No.

122 FALL 2018

 A Better Perspective
on Hydroprocessing Solutions

In the refining industry, market conditions are always evolving with new regulatory requirements,
global demand shifts, and the use of heavier feedstocks among other factors. ART Hydroprocessing
can help you take a better perspective on these challenges based on our deep understanding of
refinery operations and a full spectrum of hydroprocessing catalysts solutions that maximize profits
by balancing run length, severity, feed flexibility, contaminants, and operating constraints.

ART is a joint venture of Chevron and W. R. Grace & Co., created to bring you state-of-the-art
hydroprocessing catalyst solutions for petroleum refining applications worldwide. We collaborate
with the industry’s leading licensor, CLG, to provide complete solutions to address your needs to
extract more value from every barrel of oil. Combined with our unparalleled technical customer
service, we deliver results for you.

Contact your ART representative today for more information. [Link]

 EDITORIAL

Investments in Innovation
Scott Purnell, Vice President, Marketing,
Refining Technologies, W. R. Grace & Co.

When people today hear the word among the highest in EMEA with our in our Worms, Germany facility. We
“innovation,” they likely think of the high- ACHIEVE® 100 catalyst and OlefinsUltra® have previously announced logistics
tech industry and the rapidly evolving HZ additive. At Hellenic Petroleum we investments in the UAE, and this year
hardware and software that continues reduced FCC NOx emissions by 65% we have opened the region’s first FCC
to make us more productive and more through the combination of our CP®P equilibrium catalyst laboratory through
connected every day. For a mature and DENOX® additives. Finally, ART's a partnership with Sohar University
industry like refining, with a modern ICR® 1000 catalyst system improved the in Oman to further demonstrate our
history of more than 150 years, one economics of a major refiner's recycle commitment to the Arabian Gulf region.
might expect a slow pace of change. operation by improving the production We have also announced the signing of a
I’m pretty sure that not many people rate of transportation fuels. framework agreement including planned
would immediately associate refining or investments to support Kazakhstan’s
refining catalysts with innovation. But I refining sector and potentially the
would attest that innovation is one of the broader CIS region. Meanwhile progress
key reasons that fossil fuels still dominate
“I would attest that continues to be made on the construction
our energy supply and refining is still an innovation is one of the of ART’s new world-class resid
important industry. Innovation has allowed key reasons that fossil hydroprocessing catalyst plant in Lake
refiners to meet each new challenge and Charles, Louisiana, USA.
to do so in an profitable way.
fuels still dominate
our energy supply We are committed to helping our
Today’s refiner continues to face even customers meet today’s challenges and
and refining is still an
more hurdles – ever-tightening fuel sulfur whatever new ones might lay around
regulations, increased need for heavy oil important industry.” the corner. We aren’t successful unless
upgrading, compliance with air emission you are successful. As always, we look
requirements, and IMO marine fuel Scott Purnell forward to your feedback and continuing
specifications are just a few examples. Vice President, Marketing, the journey together.
At Grace and ART we are investing in Refining Technologies
catalyst innovation to help our customers
meet this challenge. We are investing
in research to develop and launch next Our investments go beyond new
generation catalysts and additives. In products. We are investing in
this issue you will find success stories manufacturing assets to produce
describing the value these innovations these new products as well as in
have delivered through improved yields, infrastructure capabilities to further
reduced emissions, increased catalyst support our customers. As of this
activity, and longer run lengths. At writing, we are in the process of starting
Rompetrol we increased profitability up a production line to produce our
by generating FCCU propylene yields industry-leading MIDAS® catalysts

[Link] | 1
WHAT'S INSIDE

7500 Grace Drive

Columbia, MD 21044 USA IN THIS ISSUE of Catalagram®, our experts demonstrate the value of doing
410.531.4000 business with Grace. From improved product performance to increased
[Link] profitability, Grace’s FCC catalysts and additives and ART’s hydroprocessing
catalysts and catalysts systems deliver significant value in today’s challenging
refining environment.

EDITOR-IN-CHIEF:

What’s Inside
Scott Purnell

MANAGING EDITOR:
Shelly DeButts

EDITORIAL BOARD: GRACE IN THE NEWS SUCCESS STORIES

Eboni Adams 4  COLLABORATION WITH 7  FCC SOX REDUCTION
Shelly DeButts
CUSTOMERS CREATES ADDITIVES: IMPROVING WGS
Scott Purnell
OPPORTUNITIES FOR SCRUBBER ECONOMICS
Bob Riley
IMPROVED REFINERY
Maria Luisa Sargenti
OPERATIONS 12  A CATALYTIC REMEDY
FOR ADVANCED UCO
CONTRIBUTORS:
Collin Baillie
5  FCC WORKSHOPS DELIVER BLEED REDUCTION IN
FUNDAMENTAL VALUE RECYCLE HYDROCRACKING
Derek Blackwell
OPERATIONS
Tom Burgess 5  ART AND CLG
Christophe Chau EXPERTS CONDUCT 18 IMPROVING OPERATING
Tiberiu Crudu
HYDROPROCESSING PROFITABILITY AT THE
John Cunningham
WORKSHOP REFINERY WITH ACHIEVE®
Charltos Damlanou
TECHNOLOGY
Vlorel Duma
Dimitrios Gkanis 25  REDUCING NOX EMISSIONS
Theo Maesen FROM THE HELLENIC
Valentin Nilca PETROLEUM FCC UNIT
Constantinos Plellis-Tsaltakls
Hyunuk Ryu 28  NEWEST ADDITIONS
Maria Luisa Sargenti TO SMART CATALYST
Ljubica Simic SYSTEM ® TECHNOLOGY
Vasilelos Tatsis ACHIEVE LONGER RUN
Adrian Ionut Tudose LENGTHS THROUGH
INCREASED ACTIVITY,
GRAPHIC DESIGN:
IMPROVED STABILITY
Rebecca Huynh
Lisa Schemm

© Copyright 2018 W. R. Grace & Co.

GRACE IN
THE NEWS

[Link] | 3
GRACE IN THE NEWS

Collaboration with Customers Creates Opportunities for

Improved Refinery Operations
ART Hydroprocessing hosted a IKC and KNPC, which can be built to exploring resid catalyst solutions
technical workshop at Chevron’s on for continued knowledge sharing.” together to improve overall refinery
Technology Center in Richmond, ART, KNPC, and IKC look forward economics and operations.
California, USA for customers
currently using ART’s Online Catalyst
Replacement (OCR) technology.
Engineering teams from KNPC’s Mina
Abdullah refinery and IKC’s Aichi
and Hokkaido refiners attended the
workshop, which was held June 25-27,
2018. During the three days, ART’s RDS
technical experts addressed operational
and maintenance aspects of OCR units,
the latest advances in RDS catalyst
technology and deployment of new OCR
and RDS catalysts. In addition, KNPC
and IKC participants toured the state of
the art R&D facilities.

The sessions were conducted by Robert

Wade, ART’s subject matter expert for
Resid Technology, with contributions
from Technical Service leaders Mike
Smith, Steven Song, Srihari Narisetty, Engineering teams from KNPC's Mina Abdullah refinery and IKC's Alchi and Hokkaido refiners learn
Mathew Yu, Chris Dillon, and R&D from ART Hydroprocessing experts at Chevron's Technology Center in Richmond, California, USA.
leaders Viorel Duma and Rong He.

The workshop is example of ART’s

ability to utilize its experience in
operating Chevron units and superior
hydroprocessing knowledge and data
analysis capabilities to collaborate with
customers to improve cycle length and
other performance measures. It is also
one of the ways ART’s local and global
technical service engineers provide
support to customers to improve
unit reliability. Claudia Janse van
Rensburg, KNPC Technical Service
Engineer, remarked “This workshop
provided a valuable opportunity for
KNPC, IKC, and ART Hydroprocessing
to share their experiences, best
practices and research. Critical to the
success of this event was the open
and willing communication between Workshop participants explore operational and maintenance aspects of OCR units and discuss the
latest advances in catalyst technology.

4 | Catalagram® No. 122 | Fall 2018

 GRACE IN THE NEWS

FCC Workshops Deliver Fundamental Value

In May of this year, catalyst experts Ann Benoit, Senior Technical Service Also in May, a group of engineers at
from Grace helped engineers from Manager, FCC. BP's Castellón, Spain facility attended
customer refineries to understand an on-site FCC Fundamentals Workshop
better the fundamentals of FCC unit Over three and a half days, attendees organized by Rafael Gonzalez, Technical
operation and the role catalysts play in heard presentations from our top FCC Sales Manager, FCC. Similar to the
optimizing output for greater efficiency researchers and technical service team Columbia workshop, but designed
and profitability. on topics ranging from understanding for a specific customer, the FCC
FCC heat balance to troubleshooting Fundamentals Workshop is one of
Twenty-one engineers and operators conversion shifts. In addition, they had several hosted by Grace and held at
from companies such as Phillips the opportunity to visit R&D labs on the customers' refineries to address their
66, Shell, and Philadelphia Energy Columbia campus and take a tour of unique needs. The workshops are part of
Solutions gathered at Grace's corporate Grace's Curtis Bay operations. Evenings Grace's ongoing commitment to helping
headquarters in Columbia, Maryland, included a chance to relax and socialize customers create the highest value
USA to attend the semi-annual FCC along with opportunities to discuss possible from their refinery operations.
Technology Workshop organized by further challenges at their units.

ART and CLG Experts Conduct Hydroprocessing Workshop

ART Hydroprocesing (ART) and its workshop benefited from the 80+ years ART and CLG’s practical approach
licensing partner, Chevron Lummus Global of experience provided by ART’s and to developing technology and
(CLG), which is a joint venture between CLG’s technical experts as well as the optimizing operations and SATORP’s
Chevron and McDermott, conducted deep knowledge of SATORP’s HCR commendable approach to achieving
an extensive three-day Operations and units, which were licensed by CLG. The high levels of refinery productivity
Process training workshop at SATORP workshop covered a wide range of topics and results complemented each other
in Jubail, Saudi Arabia on July 2-4, including Hydroprocessing Chemistry well and resulted in a successful
2018. The training was led by technical and Fundamentals, Unit Start-up and workshop. ART and CLG look forward
experts Michael Salyer (CLG), Atanu Operational Excellence. In addition to to conducting future workshops with
Chakraborty (ART), and Alok Srivastava the theoretical content, the participants SATORP as they continue to pursue
(ART) and was attended by an energetic shared real life experiences and case excellence in their operations.
group of SATORP refinery engineers. study reviews that highlighted methods to
Participants at the highly interactive optimize cycle length product yields.

Left to right: Atanu Chakraborty, Technical Service Engineer (ART), Michael Salyer, Technical Service Engineer (CLG), Alok Srivastava, Technical Service
Engineer (ART) with SATORP workshop attendees and Waddah Al-Zaabi, Sales Manager (ART)

[Link] | 5
SUCCESS
STORIES
FCC SOx Reduction Additives:
Improving WGS Scrubber
Economics
Colin Baillie Christophe Chau
Portfolio Manager Regional Marketing Analyst
Environmental Additives Asia Pacific
W. R. Grace & Co. W. R. Grace & Co.

SOx emission control has long been a requirement for

many refineries worldwide, but refiners in certain regions
and countries will continue to face more stringent SOx
targets in the coming years. There are various SOx
emissions abatement measures available for refiners,
including the purchase of low sulfur crude feedstocks, the
use of catalytic feed hydrotreaters or the installation of
wet gas scrubbers (WGS). Although highly effective for
reducing SOx emissions, these options can result in high
OPEX costs and high CAPEX investments.

FCC SOx reduction additives however, represent a

CAPEX-free approach with lower OPEX costs, and
provide refiners with a high degree of flexibility for
controlling SOx emissions across a wide range of
operational conditions. For this reason, FCC SOx
reduction additives have long been considered as being
extremely cost-effective and versatile, and are well
established as one of the best available technologies
for many refineries. This is highlighted by the fact that
more than 130 refiners globally have used Grace’s Super
DESOX® additives.
SUCCESS STORIES

Continued from Page 7 proportion of refiners using SOx additives and highest proportion
of refineries using WGS. The Midwest and West Coast have
WGS versus FCC SOx Reduction Additives a more balanced proportion of refiners using WGS and SOx
additives. Interestingly in most of the regions there are a handful
Two of the main regions currently using SOx additives are
of refiners using a combination of both technologies.
the US and EMEA (Europe, Middle East and Africa). Grace
recently analyzed these markets to compare the use of WGS As highlighted in Figure 2, a much lower proportion of refiners in
versus the use of FCC SOx reduction additives. Figure 1 shows EMEA are using WGS compared to their US counterparts. The
the US market, and it can be seen that proportion of refiners use of SOx additives is particularly prevalent in South Europe, but
using WGS compared to SOx additives differs considerably is also common in North Europe and the Middle East. A handful
according to the Petroleum Administration for Defense District of refiners in Eastern Europe are using SOx additives, while
(PADD), perhaps reflecting the cost of caustic in each district. there is a much smaller amount of SOx additive users in Africa,
The Rocky Mountains has the highest proportion of refiners Russia and the CIS. The EMEA analysis conservatively takes into
using SOx additives and lowest proportion of refineries using account the refiners expected to start using SOx additive later in
WGS. In contrast, the East Coast and Gulf Coast has the lowest 2018 in connection with the new European BREF legislation.

PADD 4 Refiners PADD 2 Refiners

• 71% use SOx additives • 44% use SOx additives
• 29% use a WGS (2 units • 56% use a WGS (1 unit combined
combined with SOx additive) with SOx additive)

PADD 5 Refiners PADD 1 Refiners

• 57% use SOx additives • 29% use SOx additives
• 43% use WGS (1 unit • 71% use a WGS
combined with SOx additive)
PADD 3 Refiners
• 28% use SOx additives
• 72% use a WGS (4 units
combined with SOx additive)

Figure 1: US SOx Reduction Market by PADD

North Europe Eastern Europe

• 37% use SOx additives • 8% use SOx additives
• 13% use a WGS • 4% use a WGS

South Europe Middle East

• 60% use SOx additives • 31% use SOx additives
• 7% use a WGS • 15% use a WGS

Figure 2: EMEA SOx Reduction Market by Region

8 | Catalagram® No. 122 | Fall 2018

 FCC SOX REDUCTION ADDITIVES: IMPROVING WGS SCRUBBER ECONOMICS

Economic Benefits of Using

Caustic Soda Price (US$/Dry MT)
SOx Additives
1000
Over the past two years global caustic 800
pricing has increased considerably,
600
which for those refineries operating a
400
WGS will be having a significant impact
on OPEX costs. Figure 3 highlights 200
caustic pricing in the US West Coast, 0
US West US US US NW NE
US Midwest, US Northeast, US Coast Midwest Northeast Southeast Europe Asia
Southeast, NW Europe, and NE Asia.
The pricing varies considerably by 1Q2016 1Q2018
region, but in each example a significant
increase in caustic price has been
observed in the last two years. Figure 3: Caustic Soda Market Pricing

Because SOx reduction additives are Figure 4 highlights the potential cost • Case 1 is based on the additive
a well-established, robust, and reliable savings for a typical refiner operating being used for 75% of the SOx
route to achieve emissions targets, it is a caustic WGS when deciding also to reduction, while caustic is used for
possible to make an accurate estimation use SOx additives to reduce caustic the remaining 25% SOx reduction.
of the potential cost savings associated consumption requirements. It assumes • Case 2 is based on the additive
with using an optimum combination uncontrolled SOx emissions of 800 being used for 50% of the SOx
of caustic WGS with SOx additives. ppmv, with a target SOx level of 25 reduction, while caustic is used for
The factors that impact the overall ppmv, and a flue gas flow rate of the remaining 50% SOx reduction.
economic evaluation include the level 100,000 SCFM (158 kNm3/hr, which
of uncontrolled SOx emissions (i.e., • Case 3 is based on the additive
would typically represent an FCC unit
the SOx levels that would be obtained being used for 25% of the SOx
Fig 4
without the use of any SOx reduction
processing 60-65 kBPD feedstock). It
reduction, while caustic is used for
considers a caustic soda price range
technology), the target SOx levels, the the remaining 75% SOx reduction.
of 500 to 600 $/MT, and incorporates
caustic soda price, the effectiveness of typical market pricing for SOx additives. It also takes into account that SOx
SOx additives for a given operation, and The analysis considers that SOx additive efficiency will decrease slightly
the price of the SOx additive. additives can be used to achieve for higher targets of SOx reduction. For
different levels of the SOx reduction example, at an uncontrolled SOx level
required. For example: of 800 ppmv, the SOx additive Pick Up

$/year Caustic Savings Percentage

$1,500,000 75%
$1,250,000 Case 1: 75% SOx
Reduction Through Additive
$1,000,000 50%
$750,000 Case 2: 50% SOx
Reduction Through Additive
$500,000 25%
Case 3: 25% SOx
$250,000
Reduction Through Additive
$0 0%
500 550 600 500 550 600
Caustic Price ($/MT) Caustic Price ($/MT)

Figure 4: Potential Cost Savings for Optimum Combination of Caustic WGS and SOx Reduction Additives

Continued on Page 9

[Link] | 9

1 Presentation Title | Month 00, 2018 W. R. Grace & Co. | Confidential

SUCCESS STORIES

Continued from Page 9 several factors including the inlet temperature, pressure,
caustic concentration and caustic water flowrate. The operating
Factor (PUF, mass of SOx captured per mass of SOx additive conditions of the WGS were maintained constant before and
used) will be lower when targeting 75% SOx reduction through during the additive trial period, with the exception of the caustic
use of additive compared to a target of 25% SOx reduction. It can usage. The key target and requirement was to comply with the
be clearly seen that high levels of cost savings are possible even SOx emission limits at 25 ppm in the stack after the WGS.
when using SOx additives to only achieve 25% of the required
SOx reduction. However, the cost benefits are considerably Prior to the SOx additive trial, SOx emissions were in the range
higher again when using SOx additives to achieve 75% of the of 80-100 ppmv. As highlighted in Figure 7, upon addition of
required SOx reduction, with savings of up to $1 million per year Super DESOX® additive, a rapid decrease in SOx emissions was
achievable. Another way of looking at this is that refiners can observed, and the target limit of 25 ppmv was comfortably met
save between 20 to 40% of their caustic costs by using SOx with SOx levels as low as 5-10 ppmv achieved. After stopping
additives. An additional advantage for refiners will be a reduction the Super DESOX® additive injection, the SOx emissions
in caustic disposal costs, which has not been taken into account remained below the regulatory limit for a period of seven days,
in this analysis. demonstrating the excellent activity retention of the additive.

Besides the noticeable impact on SOx levels, Super DESOX®

Grace SOx Reduction Technology additive allowed a considerable reduction of caustic usage in
Grace’s Super DESOX® additives are designed to reduce flue the WGS operation. By the latter part of the additive trial, caustic
gas SOx emissions from the FCCU regenerator. They are consumption had been reduced by 60% through use of the SOx
unique in that they incorporate a patented magnesium spinel reduction additive.
platform, resulting in an optimized system for SO2 oxidation,
the capture of SO3, and additive regeneration. Super DESOX® In addition to lower SOx levels and lower caustic usage, the
additives are typically used at dosing rates of 2-10 wt.% refinery observed an improvement in the level of particulates in
of fresh catalyst additions, and are effective for controlling the stack emissions, resulting in an estimated 10% lower level of
emissions well below 25 ppmv SOx. Super DESOX® additives fines in the TSS. This presents the refinery with a wider operating
can be preblended with fresh catalyst or delivered separately, flexibility while complying with particulates emissions regulations.
to provide refiners with a full flexibility of options. In addition to
benefits of reducing WGS caustic consumption, SOx additives
Environmental
also allow refiners to balance refinery wide SOx emissions Compliance
when operating under bubble limits, they provide economic
flexibility to process feeds high in sulfur, and can relieve
pressure on FCC feed hydrotreaters. Residual SOx
Caustic Particulates
Soda
Reducing Caustic Usage and OPEX at
Refinery A with Super DESOX® Additives Wet Gas
Scrubber
The following case study features an FCC unit from Refinery A
Filter +
in the Asia Pacific region, which processes residue with a typical Gas/Droplet
sulfur content of 0.35 wt.%. The FCCU is equipped with a flue Separator
gas scrubber using caustic water, as well as a Third-Stage Stack
Separator (TSS) for catalyst fine recovery after the primary and
secondary regenerator cyclones. The refinery recently decided
Water
to trial Grace’s Super DESOX® additive due to more stringent Make-up
regulations on SOx emissions. Refinery A use FCC catalyst from
Grace, and after an initial base loading period of SOx additive,
Flue Gas
moved to a continuous addition of 3 wt.% of Super DESOX® From FCC
additive during the trial.
Caustic Water
Recirculation
The wet gas scrubber (WGS), as depicted in Figure 6, enables
the removal of mainly SO2, as well as SO3, gaseous pollutants
and catalyst particulates by contacting the flue gas with a Figure 5: Schematic View of the Downstream Treatment of the FCC Flue
caustic water solution. The WGS efficiency is impacted by Gas Featuring a Wet Gas Scrubber

10 | Catalagram® No. 122 | Fall 2018

 FCC SOX REDUCTION ADDITIVES: IMPROVING WGS SCRUBBER ECONOMICS

In order to quantify the benefits for the refinery, a caustic

Gas Outlet
price of $600 per metric ton was used in the evaluation, and
a 60% reduction of the caustic water washing flowrate used
prior to the SOx additive trial. Based on this OPEX costs were
reduced by $4,500 on a daily basis, corresponding to yearly
Stack
savings of approximately $1.6M. Local caustic pricing has even
exceeded $600 per metric ton in the meantime, so the economic
savings using SOx additives to offset caustic costs are on the
conservative side.
Cyclones/Separators
The use of SOx reduction additives offer refiners an opportunity to
reduce OPEX costs during periods of high caustic prices. A case
study from Refinery A in Asia Pacific has been used to highlight
this, in which Super DESOX® additive demonstrated excellent Filters Caustic + Water
levels of SOx reduction to meet environmental requirements, with
SOx emissions reduced from 80-100 to as as low as 5-15 ppmv. Quench

Moreover, the use of Super DESOX® additive provided the Ex-FCC / Gas
refinery with the opportunity to decrease the consumption of Scrubber Inlet
caustic water in the wet gas scrubber, which was estimated Caustic + Water
To Purge
to have provided a reduction in OPEX costs by approximately Treatment
$1.6M on an annual basis.

Figure 6: Representative Scheme of the Wet Gas Scrubber

Figure 7: Lower SOx Emissions and Lower Caustic Usage Using Super DESOX® Additive

[Link] | 11
A Catalytic Remedy for
Advanced UCO Bleed
Reduction in Recycle
Hydrocracking Operations
Derek Blackwell Theo Maesen
Technical Service Specialist Global R&D Specialist
ART Hydroprocessing ART Hydroprocessing

Viorel Duma Hyunuk Ryu

Senior R&D Engineer Technical Service Leader
ART Hydroprocessing ART Hydroprocessing

A refinery’s flexibility and responsiveness to market

dynamics and regulatory environments has a major
impact on its competitive position. Several factors
drive this need for responsiveness including the
availability of inexpensive opportunity crudes and
compatible cutter stocks, tightening regulations
on residual fuel oil, and price differentials between
petrochemical feedstocks, base oil and transportation
fuels. Tighter specifications on refinery process
schemes combined with more robust catalyst systems
affords more sustainably turning a larger portfolio
of opportunity feedstocks into a product slate that is
more in sync with the market dynamics1.
 A CATALYTIC REMEDY FOR ADVANCED UCO BLEED REDUCTION IN RECYCLE HYDROCRACKING OPERATIONS

Dealing with Refinery Constraints into thermodynamically more favored larger configurations.
This simultaneous formation of a more aromatic solute inside
Refineries impose constraints on operations to maximize a less aromatic solvent can create nano-emulsions, which can
operational reliability. Recent process and catalyst options form mesophases (liquid crystals) that can ultimately sediment
have been developed that significantly reduce and refine these out either inside the reactor or inside equipment downstream
constraints postures. With the production of light crudes and from the reactor. A recent catalyst system has been designed
heavy crudes increasing and with medium crudes in decline, more that disrupts this sedimentation process by saturating key feed
and more refineries are feeding opportunity blends of light and components before these are stripped into their incompatible
heavy crudes. These crude blends raise compatibility concerns, aromatic cores. The efficacy of this disruptive catalyst system
and they can challenge the distillation train, which frequently is best illustrated in a hydrocracker configuration that runs in
exacerbates entrainment of residual oil in the hydrocracker feed. recycle operation.
Entrained residual oil has a deleterious impact on hydrocracker
performance even if the entrainment is so small that it is close to
the detection limit of standard analytical techniques (Table 1). If How to Disrupt Sedimentation
capital is available, one can invest in improved process options Sedimentation of molecules that have become incompatible
to improve the hydrocracker feedstock, and thereby mitigate the with the gas oil as it is being hydroprocessed is a particularly
exposure to the negative impact of opportunity crudes. A capital- acute problem in hydrocrackers running in recycle (Figure 1).
neutral solution is a catalyst system that can mitigate the risk Recycle operation augments the impact of incompatibility because
associated with only a minor increase in end boiling point of the this operation concentrates the polycyclic aromatic solute by
feedstock to the hydrocracker. hydrocracking the solvent into transportation fuels, and by distilling
these fuels away as products. This concentrates the already
Simdist (wt%), °F Bulk Saturates Aromatics Resins not overly compatible aromatic solute, and concentration further
0.5 470 489 509 584 enhances the risk of bringing the aromatic solute well above its
5 611 618 615 688 solubility limit. The associated risk of a catastrophic seizure of the
run through sedimentation inside the recycle loop is well known.
10 654 665 653 727
Sedimentation is typically controlled by carefully monitoring the
30 729 740 722 808
recycle loop for the buildup of sediment-forming heavy aromatics
50 781 792 771 861 and by bleeding the appropriate fraction of unconverted oil to
70 839 850 826 912 keep these aromatics under their solubility limit. There are several
90 923 932 912 1043 monitoring options: i) by color, visually; ii) by UV Vis spectroscopy
from which one can derive a PolyCyclic aromatic Index (or PCI,
95 962 965 953 1118
a marker for incompatibility risk); iii) by spot checking the buildup
99 1054 1021 1049 1211
of aromatic compounds with high-resolution mass spectrometry
EP 1092 1040 1081 1238 (Figure 2). This reactive approach to mitigating incompatible

Table 1: Entrainment of residual oil (i.e. oil boiling above 1050 F) often
goes undetected by a single fractionation method, such as simulated
distillation by gas chromatography. Fractionation into saturates, Make-up
Hydrogen Fuels
aromatics and resins by liquid chromatography (ASTM D2007) followed
Hydrocracker Products
by simulated distillation frequently brings residual oil entrainment into Fresh
sharp contrast. Feed
Unconverted
Oil

How to Mitigate the Impact of

Incompatibilities During Hydroprocessing Recycle Bleed

Residual oil entrained in the feed to a hydrocracker designed to

hydroprocess vacuum gas oil is a problem, because parts of the Figure 1: Converting more of the bleed stream into product is a major
residual oil frequently do not maintain their compatibility once the way of improving the economics of recycle operation. The most
feed starts to be hydroprocessed. Compatibility is lost because refractory compounds left unconverted would accumulate in the recycle
hydroprocessing strips the complex residual oil molecules loop if it were not for a bleed to e.g. an FCC unit.
initially dissolved in the feed down to polycyclic aromatic cores,
whilst simultaneously saturating the feed into a less aromatic
stream that is less hospitable to large aromatics. Compatibility
Continued on Page 14
is further reduced by the condensation of smaller aromatics
[Link] | 13
SUCCESS STORIES

Continued from Page 13 opportunity to agglomerate, to emulsify or to become recalcitrant

to hydroprocessing in other ways. Since the incompatible large
aromatics accumulation generates a low-value bleed stream of aromatic compounds agglomerate already at low concentrations
unconverted oil, which misses an opportunity to hydroprocess and since they boil toward and above the tail end of typical
this oil into high-value transportation fuel (Figure 1). We have hydrocracker feedstock boiling range, traditional hydrotreating
demonstrated the efficacy of a more proactive approach that catalysts focus at saturation of the majority of the feedstock
mitigates the risk of the buildup of incompatible compounds (the solvent) and do not start to saturate the low concentration
before it gets started. We show how this proactive approach of polycyclic aromatics (the solute) until it has built up to
minimizes the bleed stream and commensurately improves the appreciable (and undesirable) levels (Figure 3A/B). In marked
production rate of transportation fuel without a major impact on contrast, the unique pore structure and high hydrogenation
run length. activity of the new ICR® 1000 catalyst affords it to selectively
target the polycyclic aromatics even at concentration well below
One can proactively counteract sedimentation by selectively
the level at which they start to agglomerate. A comparison of
keeping the polycyclic aromatics in the hydroprocessing
the efficacy of a catalyst system with ICR® 1000 as compared
streams at their hydrogenation equilibrium before they have an

115 PCI 250 PCI 450 PCI 500 PCI 620 PCI 645 PCI

Figure 2: To assure that a recycling hydrocracker run does not fail catastrophically by refractory compounds settling out in the recycle loop, the color
and polycyclic aromatic index (PCI) are regularly monitored and maintained within an acceptable range bleeding part of the recycle stream.

Figure 3A: Traditional hydrotreating catalyst systems first hydrotreat Figure 3B: Typical catalyst systems hydrocrack the high-boiling vacuum
the bulk of the vacuum gas oil (VGO) solvent and only start bringing gas oil (VGO) solvent into a lower transportation fuel range, which
the heavy polynuclear aromatics (HPNA’s) solute to hydrogenation concentrates the refractory sediment precursors in the unconverted
equilibrium when this solute is at appreciable concentrations. By oil. Hydrocracking systems containing ICR 1000 convert some of the
contrast, hydrotreating catalyst systems with sufficient ICR 1000 focus sediment precursors, which results in a lower polynuclear aromatics
at hydrogenating the HPNA solute first. Index or PCI.

14 | Catalagram® No. 122 | Fall 2018

 A CATALYTIC REMEDY FOR ADVANCED UCO BLEED REDUCTION IN RECYCLE HYDROCRACKING OPERATIONS

to a typical catalyst system illustrates A Commercial Example the heavy polycyclic aromatic sediment
the selective hydrogenation of a precursors stay at an acceptable level.
representative polycyclic aromatic The most powerful illustration is what
compound doped into a typical vacuum happens when this concept is taken into Recently, ICR® 1000 was added to the
gas oil (Figure 3A). Another illustration is practice at a commercial hydrocracker catalyst system of one hydrocracker
the significant reduction of PCI (a marker that hydroprocesses RDS VGO in to catalytically disrupt the buildup of
for incompatibility risk) by adding ICR® recycle operation (Figure 1) Interestingly, sediment precursors in the UCO, and
1000 to a catalyst system deployed to the bulk properties (more saturated, the results are compared with the other
hydroprocess a vacuum gas oil (VGO) lower boiling range) of RDS VGO hydrocracker’s most recent two cycles
feed derived nearly exclusively from suggest that it should be significantly which use virtually the same catalyst
residue desulfurization (RDS) in once- more amenable to hydroprocessing than system but without ICR® 1000. Due to
through operation (Figure 3B). a typical Straight-Run (SR) VGO (Table changes in the refinery stock balance,
2), whereas the exact opposite is true the refiner had to increase the feed end
Simdist (wt%), °F SR VGO RDS VGO in that RDS VGO is significantly more boiling point (Figure 4), and had to add
recalcitrant to hydroprocessing. some highly aromatic CGO (Figure 5)
Saturates (wt-%) 50 54
to the cycle containing ICR® 1000. As a
Aromatics (wt-%) 44 42 A refiner recently deployed the ICR® 1000 result, feed nitrogen content increased
Resins (wt-%) 6 4 technology to sustainably minimize the (Figure 6), feed PCI increased (Figure
API 21.7 24.9 low-value bleed of UnConverted Oil(UCO) 7), and the feed became more aromatic.
and produce commensurately more value- Even at about 450 days on stream the
S (ppm) 22056 5654
added fuel. refiner kept the feed more aromatic as
N (ppm) 996 915
compared to the cycles without ICR® 1000
H by NMR (wt-%) 12.26 12.52 This refiner has two virtually identical
(Figures 4-7). Even though the properties
PCI 2293 791 hydrocrackers which have the same
of the feed for the ICR® 1000 run suggest
configuration, operating conditions and
MCRT 0.29 0.05 that it is considerably more challenging,
feed. The feed consists of RDS VGO,
HHA* (ppm) 67 127 the PCI of the UCO in the recycle stream
SR VGO and Coker Gas Oil (CGO). The
of the ICR® 1000 run remained at a similar
SimDist (wt-%) F hydrocrackers are targeting maximum
level, if not lower than the runs without
0.5 624 595 middle distillate product yield (mainly
ICR® 1000 (Figure 8).
5 689 680 jet) and maximum overall conversion of
the feed. The feed conversion has been
10 723 710
limited by the need to bleed UCO from
30 793 775 the recycle loop so as to assure that
50 845 825
70 899 880
90 979 950
95 1018 975
99 1092 1035

Table 2: Typical physical properties suggest

that a vacuum gas oil (VGO) derived from an
residual oil hydrodesulfurization (RDS) unit is
more saturated and should hydroprocess with
more ease than a straight run VGO, whereas
the reverse is true.

Figure 4: For the ICR® 1000 cycle the feed end boiling point was increased.

Continued on Page 16

[Link] | 15
SUCCESS STORIES

Continued from Page 15

In addition to addressing stock balance

issues, (and more impactfully), the
refiner increased the product value
by significantly reducing the bleed
rate (Figure 9A). This bleed reduction
appears not to have reduced the cycle
length. The total UCO bleed reduction
in the ICR® 1000 cycle is projected
to be approximately 2,000 Mbbl over
the three years’ cycle length, and
the corresponding middle distillate
production increase is estimated to be
approximately 1,500 Mbbl (Figure 9B).
The resulting economics can vary widely Figure 5: For the ICR® 1000 cycle the coker gasoil (CGO) content of the feed was increased.
depending on the specific refinery’s
situation and the local, regional and
global market conditions. However, if we
assume an average $10/bbl differential
between middle distillates and UCO,
the impact of the bleed reduction alone
easily amounts to $15-16 MM for the
current cycle.

Operating hydrocrackers in recycle

operation with RDS VGO and CGO
feed is a major challenge due to the
risk of high polycyclic aromatics build-
up and sedimentation terminating the
run prematurely. Controlling the buildup
of refractory aromatics becomes more
challenging as the hydrocracker is
running more toward full conversion Figure 6: For the ICR® 1000 run the organic nitrogen content of the feed increased as a corollary of
of the feed to maximize diesel or jet the end boiling point increase and of the CGO addition.
production. Typically, the buildup of
polycyclic aromatic sediment precursors
and run length is thereby maintained by
the judicious bleeding of unconverted oil.

Here we demonstrate how a close

cooperation with a client led to the
commercial introduction of a catalytic
solution, ICR® 1000, by Advanced
Refining Technology (ART) that converts
more feed into jet by lowering the bleed
rate without impacting run length.

References
1. U Mukherjee, D. Gillis, PQT Q1 2018 75-83
2. J.G. Fetzer, D.G. Lammel, US 5190633, 1993;
G.W. Henriks, E.C. Attane, J.W. Wilson, US Figure 7: For the ICR® 1000 run, the PCI of the feed increased as a corollary of the end boiling point
3619407, 1971. increase and of the CGO addition.

16 | Catalagram® No. 122 | Fall 2018

 A CATALYTIC REMEDY FOR ADVANCED UCO BLEED REDUCTION IN RECYCLE HYDROCRACKING OPERATIONS

Figure 8: Despite the higher PCI of the feed, the unconverted oil maintains PCI.

Figure 9A: Despite the more challenging feed, there is less unconverted oil (less bleed) and
commensurately more product.

Expected UCO Bleed Rate per Proposal

Figure 9B: Despite the more challenging feed and the lower bleed rate, the unit is slated to make it
usual cycle length.

[Link] | 17
Improving Operating
Profitability at the Refinery
with ACHIEVE® Technology
Tiberiu Crudu Maria Luisa Sargenti
FCC Plant Manager Marketing Manager
KMG Rompetrol W. R. Grace & Co.

Valentin Nilca Ljubica Simic

FCC Senior Process Engineer Technical Sales Manager
KMG Rompetrol W. R. Grace & Co.

Adrian Ionut Tudose

Production Planner
KMG Rompetrol

KMG Rompetrol are addressing current market

challenges through a strategy of downstream
integration with petrochemicals, taking advantage
of the flexibility that the Fluid Catalytic Cracking
(FCC) unit offers for maximum light olefins
production. In this article, KMG Rompetrol and
Grace provide an overview on how refineries can
increase the profitability of their FCC operation by
maximizing the production of propylene and iso-
butylene using the latest FCC catalyst and additive
technology. ACHIEVE® technology from Grace has
contributed sustaining the refinery’s profitability,
as well as improving its competitive position in the
marketplace. This technology has resulted in yields of
11 wt% propylene, which ranks the refinery’s FCC unit
among the top five propylene producers in EMEA.
 IMPROVING OPERATING PROFITABILITY AT THE REFINERY WITH ACHIEVE® TECHNOLOGY

Maximization of propylene production has become the focus

of many refineries because propylene consumption continues Volume Change (mb/d)
to grow and there is a supply shortage, resulting in a supply- 2016-25 2025-35 2016-35
demand gap. Demand for propylene is driven mainly by the Transport 4.5 0.8 5.3
global polypropylene industry, which has seen historical growth Petchem (includes ethane) 2.8 3.4 6.2
14
of 5.0-6.0 %/year1. As shown in Figure 1, by 2035 petrochemical Other 0.1 0.6 0.7
products will account for almost 50% of the expected growth
in demand for crude-oil based products, of which a significant 12
portion will be propylene.

In Asia-Pacific (and to a large but slightly lesser extent in the 10

EMEA region) propylene demand is high; therefore, many
refineries that have the potential to produce more propylene are

Million b/d
8
enjoying a competitive edge in the industry. There are different
ways for refineries to increase production of light olefins, for
example through a revamping and debottlenecking of the 6
entire FCC unit. However, using the latest catalyst and additive
technology offers a reliable, quick, and flexible route.
4

KMG Rompetrol Unit and Operating Focus

2
The KMG Rompetrol company operates two production facilities:
Petromidia, consisting of a refinery and a petrochemical
complex, as well as the Vega refinery. Petromidia is located in
Constanta close to the Black Sea, which gives KMG Rompetrol 2017 2019 2021 2023 2025 2027 2029 2031 2033 2035
several strategic advantages. The Petromidia Refinery Nelson Transport Other Petchem Ethane Other
Complexity Index is 10.5 and is usually processing URAL crudes Source: Wood Mackenzie
but also blends with other crudes such as Kirkuk, Azeri, and
Siberian. The FCC unit is a 24,000 bbl./day UOP Side-by-Side
design and is processing 100% hydro-treated feed coming from Figure 1: Supply-demand of Propylene
a Mild Hydrocracking Unit.

Petrochemical Complex

Propane
C3
C3 Cut
Splitter Polymer Grade
Column Propylene Polypropylene Polypropylene
Unit
AGO
Light C4 Cut MTBE
MTBE Unit
Atmospheric Mild
LVGO UCO
and Vacuum Hydrocracking Fluid Catalytic Heavy C4 Cut
Distillation Units Unit LPG Blending
Cracking Unit
HVGO Gasoline
Gasoline Blending

Light Cycle Oil

Diesel Hydrotreaters

Slurry / Decanted Oil Delayed Coker Unit

Fuel Oil

Figure 2: Refinery Block Diagram

Continued on Page 20

[Link] | 19
SUCCESS STORIES

Continued from Page 19 Improved Performance through FCC

Solomon Benchmark Related Figures Catalyst Optimization
Every two years, Rompetrol Rafinare participates in the Solomon The refining market is more global and more competitive
Worldwide Fuels Refinery Performance Analysis (Fuels Study) than ever and Grace recognizes the importance of providing
and receives the graphs below, which shows the Conversion value to its customers through new product development.
Units’ performance. The KMG Rompetrol and Grace teams have worked closely
together to better identify refinery opportunities, as well as to
Figure 3 highlights the FCC unit performance related to the understand challenges and limitations in more depth, which
1st quartile / 2nd quartile break (black line), and with respect has been essential for overall success. The following objectives
to the world’s top 10% of performers (green line). FCC unit were identified as the main drivers to help increase FCC unit
performance is based on SOLOMON methodology, using a profitability²:
correlation between Dynamic Activity (measure of catalyst
performance) and Feed UOP K Factor. The graph demonstrates • Maximum propylene yield • High RON
that the Rompetrol FCC unit (red dot ‘2016’) is placed in the 1st (min.10 wt% of FF) • Higher delta coke
quartile and close to world’s top 10% performers. • Maximum iso-butylene yield • Minimize dry gas
• Maximize LCO

Maximum propylene is driven by demand from the nearby

petrochemical plant, while maximum iso-butylene is highly
desired to boost MTBE unit capacity. Grace executed a rigorous
process to qualify and verify selected catalyst performance,
including ACE™ pilot plant testing, which minimizes the financial
risk associated with unsuccessful catalyst trials in the unit 3,4.

Based on extensive ACE™ pilot plant testing utilizing a

representative feedstock from the KMG Rompetrol Petromidia
refinery, various new catalyst formulations were screened versus
the base catalyst. This enabled Grace to identify a combination
of the ACHIEVE® 100 catalyst and OlefinsUltra® HZ light olefins
additive as the leading formulation to provide the optimum
performance in terms of the desired operating targets. As
Figure 3: Solomon - FCC Yield Gaps
shown in Figure 5, this catalyst system resulted in a significantly
higher propylene and iso-butylene yields, as well as higher LCO
This gap in yield performance, as measured by a Dynamic and lower slurry (decanted oil), which demonstrates a clear
Activity gap compared to world’s top 25% of performers, can improvement in bottoms upgrading.
then be translated to a gap in product yields and then into a
gap in USD/bbl. Figure 4 shows that in both 2014 and 2016 iC4=/L PG
Solomon Worldwide Fuels Studies, the Rompetrol FCC Unit is iC4=/t o t al C4
placed at the border between 1st and the 2nd quartile from a t o t al C4
iC4=
total of approximately 300 FCC units in the Solomon Worldwide C3=
Fuels Study. HCO , 3500C
L CO
G aso lin e
In Figure 4 each FCC Unit is placed in one of the 4 quartiles (red L PG
color represents the 4th quartile and the green color represents Dry G as
the 1st quartile). d co ke
Co ke
C/O
Catalytic Cracking (303 units)
-1.5 -1 -0.5 0 0.5 1 1.5

2014 2015
Figure 5: ACE Performance Deltas (wt.%)

Figure 4: Solomon – Yield Gap Quartile of Performance

20 | Catalagram® No. 122 | Fall 2018

 IMPROVING OPERATING PROFITABILITY AT THE REFINERY WITH ACHIEVE® TECHNOLOGY

ACHIEVE® and OlefinsUltra® HZ Base Catalyst ACHIEVE® Base Catalyst ACHIEVE®

Technologies

ECAT ACE Propylene, wt%

11.0
10.5
The ACHIEVE® catalyst series comprises state-of-the-art 10.0
technologies designed to maximize refinery profitability for 9.5
a wide range of FCC feedstocks and yield objectives. When 9.0
processing lighter feedstocks, insufficient catalytic activity 8.5
8.0
requires that the catalyst circulation rate increase so that
7.5
conversion, and thus the coke yield from the catalyst, increases 7.0
to satisfy the FCC heat balance. If the FCCU cannot physically 6.5
circulate enough catalyst, it will be necessary to reduce the 6.0
unit charge rate or the reaction severity to stay within the FCC 71 72 73 74 75 76
catalyst circulation limit. Use of a high activity catalyst can Conversion, wt%
counter the effects of low delta coke, highlighting the importance
to select a catalyst with the proper coke selectivity (coke to
Figure 6: E-cat Propylene Selectivity
conversion relationship).

ACHIEVE® 100 catalyst is designed for use with hydro treated

Base Catalyst ACHIEVE® Base Catalyst ACHIEVE®
and light VGO feedstocks, with a low-to-moderate level of 3.5
contaminant metals. ACHIEVE® 100 catalysts are formulated
with ultra high activity zeolite to support conversion and counter IC4=, wt% 3.0
the effects of low delta coke, while delivering the proper coke
selectivity. The high diffusivity of ACHIEVE® 100 catalyst
2.5
increases distillate yield, while an optimized rare earth exchange
results in the required hydrogen transfer activity to balance LPG
2.0
and gasoline production.

Launched in 2010, OlefinsUltra® HZ additive is part of Grace’s 1.5

71 72 73 74 75 76
OlefinsUltra® family of propylene maximization additives. The
family includes OlefinsUltra® additive for moderate-to-high Conversion, wt%
propylene yields, OlefinsUltra® HZ additive for high propylene
yields, and OlefinsUltra® MZ additive with industry leading Figure 7: E-cat Iso-butylene Selectivity
activity, for very high propylene yields.

The entire OlefinsUltra® family of additives is manufactured with

Base Catalyst ACHIEVE® Base Catalyst ACHIEVE®
Operating Data Propylene, wt%

excellent attrition resistance and low 0–40%. Our testing has

12
demonstrated that OlefinsUltra® HZ shows excellent activity
retention achieving required maximum unit performance. 11

10
Validating Catalyst and Additive 9
Performance 8
When the ACHIEVE® 100 catalyst preblended with OlefinsUltra®
7
HZ additive was added to the FCC unit, the turnover of the
circulating inventory to the new catalyst was carefully evaluated. 6
Typically, the impact of new catalyst grades on FCC product 80 85 90 95

yields can be observed by the time 60% catalyst turnover is Conversion, wt%
achieved. In parallel to this, E-cat analysis was performed using
samples received from the refinery on a weekly basis. This Figure 8: FCC Unit Propylene Yields
allows catalyst performance to be evaluated independently
of the daily variations that occur in FCC unit, as the testing is
performed using standard feedstock and constant operating
conditions. ACE™ E-cat testing is shown in Figures 6 and 7. At
constant conversion, the new catalyst system delivered higher
selectivity towards propylene and iso-butylene. Continued on Page 22

[Link] | 21
SUCCESS STORIES

Continued from Page 21

Base Catalyst ACHIEVE® Base Catalyst ACHIEVE®
As shown in Figures 8, 9, and 10, the trends observed in ACE™ 54
testing of equilibrium catalyst were also observed in the FCC
52
unit. Using the combination of ACHIEVE® 100 and OlefinsUltra®

Gasoline, wt%
HZ technologies, both propylene and iso-butylene yields were 50
increased significantly at constant conversion. 48

Gasoline yields are reduced using ZSM-5 additive due to the 46

cracking of gasoline range olefins into lighter olefins. However, 44
the enhanced activity of ACHIEVE® 100 catalyst enabled a
deeper cracking of heavier molecules into gasoline, therefore 42
80 85 90 95
minimizing the loss of valuable gasoline despite the higher light
Conversion, wt%
olefin yields (Figure 11). The gasoline octane RON and MON
also slightly improved as a result of the new catalyst system. The
improved bottoms cracking obtained through the ACHIEVE® 100 Figure 11: FCC Unit Gasoline Yield
catalyst in the commercial unit is shown in Figure 12 and 13.

Base Catalyst ACHIEVE® Base Catalyst ACHIEVE® Base Catalyst ACHIEVE® Base Catalyst ACHIEVE®
4.0
Iso-Butylene, wt%

12
3.0
LCO, wt%

2.0 8

1.0 4

0.0 0
80 82 84 86 88 90 92 94 80 85 90 95
Conversion, wt% Conversion, wt%

Figure 9: FCC Unit Iso-Butylene Yield Figure 12: FCC Unit Light Cycle Oil Yield

Base Catalyst ACHIEVE® Base Catalyst ACHIEVE® Base Catalyst ACHIEVE® Base Catalyst ACHIEVE®
0.5 10

8
iC4= / C4=e, wt%

0.4
Slurry, wt%

0.3 6

0.2 4

0.1 2

0.0 0
80 82 84 86 88 90 92 94 80 85 90 95
Conversion, wt% Conversion, wt%

Figure 10: FCC Unit Iso-Butylene Content in C4 Olefins Yield Figure 13: FCC Unit Slurry Yield

22 | Catalagram® No. 122 | Fall 2018

 IMPROVING OPERATING PROFITABILITY AT THE REFINERY WITH ACHIEVE® TECHNOLOGY

Unit Test Run PIMS Value added Calculation

KBC’s FCC-SIM simulation tool was used to evaluate the
®
Figure 14 outlines what steps are accomplished from catalyst
performance of ACHIEVE® 100 catalyst vs. the base catalyst selection using ACE™ testing to the unit performance
at constant coke. The test runs selection criteria to obtain evaluation using refinery PIMS model. As already said the
calibration factors were based on the following: lab scale-testing goal is to match the commercial FCC unit
performance estimate5.
• Complete and robust set of feed, operating and product data
• Heat of cracking ratio within acceptable range (0.7-1.3) However, the refinery is only focusing on real unit
and consistent kinetic coke make and conversion kinetic performance results.
parameters.
The benefit calculation coming from the new re-formulated
• Calibration of selected FCC unit weekly test data to obtain a ACHIEVE® 100 catalyst vs the base catalyst was performed
reliable set of calibration factors by running two scenarios with the help of AspenTech PIMS™
Model. PIMS (Process Industry Modelling System) is the refinery
In the simulation exercise, the ex-reactor product standard yields production optimization tool based on linear programming.
were considered: (gasoline C5-221ºC, LCO 221-343ºC and FCC
Bottoms +343ºC). The yields shifts with operation parameters Main assumptions of the two scenarios were:
and equilibrium catalyst physical and chemical properties are
given in Table 1. • similar refinery run rate and similar FCC Unit Feed Rate both
in terms of quantity and quality;
Performance ACHIEVE® vs. Base • similar FCC Unit Operating Conditions: Reactor Overhead
Conversion, wt% -0.02 Temperature & ZSM-5 additive injection;
Dry Gas, wt% 0.29 • degrees of freedom were provided to the Finished Products
C3=, wt% 1.26 selling operations to capture the impact of new FCC Unit re-
formulated ACHIEVE® 100 catalyst in refinery operation;
iC4= , wt% 1.05
LPG, wt% 1.68 After running the two scenarios, an annualized benefit of ~ $2.3
Total Naphta, wt% -1.77 MM USD has been obtained. The benefit is mainly coming from
LCO, wt% 2.03 higher Light Olefins production – higher content of Propylene in
Slurry, wt% -2.10 C3 Cut and higher content of iso-butylene in Light C4 cut. Since
the Light C4 Cut is the feed to MTBE (Methyl-Tertiary-Buthyl-
Coke, wt% -0.13
Ether) unit, increased content of iso-butylene led to increased
MTBE production (MTBE product is the “octane booster” used
Operating Conditions ACHIEVE® vs. Base within the gasoline pool). As the refinery is integrated with a
Unit throughput, t/h 142 petrochemical complex, increased content of propylene in the
ROT, Co
541 C3 cut and the increased production of the C3 cut, helped in
debottlenecking the C3 splitter column and allowed Rompetrol to
Feed pre heat temperature, 0C 215
sell chemical grade propylene on the domestic market. A benefit is
Specific Gravity 0.885 also coming from slightly higher LCO (Light Cycle Oil) production
ZSM-5-additive, % 7 and lower production of slurry (decanted oil), and Heavy C4 cut.
Operation Mode Full Burn
The above benefit was calculated in a 2017 price scenario with a
crude oil quotation of about 55 $/bbl, this being in line with 2017
ECAT Properties ACHIEVE® vs. Base average price, a price difference between propylene and MTBE
Activity (wt%) 73.5-75.0 vs gasoline of ~170 $/t and a price difference between slurry
SA (m2/g) 182-192 (decanted oil) vs. auto diesel of ~250 $/t.
UCS (Å) 24.26
Make-up Rate (MT/d) 2.3

Table 1: FCC Unit Test Run Data

Continued on Page 24

[Link] | 23
SUCCESS STORIES

Continued from Page 23

ACE™ Study FCC Simulation Model Unit Performance

PIMS Model
Used For Refinery Profit Calculation

Figure 14: Process Flow to Refinery Value

Continued Innovation Enhances Profitability References

Evolving market drivers continue to provide refiners with 1. Wood Mackenzie, Macro Oils Global Demand Outlook, June 2017,
[Link].
opportunities to improve refining margins6. The FCC unit is
the most flexible unit in the refinery in terms of capability to 2. Maximize propylene from your FCC unit, [Link] and R. Mehlberg, UOP
LCC, A Honeywell Co., Des Plaines, Illionis, Hydrocarbon processing,
process different feeds, and achieve different yields. The more
September 2011
flexible the FCCU operation is, the greater the potential to take
3. The importance of using pilot plant testing for FCC catalyst selection, M.
advantage of market opportunities. Melin, [Link], [Link], D. McQueen, Grace Catalyst Technology, Digital
Refining, June 2013
KMG Rompetrol and Grace worked closely on enhancing unit
4. Joyal,C.M.,Westby.M.J, Lappas,A.A., Pilot Plant Evaluation of FCCU Catalyst
performance through incorporation of high-performance catalytic Technology and Use of data for Commercial Catalyst Application, AM-08-52,
solutions, and optimizing operational parameters within the unit present at the 2008 NPRA Annual Meeting, March 9-11, 2008, San Diego,CA
constraints. Continued innovation in FCC catalyst and additive 5. Bryden,K., Predicting FCC unit performance with laboratory testing, PTQ
technology, as illustrated in this article, enables refineries to Catalyst 2013
enhance refinery profitability. Combining ACHIEVE® 100 state- 6. [Link], [Link], W. R. Grace,Columbia, Maryland, Raising the propylene
of-the-art catalyst technology with OlefinsUltra® HZ additive bar: Increase FCCU profitability in dynamic market conditions, Hydrocarbon
enabled the refinery to capture opportunities in a dynamic Processing, June 2017

market, achieving higher propylene and iso-butylene yields. 7. [Link], [Link], Javier Llano, B. Armburu, R. Larraz, Cepsa’s Gibraltar-
San Roque Refinery: A Case Study for Boositng Unit profitability through FCC
Test run results at maximum unit throughput and maximum unit
catalyst Selection for Propylene Maximization, Grace Catalagram, No.119,
severity demonstrate improved refinery profitability of $2.3 MM Spring 2017
USD/yr 7.

[Link]
Grace offers customers a custom portal for troubleshooting with sample analysis and other tools to help you manage
catalysts in your FCC unit.

Talk to your Grace representative today about how [Link] can work for you.

24 | Catalagram® No. 122 | Fall 2018

Reducing NOx Emissions from the
Hellenic Petroleum FCC Unit
Charitos Damianou Constantinos Plellis-Tsaltakis
Process Engineer Aspropyrgos Refinery
Hellenic Petroleum Technical Director
Hellenic Petroleum
Dimitrios Gkanis
Process Engineer Tom Burgess
Hellenic Petroleum Technical Sales Manager
W. R. Grace & Co.
Vasileios Tatsis
Head of Process Department
Hellenic Petroleum

Refinery processes account for a considerable share of the

overall emissions of air pollutants in Europe. The Industrial
Emissions Directive (IED) is the main EU instrument
regulating pollutant emissions from industrial installations.
The IED entered into force in 2011 and had to be transposed
by Member States by 2013. As a result, many refiners in the
EU are facing more stringent SOx and NOx emissions with
additional emission reduction targets coming into effect in
2018. One such refinery is Hellenic Petroleum’s, Aspropyrgos
Refinery in Greece who have successfully managed to reduce
NOx emissions using Grace FCC additive technology.
SUCCESS STORIES

Continued from Page 25 The next step of the project was to examine the additional
benefits of combining the low NOx combustion promoter with
Options for NOx Reduction Grace’s DENOX® technology, a standalone additive for NOx
reduction. The target was to reduce the NOx emissions as low
One route to lower NOx is through choice of feedstock, which
as possible. The DENOX® additive was preblended with the
is a costly approach and not particularly flexible. Regenerator
fresh catalyst to ensure consistent additive injection. Elemental
conditions also play a big role in NOx formation and can
analysis of the E-cat was again used to monitor the level of
present an easier route for NOx reduction. For example, lower
additive technology in the circulating inventory. The target level
oxygen levels and regen temperatures typically help to reduce
of DENOX® additive was 0.6 wt.%, and this was achieved over a
NOx. In addition, optimizing air distribution and regen bed
4-month period without the use of a baseloading period. During
levels can be beneficial.
this time the frequency of NOx measurement was increased to
The use of platinum based combustion promoters can lead to ensure the performance of the additive was determined in the
excessive NOx formation, with many refiners switching from most accurate way possible. Using a combination of CP® P and
platinum to palladium based promoters, such as Grace’s CP® P DENOX® technologies enabled NOx emissions to be reduced by
combustion promoter in recent years. After combustion promoter 65% fully meeting the ambitious expectations of the refinery.
usage has been optimized, specific NOx reduction additives
The 45% reduction of NOx using CP® P, followed by the
such as DENOX® additives can provide additional levels of
additional NOx reduction through the use of DENOX® addditive
NOx reduction.
is shown in Figure 1.

Decreasing NOx Emissions at Aspropyrgos The use of the NOx reduction technologies described had
Refinery Petroleum no negative impact on unit performance or the FCC products
yield structure.
The FCC unit at Aspropyrgos Refinery is an Exxon®
FlexiCrackeR® design operating in full burn with close-coupled By establishing the levels of NOx emissions achievable using
cyclones and modern feed nozzles. The unit processes a Grace’s CP® P and DENOX® technologies, Aspropyrgos refinery
combination of hydrocracker unconverted oil and atmospheric are well prepared for the upcoming impact from BREF limitations
residue. Hellenic and Grace initiated a NOx reduction project and expect to be able to mitigate any potential CAPEX impact.
at the start of 2017, involving commercial trials of FCC additive
technology. The objective was to determine the lowest
achievable emissions of NOx, to avoid the future need for high
CAPEX modifications such as retrofitting furnaces with low-NOx
burners, while remaining within compliance of future BREF NOx
emission legislation.

Until 2017, Aspropyrgos Refinery had been using Grace’s

traditional platinum based combustion promotor technology for
afterburn control. The first step of the NOx reduction project was
to transition to CP® P, a non platinum based low-NOx combustion
promoter. A key consideration in addition to NOx reduction was
not to compromise the level of afterburn in the regenerator. NOx
emissions from the FCC unit are measured using a portable flue
gas analyser, and based on a 5-year period of operational data
the baseline NOx emission levels could be determined.

During the switch from a platinum to a palladium based

combustion promoter, elemental analysis of the equilibrium
catalyst (E-cat) enabled the technology change out to be
monitored. Once complete change out was achieved, a NOx
emission reduction of 45% was consistently noted using the
CP® P combustion promoter. Importantly, the catalyst remained
well promoted using CP® P with no afterburn issues observed.

26 | Catalagram® No. 122 | Fall 2018

 REDUCING NOX EMISSIONS FROM THE HELLENIC PETROLEUM FCC UNIT

Figure 1: NOx Reduction Achieved with CP® P and DENOX® Additives

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[Link] | 27
Newest Additions to SmART Catalyst
System® Technology Achieve Longer
Run Lengths Through Increased
Activity, Improved Stability
John Cunningham
Technical Service Specialist
Advanced Refining Technologies (ART)

Refiners demand higher activity catalysts as global sulfur

specifications continue to tighten. Advanced Refining
Technologies (ART) continues to expand its portfolio of ultra-
high activity catalysts to meet oil refiner’s needs. ART’s DX®
Catalyst Series has demonstrated superior performance in
ULSD applications, exceeding expectations for many years.
ART’s 425DX® and 545DX® catalysts continue to excel in middle
distillate after worldwide acceptance. Responding to the need
to balance feedstock flexibility, cycle length, and product
flexibility, ART developed ICR® 316 and 548DX®, the newest
catalysts in a long line of innovation. The addition of ICR® 316
and 548DX® allows refiners to process tougher feeds, meet tighter
specifications, improve product quality, and expand capacity with
no additional capital costs.

ICR® 316 and 548DX® catalysts capture recent advancements

in alumina technologies made by the ART research team.
Innovations in surface chemistry and new pore structures
provide a significant boost in HDS, HDN, and HDA activity, with
improvements exceeding 20% in some applications. Chelate
enhancements also make each catalyst more robust and forgiving
for start-up. Both catalysts will excel as stand-alone catalysts or as
an integral part of the SmART Catalyst System® technology.
 NEWEST ADDITIONS TO SMART CATALYST SYSTEM® TECHNOLOGY ACHIEVE LONGER RUN
LENGTHS THROUGH INCREASED ACTIVITY, IMPROVED STABILITY

ICR® 316 the significant gains in API gravity and Cetane Index at ULSD
conditions, as shown in Figure 3. This translates directly into
ICR® 316 offers improvement opportunity to every diesel increased volume swell and refinery profitability.
hydrotreating unit. Its benefits have been demonstrated on
both straight run and cracked stocks, and at low and high
operating pressures. Figure 1 shows a comparison of ICR® 316 30
to its predecessor, 425DX®, in a ULSD protocol using a feed
containing 15% cracked stocks. ICR® 316 shows a clear activity 25
gain in the low-pressure ULSD test, and further extends its
advantage in the higher-pressure test. This increased activity
20
enables refiners to process more opportunity feed stocks and
increase hydrotreater cycle length.
15

Feed: 31.9 API, 1.14 wt.% Sulfur, 288 ppm Nitrogen

10

140 ICR 316 5

425 DX
0
HDS HDN
120
548DX 545DX NDXi
HDS RVA

100 Figure 2: 548DX® offers significant advantages in HDS and HDN activity
in high-pressure ULSD testing (1000 psig).

80
Feed: 30 API, 0.8 wt% S, 187 wppm N, 40.2 wt% Aromatics

9 9

60
625 Psig 425 Psig 8 8
Cetane Index Improvement

API Upgrade, °API

7 7
Figure 1: Relative Volume Activity (RVA) of ICR® 316 significantly
exceeds 425DX® in both low and medium pressure ULSD applications.
6 6

548DX® 5 5
548DX® utilizes ART’s newest technology in advanced chelate
enhancement and alumina surface modification to provide the
highest activity for HDS, HDN, and HDA, making it ideal for use 4 4
NDXi 545DX 548DX
in both ULSD and other applications. It is commercially proven
and is currently in use in units around the world. High pressure
Cetane API
ULSD testing reveals a substantial improvement for both sulfur
and nitrogen removal, as shown in Figure 2.

The same ULSD testing protocol also shows a significant Figure 3: 548DX® shows a significant improvement in product quality in
boost in aromatic saturation activity for 548DX® relative to its high pressure ULSD testing (1000 psig).
predecessor, 545DX® catalyst. This is readily demonstrated by

Continued on Page 30

[Link] | 29
SUCCESS STORIES

Continued from Page 29

SmART Catalyst System® Technology

Platform
ICR® 316 and 548DX® are the newest high-activity catalysts
for use in the SmART Catalyst System® technology. ART
pioneered the combined use CoMo and NiMo catalysts with
the introduction of the SmART Catalyst System® technology in
the early 2000s. It has since become widely accepted as the
premier method to fully utilize existing assets within a refinery’s
individual constraints. Figure 4 shows how catalyst selection and
placement can be tailored to provide the optimum balance of
maximum HDS and hydrogen consumption.

Conditions: 1.0 LHSV, 600 Psi and 2000 SCFB H2/Oil

Feed: 30% FCC LCO with 28.7 API and 1.78 wt.% sulfur
Relative H2, Consumption
Product Sulfur, ppm

All CoMo All NiMo

SmART Systems

Figure 4: ART uses its SmART Catalyst System® technology to optimize

activity with hydrogen consumption and product quality for maximum
refinery profit.

The SmART Catalyst System® technology design is the

culmination of an extensive effort put towards understanding the
chemistry and process conditions required for ultra-low sulfur
fuels. ART has devoted significant resources to designing the
most active and robust ULSD catalysts for use in the SmART
Catalyst System® technology. This effort has led to the recent
commercialization of ART’s new CoMo catalyst, ICR® 316, and
new NiMo catalyst, 548DX®. These new technologies capitalize
on the extensive material science and catalyst knowledge
encompassed in the ART joint venture.

Contact your ART representative today to learn more about

ICR® 316, 548DX®, the SmART Catalyst System® technology,
and how our hydroprocessing expertise can maximize your
refinery profitability.

30 | Catalagram® No. 122 | Fall 2018

 Let’s do
the math.
Grace custom catalyst solutions,
co-developed with you, are about more
than performance—and more than
chemistry. They’re designed to add to
your bottom line.

In some cases, the difference between

our refinery customers’ financial return
on Grace technologies versus the
alternative has reached into eight figures.

If you’re ready to put Grace chemistry to

work to strengthen your business, we’re
ready to show you how we can help. Call
us to get started with the calculations.

Tested. Proven. Valued.

[Link]

At Grace, value is all about our

customers’ financial success.

Learn more at [Link]/value.

[Link] | 31
GRACE®, ACHIEVE®, Catalagram®, CP ®, DENOX®, DESOX®,
GSR®, OLEFINSULTRA®, and SMART CATALYST SYSTEM ®
are trademarks, registered in the United States and/or other
countries, of W. R. Grace & Co.-Conn. or Advanced Refining
Technologies.
TALENT | TECHNOLOGY | TRUST™ and DCR™ are
trademarks of W. R. Grace & Co.-Conn.
ART®, ART & Design®, and ADVANCED REFINING
TECHNOLOGIES® are trademarks, registered in the United
States and/or other countries, of Advanced Refining
Technologies LLC.
CHEVRON ® and ICR® are trademarks, registered in the
United States and/or other countries, of Chevron Intellectual
Property LLC.
FlexiCrackeR® is a trademark, registered in the United States
and/or other countries, of Exxon.
BELCO ® is a trademark, registered in the United States and/
or other countries, of Belco Technologies Corporation.
FCC-SIM ® is a trademark, registered in the United States
and/or other countries, of Advanced Technologies PLC.
This trademark list has been compiled using available
published information as of the publication date of this
brochure and may not accurately reflect current trademark
ownership or status.
© Copyright 2018 W. R. Grace & Co.-Conn.
All rights reserved.

To learn more about Grace,

please visit us at [Link].