustic consumption. To illustrate the potential savings, consider an FCCU with uncontrolled SOx emissions

of 700 ppmv upstream of the WGS. A moderate pick-up factor (PUF) of 30 at 40% SOx reduction is as-

sumed for Super DESOX® MCD efficiency. Also assumed is that for every one mole of SOx removed, 2.2

moles of caustic could be elimi-

nated. Optimal savings occur near

40% SOx reduction, potentially ex-

ceeding $220,000 annually in caus-

tic consumption alone, while also

taking into account the cost of the

additive. Additional savings may

result from reduced water, utilities,

and waste disposal.

For more information on reducing

WGS caustic consumption, please

contact your Grace technical sales

representative.

20 30 40 50 60 70

% SOx Reduction

$50,000

$100,000

$150,000

$200,000

$250,000

$300,000

Net

An

nu

alN

aOH

$S

avin

gs

NaOH Savings Peak at 40% SOx Reduction Using SuperDESOX® MCD Additive

Super DESOX® MCD (NaOH $620/TON)



Eric GriesingerMarketingManager



Improve Contaminant MetalsFlushing with TITAN™

TITAN™

The escalating price of rare

earth in fluid cracking cata-

lyst sparked increased de-

mand from refiners for

equilibrium catalyst (Ecat) as

a means to control ex-

penses. During this same

period, the available supply

of high quality, low metals

Ecat had decreased. In re-

sponse to the shrinking sup-

ply of Ecat, Grace introduces

TITAN™, a unique catalyst

solution for removing con-

taminant metals from refin-

ing operations.

Unlike traditional equilibrium

catalysts, TITAN™ is com-

pletely free of nickel, vana-

dium and additives. These

contaminants can lead to el-

evated NOx, H2, dry gas or

coke, making TITAN™ a pre-

ferred option to avoid addi-

tional operating constraints.

As shown in Figure 1,

TITAN™ yields 2.5# lower

cat-to-oil when compared

with a standard 75 MAT

equilibrium catalyst, provid-

ing even more value.

Conversion, wt.%

C/O

Rat

io

50 55 60 65 70 75 80

9

8

7

5

4

3

6

2.5# less C/O

TitanTM Ecat

As with all Grace products,

TITAN™ can be offered in

blends with any combination

of fresh catalysts, equilibrium

catalysts and additives. Al-

though TITAN™ is a manu-

factured as a fresh catalyst

product, Grace’s continuous

improvement initiatives along

with investments in new pro-

cessing equipment allows for

Figure 1: TITANTM Delivers Lower Cat-to-Oil Ratiovs. a Standard Ecat.

Stuart KipnisMarketingManager


TITAN™ to be offered with-

out a rare-earth surcharge.

TITAN™’s performance is

backed by the support of our

Grace world-class Technical

Service team.

For additional information on

TITAN™, please contact

your Grace representative.

18 Issue No. 111 / 2012

Grace Upgrades Ecat TestLaboratory in North America

In an effort to improve our level of customer service, Grace has

completed a major upgrade to our routine equilibrium catalyst (Ecat)

evaluation program. This past September, we renovated the Ecat

testing laboratory in Curtis Bay, MD and commissioned Advanced

Cracking Evaluation (ACE®) units for routine sample analysis. The

new ACE units replaced the Micro Activity Test (MAT) which was his-

torically used to evaluate Ecat performance.

Transition from MAT to ACE is a significant step forward and en-

hances the quality of our Ecat testing. The new ACE testing will im-

prove the precision of the Ecat activity measurement.

Did you know?The feed rate in a MAT or ACE unit is 1/1,000,000of the size of a commercial FCCU, hence theconversion measured is the 10-6 activity ormicroactivity.

In addition to the instrument upgrade, we have also changed our

standard feedstock to reflect the observed increase in industry resid

processing. The new feedstock is heavier, containing more ConCar-

bon and 1050°F+ material than the previous benchmark.

Grace remains committed to providing our customers with superior

technical support and in 2012, we will be completing a similar ACE

upgrade in our Ecat testing laboratory in Worms, Germany.


Maximize Yields of HighQuality Diesel

Greg RosinskiTechnical ServiceEngineer

Brian WatkinsManagerHydrotreatingPilot Plant, TechnicalService Engineer

Charles OlsenDirector, Distillate R&Dand Technical Services

AdvancedRefiningTechnologiesChicago, IL, USA

Global growth in distillate demand has driven refiners to investigate ways to increase middle distillate yields.

Figure 1 shows the diesel-gasoline spot price differential for the Gulf Coast. As the figure demonstrates,

diesel prices have remained strong relative to gasoline prices which are incentivizing refiners to look for

more opportunities to increase diesel yield. Options for refiners include increasing diesel yield from FCC

Pretreat units by operating in a mild hydrocracking (MHC) mode or extending the endpoint of the feed to a

diesel unit and converting the heavy fraction into distillate range material.

There are many challenges associated with both approaches utilizing the mild hydrocracking (MHC) ap-

proach, with a significant one being the need to minimize production of excess light ends and naphtha to

avoid overloading the existing downstream fractionation system. These issues become even more impor-

tant as end of run approaches and the reactor temperatures are higher which increases the conversion of

the MHC catalyst. Another potential obstacle is dealing with the possible negative impacts on other diesel

from product properties such as diesel product color and cold flow properties.

Many of these concerns can be alleviated through the proper design and selection of a catalyst system for

the hydrotreater. Advanced Refining Technologies® (ART) has conducted extensive pilot plant work in an ef-

fort to better understand these potential options for refiners wishing to increase diesel yields. This work has

shown that a catalyst system design approach incorporating a mild hydrocracking component is a viable op-

tion for the production of higher yields of middle distillate.

The use of an MHC catalyst component in the FCC pretreater allows for an opportunity to achieve incre-

mental conversion above that typically experienced with a hydrotreating catalyst system. In addition, the op-

erating mode of the FCC pretreater can be used to adjust overall yields of gasoline and middle distillate

giving the refiner more flexibility to change the product mix to meet market demands. In order to assess the

effectiveness of the MHC catalyst it is important to understand the level of boiling range shift that can be

achieved simply thought hydrotreating. Table 1 shows a variety of sulfur, nitrogen and aromatic compounds

and the corresponding change in boiling point that occurs upon removal of sulfur and nitrogen, and through

saturation of aromatic rings. The table demonstrates that a fair amount of boiling point shift occurs through

hydrotreating.

20 Issue No. 111 / 2012

Understanding the different catalyst attributes and their impact on

unit performance is important to designing the best catalyst system.

Most hydroprocessing catalysts have an acidic and an active metals

component. For typical hydrotreating catalysts these metals are ei-

ther cobalt-molybdenum or nickel-molybdenum on an alumina or sil-

ica-alumina support. In a hydrocracking catalyst a significant

amount of the support is made with amorphous silica-alumina or ze-

olite. This substantially increases the acidity of the catalyst and is

what gives hydrocracking catalyst cracking activity. In a typical hy-

drocracker NiMo hydrotreating catalyst is used to convert organic ni-

trogen to ammonia since hydrocracking catalysts are poisoned by

organic nitrogen. This allows the hydrocracking catalyst to effec-

tively perform its cracking function.

$(1.00)

$(0.80)

$(0.60)

$(0.40)

$(0.20)

$-

$0.20

$0.40

$0.60

$0.80

$1.00

Gu

lfC

oas

tP

rice

Dif

fere

nti

al(U

LS

D-

Gas

olin

e)[$

/gal

]

Apr 12006

Aug 142007

Dec 262008

May 102010

Sep 112011

FIGURE 1: Gulf Coast Diesel-Gasoline Differential

TABLE 1: Boiling Point Shifts Achieved From Hydrotreating

UntreatedCompound Boiling Point, ˚F Treated

Compound Boiling Point, ˚F

SulfurCompounds

Benzothiophene 430 ethyl Benzene 277

Decylmercaptan 465 n-Decane 345

Dibenzothiophene 630 Biphenyl 493

NitrogenCompounds

2-methyl Indole 522 propyl Benzene 319

Isoquinoline 468 2-ethyl toluene 329

β –Naphthoquinoline 662 ɑ-propyl Naphthalene 526

Aromatics

Naphthalene 424 Tetralin 406

β-ethyl Naphthalene 496 2-ethyl Tetralin 459

Anthracene 644 Octahydro Anthracene 561

In mild hydrocracking (MHC) the goal is to achieve a lower amount

of cracking conversion compared to a full conversion hydrocracker,

so organic nitrogen levels can be relaxed. It does, however, require

properly balancing the amount of hydrocracking catalyst with hy-

drotreating catalyst in order to achieve the optimum in terms of

yields and product qualities.

One recent study completed by ART investigated the tradeoffs ob-

served by adding MHC catalyst to the catalyst system in an FCC

pretreater. The feedstock used in this work is shown in Table 2. The

feed is full range vacuum gas oil (VGO) with just over 1600 wppm

nitrogen and 2.75 wt.% sulfur. The breakdown of the aromatic com-

pounds present in the feed is also given. The feed is relatively aro-


matic and has a significant quantity of poly aromatic compounds.

One of the goals of this work was to investigate the tradeoff in

HDS/HDN activity with cracking activity as more MHC component

was incorporated in the catalyst system. The hydrotreating catalysts

selected were current generation Type II catalysts from ART’s DX®

catalyst series. The MHC components were selected based on

cracking activity and selectivity to diesel products.

Figure 2 shows how the HDS activity of the catalyst system changes

as the fraction of the MHC component increases. Not surprisingly,

the base case hydrotreating catalyst system, which contains no

MHC catalyst, shows the highest activity for HDS. Adding in 10%

MHC catalyst results in essentially the same HDS activity as the

base case system. Increasing the MHC component to 20% results

in a slight decrease in HDS activity at low temperatures, but the

same HDS activity at higher temperatures. Finally, at the highest

fraction of MHC catalyst (35%) the HDS activity is consistently lower

than the base case activity suggesting that the system contains too

much MHC catalyst relative to hydrotreating catalyst.

A comparison of the HDN activity of the different catalyst systems is

shown in Figure 3. Again the base case system shows the highest

activity, but only for lower HDN conversion (higher product nitrogen).

Interestingly, the data shows that adding in MHC catalyst results in a

system which has higher HDN activity relative to the base case for

higher nitrogen conversions. This suggests that the stronger acidic

function of the MHC catalyst improves nitrogen removal of the cata-

lyst activity. Note that increasing the fraction of MHC catalyst too far

does result in a decrease in HDN activity except for very high nitro-

gen conversions.

TABLE 2: Feedstock Analysis

API Gravity 19.5

Specific Gravity 0.936

Sulfur, wt.% 2.75

Nitrogen, wppm 1622

HPLC Core Aromatics, wt.%

1 Ring 24.3

2 Ring 21.6

3 Ring 9.2

4 Ring 7.0

Polar 1.1

Distillation, D2887, ˚F

IBP 549

10 695

30 792

50 850

70 907

90 983

FBP 1091

670

690

710

730

750

770

790

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16

Tem

per

atu

re,°

F

Product Sulfur, wt.%

10% MHC 20% MHC 35% MHCBase Case

FIGURE 2: Comparison of HDS Activity

22 Issue No. 111 / 2012

In terms of HDS and HDN activity there is an interesting interaction

between the hydrotreating and MHC catalyst components. HDS ac-

tivity is not significantly affected by the addition of MHC catalyst until

higher percentages are reached. For HDN activity there is an opti-

mum level of MHC catalyst where HDN activity is improved over the

base case performance. Figure 4 summarizes how the cracking

conversion is impacted by the addition of MHC catalyst to the sys-

tem. The conversion is defined as the difference between the

amount of 680°F+ material in the feed and product. The figure

shows that at lower temperatures all the catalyst systems behave

similarly and show the same level of boiling range shift as achieved

with hydrotreating alone. As the temperature is increased there is a

point at which the conversions for the MHC catalyst systems start to

differentiate themselves from the base case.

The conversion observed for the base case increases only gradually

as temperature is increased. Adding only 10% MHC catalyst results

in a slightly faster increase in conversion with increasing tempera-

ture, and adding 20% MHC catalyst results in an even faster in-

crease in conversion. The 20% system provides 10 numbers higher

conversion relative to the base case with only about a 10-15˚F in-

crease in temperature.

Figure 4 also shows that there can be too much MHC catalyst in the

system. Adding as much as 35% MHC catalyst actually results in a

decrease in conversion relative to the 20% system. This is primarily

due to the fact that the 35% MHC system no longer has enough hy-

drotreating activity, so the MHC catalyst is severely poisoned by or-

ganic nitrogen slipping though the hydrotreating catalyst bed.

Figure 5 summarizes the middle distillate yield (360-680°F)

achieved from each catalyst system. The distillate yield is essen-

tially the same for all catalyst systems at low temperature similar to

what was observed in Figure 4. At higher temperatures the systems

again begin to differentiate themselves. The distillate yield in-

creases with increasing amounts of MHC catalyst, but again there is

an optimum amount of MHC catalyst which maximizes the diesel

yield beyond which the diesel yield decreases.

The mild hydrocracking approach to increase distillate yields will re-

sult in an increase in hydrogen consumption over a hydro-

treating base case. Product API increase is often used as a rough

indication of hydrogen consumption, and is shown in Figure 6 for the

different catalyst systems in this study. Not surprisingly, the data ex-

hibits similar behavior as described for conversion and distillate yield

where there is a point where too much MHC catalyst has a negative

impact on unit performance. The systems all provide about the

same increase in API gravity at lower temperatures, and, similar to

what was observed with cracking conversion, the various systems

provide different degrees of API uplift at higher temperatures. Note

again that the system containing 20% MHC catalyst stands out in

terms of the whole liquid product API increase.

650

670

690

710

730

750

770

790

0 100 200 300 400 500 600 700 800 900

Tem

per

atu

re,°

F

Product Nitrogen, wppm


FIGURE 3: Comparison of HDN Activity

670 680 700 710 720 730 740 750 760 770

Temperature, ˚F

6900%

10%

20%

30%

40%

50%

60%

Co

nve

rsio

n,w

t.%

FF

Bas

is


FIGURE 4: Comparison of Conversion

670 680 700 710 720 730 740 750 760 770

Temperature, ˚F

6900.0

5.0

10.0

15.0

20.0

35.0

40.0

Dis

tilla

teY

ield

,wt.

%

25.0

30.0


FIGURE 5: Comparison of Distillate Yield

In addition to increased diesel yields and an increase in hydrogen

consumption, it is important to consider the impact of MHC on the

diesel product properties. In most cases the diesel resulting from an

MHC operation will have to be further hydrotreated in order to be

used in the ULSD pool. Operating in areas of lower conversion, the

sulfur in the diesel fraction is similar with the lower levels of MHC

catalyst, and decreases as the system approaches 35% MHC cata-

lyst as shown in Figure 7. When changing the operation to higher

conversion targets in order to produce more distillate products, the

product sulfur can drop to what appears to be quite low until the

quantity of MHC catalyst goes beyond the point where the hy-

drotreater can actually remove the sulfur efficiently. In this case, it

makes a higher sulfur product.

The diesel product nitrogen shows a slightly different response. As

one might expect, as the MHC catalyst concentration is increased,

the system is more efficient in nitrogen removal. Figure 8 compares

the diesel product nitrogen with the percent MHC catalyst at both

lower conversion and high conversion points. The data show that at

high conversion there is an optimum quantity of MHC catalyst in

order to achieve the lowest product nitrogen. Lower product nitro-

gen can also be associated to some degree with lower aromatic

content due to the need to saturate or open ring molecules to re-

move the bound nitrogen.

There are also other improvements in the diesel quality that can be

affected with MHC. Figure 9 compares the improvement in cetane

index at three MHC conditions. At lower operating temperatures

and conversion, the addition of excess MHC catalyst can have a

negative impact on cetane index relative to simple hydrotreating.

This does not make the cetane index poor, simply that it is lower

than conventional hydrotreating. Increasing conversion shows that

there is an improvement in cetane index, which when coupled with

the product sulfur and nitrogen data, indicate that there is an opti-

mum in order to achieve the greatest yield of distillate products with

the greatest value to the refinery.

Choosing the correct MHC catalyst system is critical to avoid too

much conversion throughout the cycle as well as being able to tailor

the HDS and HDN activity. Excess or undesirable cracking or poor

hydrotreating performance can cause a refiner to be limited on avail-

able hydrogen or short on cycle life, thus hurting the performance of

the hydrotreater. Balancing the differences between selectivity for

cracking and the HDS/HDN activity is critical to a stable system as

well as the yield slate.

Figure 10 shows the differences in conversion between two different

MHC catalysts. MHC 1 exhibits a higher hydrocracking activity as

compared to hydrogenation activity, whereas the reverse is the case

for MHC 2. It is apparent from the figure that a more active MHC

catalyst can achieve higher conversions even when a lower volume

is used in the system. This adds another degree of flexibility when

designing a system to meet specific objectives, as less MHC cata-

lyst allows for improvements in HDS, HDN and HDA.

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0A

PII

ncr

ease

670 680 700 710 720 730 740 750 760 770

Temperature, ˚F

690


FIGURE 6: Comparison of API Uplift

0

100

200

300

400

500

600

700

0

500

1000

1500

2000

2500

3000

3500

0 5 10 15 20 25 30 35 Pro

du

ctS

ulf

ur,

wp

pm

Hig

hC

on

vers

ion

Pro

du

ctS

ulf

ur,

wp

pm

Lo

wC

on

vers

ion

% MHC Catalyst

Low Conversion High Conversion

FIGURE 7: Diesel Product Sulfur

0 5 10 15 20 25 30 35

% MHC Catalyst

Pro

du

ctN

itro

gen

,wp

pm

Hig

hC

on

vers

ion

0

100

200

300

400

500

600

500

600

650

700

800

850

900

950

Pro

du

ctN

itro

gen

,wp

pm

Lo

wC

on

vers

ion

750

550

Low Conversion High Conversion

FIGURE 8: Diesel Product Nitrogen


24 Issue No. 111 / 2012

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

Low Medium High

Del

taC

etan

eim

pro

vem

ent

10% MHC 20% MHC 35% MHC

FIGURE 9: Diesel Cetane Index Improvement

0%

10%

20%

30%

40%

50%

60%

670 680 690 700 710 720 730 740 750 760 770

Co

nve

rsio

n,w

t.%

(FF

Bas

is)

Temperature, °F

25% MHC 2 20% MHC 1Base Case

FIGURE 10: Comparison of MHC Catalysts

There is an optimum in terms of the relative amounts of MHC and

hydrotreating catalysts which delivers the best combination of HDS,

HDN and conversion activity. Clearly there is a need to maximize

the HDS and HDN activity as well as saturation when trying to deter-

mine the optimum system. As the data just discussed indicates the

catalyst selection has a significant impact as does the quantity of

MHC catalyst in the hydrotreater. High activity MHC catalysts are

better at boiling point conversion and can be utilized in a system that

is limited in HDS and HDN in order to minimize the impact on the

downstream FCC. The use of even a small amount of MHC catalyst

will prove to be beneficial in order to alter the boiling range of the

product and to minimize any impact on the removal of the difficult

sulfur and nitrogen.

Advanced Refining Technologies can work closely with refining tech-

nical staff to help in selecting the appropriate MHC system to take

advantage of this opportunity. One of the keys is being aware of the

potential impacts MHC operation will have on unit performance.

This process presents unique challenges and ART is well positioned

with its experience at providing customized catalyst systems for FCC

and MHC FCC applications. Opportunities exist for the refiner to

consider when choosing the appropriate catalyst system to maxi-

mize unit yields and performance.

SAVETHEDATEJoin Grace and Advanced Refining Technologies

for our Biennial SeminarThursday, August 23, 2012

Location TBAHouston, Texas

Save the date to hear the latest on FCC and hydroprocessing catalyststechnologies. Industry experts will also be on hand to

discuss trends on catalysts and processes.

For more information or to be put on the mailing list, contact [email protected].

Orginal sketch of the Fred Hartmann Bridge and the Houston Ship Channelby Mick Williams of Frederick, MD.

©W. R. Grace & Co.-Conn.

[email protected] www.e-catalysts.com

GRACE®, GRACE DAVISON®, ENRICHING LIVES, EVERYWHERE®, CATALAGRAM®, REPLACER®, OLEFINSULTRA®, OLEFINSMAX®, CP®,LIBRA®, XP®, SATURN®, D-PRISM®, SURCA®, DESOX®, GENESIS®, IMPACT®, AURORA®, ALCYON®, MIDAS®, GSR®, are trademarks,registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. REMEDY™, RESIDULTRA™, REACTOR™, REDUCER™,RESID MX™, REBEL™ and TITAN™ are trademarks of W. R. Grace & Co.-Conn.

ART® AND DX® are trademarks, registered in the United States and/or other countries of Advanced Refining Technologies, LLC.

This trademark list has been compiled using available published information as of the publication date of this brochure and may not accuratelyreflect current trademark ownership or status.

© Copyright 2012 W. R. Grace & Co.-Conn. All rights reserved.

The information presented herein is derived from our testing and experience. It is offered, free of charge, for your consideration,investigation and verification. Sinceoperating conditions vary significantly, and since they are not under our control, we disclaim any and all warranties on the results which might be obtained from theuse of our products. You should make no assumption that all safety or environmental protection measures are indicated or that other measures may not be required.

catalagram no. 111 / spring 2012/ww w.grace · 2014. 4. 3. · 1000/2000 2000/3000 z-21 reusy...

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