special features gas processing developments mass transfer refining gas processing petrochemicals

156 Pages·2014·23.8 MB·English

ptqQ4 2014
PETROLEUM TECHNOLOGY QUARTERLY
REFINING
GAS PROCESSING
PETROCHEMICALS
SPECIAL FEATURES

GAS PROCESSING DEVELOPMENTS
MASS TRANSFER
cover and spine copy 22.indd 1 15/09/2014 10:32
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3 Fencing with rules
ptq
Chris Cunningham

5 ptq&a

21 Tail gas catalyst performance: part 2
Michael Huffmaster Consultant
Fernando Maldonado Criterion Catalysts
PETROLEUM TECHNOLOGYQUARTERLY
37 Predicting future FCC operations via analytics
Patrick J Christensen, Touseef Habib, Thomas B Garrett and Thomas W Yeung
Hydrocarbon Publishing Company
Q4 (Oct, Nov, Dec) 2014
www.eptq.com
47 Predicting reactive heavy oil process operation
Glen A Hay, Herbert Loria and Marco A Satyro Virtual Materials Group, Inc
Hideki Nagata Fuji Oil Company Ltd
55 Integrated hydrogen management
Saša Polovina, Danijela Harmina and Ana Granic Šarac INA Rijeka refinery
69 Structured packing in a CO absorber
2
Ralph Weiland and Nathan Hatcher Optimized Gas Treating, Inc.
75 Reflux in a gas dehydration plant
Sajad Mirian and Hossein Anisi Nitel Pars Co (Fateh Group)
Xiang Yu Hengye Chemical Co
Sepehr Sadighi Research Institute of Petroleum Industry
81 Override control of fuel gas
Rainer Scheuring Cologne University of Applied Sciences
Albrecht Minges and Simon Griesbaum MiRO Mineraloelraffi nerie Oberrhein
Michael Brodkorb Honeywell Process Solutions
87 ‘Snakes and ladders’ for maximising propylene
Bart De Graaf, Mehdi Allahverdi, Martin Evans and Paul Diddams
Johnson Matthey Process Technologies
97 Troubleshooting a C splitter tower. Part 1: evaluation
3
Henry Z Kister Fluor
Brian Clancy-Jundt and Randy Miller PetroLogistics
105 Overcoming tight emulsion problems
Hernando Salgado Cartagena Refinery, Ecopetrol
Luis Mariño Ramgus S. A. – Pall Corp.
Rosángela Pacheco Barrancabermeja Refinery, Ecopetrol
111 Enhancing bottoms cracking and process flexibility
Yee-Young Cher, Rosann Schiller and Jeff Koebel Grace Catalysts Technologies
119 Preventing emissions in coke removal
Artur Krueger, Bernd Lankers and Josef Wadle TriPlan AG
125 Troubleshooting steam ejectors
Norman Lieberman Process Improvement Engineering
131 Asphalt quality prediction and control
Zak Friedman Petrocontrol
137 Technology in Action
Marathon Petroleum’s Detroit, Michigan refinery. Photo: Marathon Petroleum Corporation
©2014. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.
ed com copy 6.indd 1 13/09/2014 11:38
KBC Adv - PTQ Q4 2014.pdf 1 9/3/2014 8:40:35 AM
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kbc.indd 1 10/09/2014 11:50
ptq
T Fencing with rules
he European Union has arguably
been the global leader in biodiesel
production and use, with overall
biodiesel production increasing from 1.9
PmEiTlRliOoLnE tUoMn nTeEsC iHnN 2O0L0O4G tYoQ nUeAaRrlTyE 1R0LY.3 million
tonnes in 2007. Biodiesel production in the
US has also increased dramatically in the
pVaoslt 1f9ew N oy e5ars from 2 million gallons in
2Q0040 (toO acptp, rNoxoimva,t eDlye 4c5)0 2m0il1li4on gallons
in 2007. According to the National Biodiesel
E
Board, 171 companies own biodiesel nvironmental regulation is the mother of invention in refining technology.
mEdaintourf acturing plants and are actively The impact of successive clean fuels measures, originating in Europe and
mCharrikse Ctiunngn ibnigohdaimes el.1. The global biodiesel the US, continues to reverberate at refinery sites around the world as the
medairtkoer@t piest reosletiummatteecdh ntoolo grye.accohm 37 billion technology developers’ output works to continually upgrade the refining
gallons by 2016, with an average annual industry’s impact on air quality, directly or via its products. With poorer
Production Editor
growth rate of 42%. Europe will continue to quality crudes entering the mainstream of raw material flows into refineries,
Rachel Storry
be the major biodiesel market for the next the pressure for further and better invention does not ease up.
[email protected]
decade, followed closely by the US market. This all, of course, means additional expenditure for the refiners them-
GrAaplthhicosu Egdihto r high energy prices, selves. It is no surprise when they demand a long, hard look at any proposal
iRnocbr eFarissi ng global demand, drought to require that cleaner products or cleaner emissions leave a refinery.
agnradp hiocst@hepre trofalecutmortse chanroel ogtyh.ceo mprimary The latest significant step along the road to regulation in the US was due
drivers for higher food prices, food late in October when the call for evidence was scheduled to close on the
Editorial
competitive feedstocks have long Environmental Protection Agency’s (EPA) proposed extension of emissions
tel [phone]
been and will continue to be a major limits from refineries. Introduced in May, the proposed rule arises from the
fax [phone]
concern for the development of biofu- EPA’s risk and technology review of two existing emissions standards for
eBluss. inTesos Dceovemloppemtee,n t Dthiree ctionrdustry has refineries. This extension of the rules calls for additional emission control
rPeasupl oMnadsoend by developing methods to requirements for storage tanks, flares and coking units at petroleum refiner-
isnaclerse@apseet rpolreoucmetsesc henfofilocgieyn.ccoym, utilise or ies, as well as a requirement – with refiners’ neighbours in mind – to monitor

upgrade by-products and operate air concentrations at the fenceline to check for accidental emissions.
Advertising Sales Office
with lower quality lipids as According to the EPA, implementing the rule will result in a reduction in
tel [phone]
feedstocks. the US of 5600 t/y of air pollutants, and 52 000 t/y of volatile organic com-
fax [phone]
pounds (VOC). More specifically, the EPA wants to amend the operating
FPeuebdlsisthoeckrs requirements for refinery flares to ensure a “high level” of combustion effi-
BNiiocd Ailelesnel refers to a diesel-equivalent ciency for waste gases that go to flare. The agency also wants controls on
fpuuebll ischoern@spisettirnolge umoft ecshhnoolrotg-cyh.caoimn alkyl delayed coking units with the aim of preventing exemptions to emission lim-
(methyl or ethyl) esters, made by the its during start-up and shutdown. It expects that the measures will lead to a
Circulation
transesterification of triglycerides, reduction in emissions of BTX of 1800 t/y and VOC emissions would fall by
Jacki Watts
commonly known as vegetable oils or 19 000 t/y. The additional flaring measures would result in significant reduc-
Louise Shaw
acniricmulaatli [email protected] tTrohleeu mmtoescth ncoolomgym.coomn form tions in particulate emissions and VOCs.
uses methanol, the cheapest alcohol Upgrading and tweaking the technologies to achieve all of this would also,
aCvraamilabbetlhe ,A ltleon Ppurboldishuicneg Lmtdethyl esters. says the EPA, lead to 700 000 t/y less carbon dioxide entering the atmo-
THhoep esmayo, lCercauvelens A rimns SbYi7o d8HieDs,e Ul Kare pri- sphere. The all-in cost of implementing the rule would be $240 million, with
tel [phone]
marily fatty acid methyl esters annual running costs of $40 million, with resulting “negligible impact” on
fax [phone]
(FAME), usually created by trans- product costs.
esterification between fats and metha- Refiners are not so sure about the EPA’s latest certainties. The American

nol. Currently, biodiesel is produced Fuel & Petrochemical Manufacturers (AFPM), the US refiners’ trade body
fPrToQm (Pe tvroaleruimo Tuecsh nvoeloggye Qtauabrtleerl ya) n(ISdSN p lant oils. and voice in Washington, takes the view that further tightening of the emis-
No: 1632-363X, USPS No: 014-781) is published
First-generation food-based feedstocks sions rules is not cost effective. The AFPM said earlier in the year that it had
quarterly plus annual Catalysis edition by Crambeth
aArlleen Psutbrliashiigngh Lttd avnde igs editsatribbulete d ion itlhse USs uch as evaluated the EPA’s analysis of risk on the basis of emissions data provided
by SP/Asendia, 17B South Middlesex Avenue,
sMooynrboee aNJn 0 8o83i1l. Paenrioddi caalsn piomstaagle pfaaidt ast Nseuwc h as to the agency. That analysis, according to the AFPM, showed that risk levels
tBarullnoswwic,k , lNaJr. dPo,s tymealslteorw: se ngd raeddarseses ,c hcahngiecsk toe n fat were “not appreciably higher” than they were when the rule was applied
PTQ (Petroleum Technology Quarterly), 17B South
aMnidddl etshexe A vbeynu-ep, Mroondroue cNtJ s0 8o83f1 t.he production first time around, pointing out that the EPA determined at that time that fur-
oBfa ckO nummbeegrsa a-va3il afbalet ftroym athce iPdubsl isfhrero m fish oil. ther action was unnecessary.
at $30 per copy inc postage.
Soybean oil and rapeseeds oil are the The AFPM went on to say that the level of concern for risks expressed in
common source for biodiesel produc- the original rule does not justify the further actions that the EPA wants to put
tion in the US and Europe in quanti- forward. Fenceline monitors, for instance, are “not justified” by the latest risk
ties that can produce enough biodie- analysis. This critique signed off by saying that the EPA’s latest proposed
sel to be used in a commercial market steps are neither cost effective, nor do they provide substantial health benefits.
with currently applicable
CHRIS CUNNINGHAM
PTQ Q4 2014 3
ed com copy 6.indd 2 15/09/2014 11:14
“ Advanced R & D means results,
like our newest tail gas catalyst: C-834.”
Meet Karl Krueger:
Research Scientist. Tail Gas Catalyst Expert.
Activity, pressure drop, cost... According to Karl Krueger, Criterion research scientist, these among
other factors are critical considerations when selecting a tail gas catalyst. He should know. Karl and
his colleagues have just designed C-834, specifi cally to provide exceptionally high activity in low
temperature operations while continuing to help refi ners realize lower operating costs and extended
cycle lengths. This breakthrough catalyst joins the ranks of Criterion’s range of advanced tail gas
treating catalysts including C-234, C-534 and C-734, which account for the majority of the world’s
installed capacity.
Leading minds. Advanced technologies.
www.CRITERIONCatalysts.com
criterion.indd 1 10/09/2014 11:40
ptq&a
Q
Suspended catalyst in our FCC fractionator is some of the best solid separation performance.
accumulating in the bottom fraction. What is the most However, the capital cost and operating cost (energy
effective way of clarifying this slurry oil? consumption) need to be considered. Furthermore, the
maintenance of a centrifugal slurry separator is more
A
Zhe Cui, FCC Technologist, [email protected], extensive compared to other separation technologies.
Bob Ludolph, Principal Technologist - Catalytic Cracking, Each technology has its advantages and disadvan-
[email protected] and Kevin Kunz, Team Lead, FCC tages, and applications are unit specific. For a specific
Design & Licensing, [email protected], Shell Global Solutions application, a comprehensive analysis, including the
The suspended catalyst in the FCC fractionator bottom source of the catalyst fines, temperature, residence
fraction (slurry oil) is uncaptured catalyst leaving with time, pressure drop, fines concentration, flow rates,
the reactor overhead vapour (feed for main fraction- unit capacity, particle size distribution, and desired
ator). The slurry yield is determined by the FCC unit’s capital cost budget is necessary. Working closely with
riser/reactor design, feed and catalyst properties, reac- vendors of the various solutions will provide guidance
tor conditions, desuperheating section temperatures, in resolving the excessive fines content in slurry oil
and by the design and operation of the bottoms circu- effectively and economically.
lating reflux and bottom quench. With a properly The catalyst concentration in the slurry oil should be
operating reactor cyclone system, a catalyst in slurry minimised not only from an erosion point of view; it
concentration of 0.15% is usually achieved (typical can also impact the sale value of the slurry oil.
bunker fuel oil, 0.03-0.15 wt% catalyst in slurry). Therefore, it is of great importance to select a proper
However, if the solid concentration in the slurry oil is solid separation technology especially when higher
higher, either some slurry clean-up system is needed, catalyst concentration is observed, which can happen
or the operating condition of the FCC unit needs to be later in the FCC operating cycle. In Shell units, as the
reassessed and optimised. This could include redesign first barrier, a high efficiency cyclone system is
or repair of the existing reactor cyclones. installed in the reactor to minimise the catalyst
Shell has evaluated all major technologies for appli- fines loss to the main fractionator. Furthermore, with
cation in removing catalyst fines from the slurry oil. the help of the technologies mentioned, catalyst
These options include hydrocyclone, electrostatic concentration in the slurry oil can be controlled to
separator, backwash filtering, and centrifugation. below 0.05%.
A hydrocyclone separates FCC particles from slurry
A
oil based on centripetal force and fluid resistance. Due Joe Nguyen, Research Associate, Baker Hughes,
to the advantages of low cost, no moving parts, low [email protected]
pressure drop and low maintenance requirement, Slurry oil has historically been clarified – that is,
hydrocyclones are the first choice for resolving slurry reduced in solids content – by one of three general
ash issues when a cyclone redesign is not possible. methods. These are centrifuging, filtration, and longer-
However, the performance of the hydrocyclone is rela- term passive settling. Centrifuging is not as effective as
tively sensitive to the feed parameters (temperature, other methods since the particulate solids in a slurry
flow rate, solid concentration). So hydrocyclones are oil (mostly FCC catalyst fines) are not removed by the
specifically designed for individual FCCs. FCC reactor’s cyclones and are finely divided and
Electrostatic separators are designed and made light. Filtration systems can be effective at removing
specifically for slurry oil so they can provide the solids, but these filtration systems can also be costly in
required separation with fairly low pressure drop. But terms of equipment and operation. The most cost-
the capital cost and footprint requirement can limit the effective method is passive settling in storage vessels
application. Also, direct experimentation is required aided by temperature and slurry settling chemicals.
for a good design for a specific FCC system. Elevated storage temperature reduces viscosity, allow-
Backwash filtration can also provide highly efficient ing solids to settle more easily. Chemical surfactants
solid separation. Backwash filtration does require high added to the slurry oil can promote agglomeration of
energy consumption, higher pressure drop, and higher smaller fines into larger particles, which settle at faster
capital cost than hydrocyclones. rates. The one drawback to passive settling is that time
Centrifugation technology has advantages of small is required for slurry settling, even allowing for the
volume and low pressure drop. Also, it can provide temperature and chemical aids.
Additional Q&A can be found at www.eptq.com/QandA
www.eptq.com PTQ Q4 2014 5
Q&A copy 15.indd 1 10/09/2014 12:36
A
Charles Radcliffe, Technical Service Engineer Europe, desired. This scenario increases both feed severity and
Johnson Matthey, [email protected] catalyst deactivation rate in the hydrocracker process-
I read this as being a problem of catalyst fines settling ing the DAO stream. Typical DAO stream composition
in the bottom of the main fractionator. The important metals (5-100 wppm), Conradson carbon (2–10 wt%),
thing with handling slurry oil is to maintain a high asphaltenes (heptane insolubles of 500-1000 wppm or
enough velocity to ensure that catalyst cannot settle. more) and distillation end-point (1300-1500°F or more)
High velocities also reduce residence times and so are detrimental to achieving economic catalyst life and
reduce coke formation due to thermal cracking. For conversion at hydrocrackers. There are several ways to
this reason, main fractionator slurry systems are reduce contaminants in a DAO stream. Once the
normally designed with a small diameter, <50% of the process to reduce contaminant carry-over is in place,
main column diameter heel. A short-term fix for the effective use of catalysts is the key factor to success.
questioner is to try and increase slurry pumparound, For new unit design, a separate guard reactor could
and if they have a large heel to install a lining in the be designed for contaminant removal. For an existing
b o t t om of the fractionator with steel skinned hydrocracker, a proper choice of the Demet catalyst
refractory. system will be required to handle the contaminants in
Catalyst fines can be removed using a gravity settler the DAO stream. From a hydrocracking perspective,
or filter system. The problem with settlers is that to the ‘contaminants’ most detrimental to pretreat and
work efficiently they need to have residence time at cracking catalyst performance are metals and
high temperature to lower viscosity. This leads to coke asphaltenes. Fortunately, both these show the sharpest
formation and potentially flash point problems on partitioning in SDA units, with DAO, even from deep
slurry product. There is also the problem of what to do extraction, often having a lower C-insolubles
7
with the settler underflow. Recycling will increase FCC (asphaltenes) value than the corresponding HVGO.
delta coke. Filtration systems reduce the amount of With proper understanding of the DAO chemistry, a
high fine material (from back washing) but are high ‘demetallisation’ catalyst system can be individually
maintenance equipment. designed to protect the downstream hydrocracking
Most refiners work to ensure good reactor cyclone catalysts. This has been fully proven by the successful
efficiency to minimise fines carry-over, and purge this operation at a European refinery of the combination of
with the slurry product. a KBR ROSE solvent deasphalting unit with a Shell
fixed-bed hydrocracker, specifically designed to
A
Eva Andersson, Market Manager Refinery, Alfa Laval, process a high percentage of deeply extracted DAO in
[email protected] combination with VGO. The upgrading complex deliv-
High speed centrifugation technologies have been used ers high conversion coupled with high distillate yields
for decades to remove cat fines onboard marine vessels, of high quality and with a long, sustained run length.
where engines demand less than 10-15 ppm cat fines in After three years’ continuous operation, the demetalli-
the oil. The same technology can be applied on sation catalyst was replaced, while both pretreat and
unblended FCC slurry in refineries but the high speed cracking catalysts were retained for the ‘next’ cycle.
centrifuge used must be designed to handle higher It is important to know the level of removal of
temperatures in combination with more abrasive sludge. metals, heteroatoms, Conradson carbon residue (CCR)
and asphaltenes. The feed composition and operating
conditions determine the right catalyst choice. These
Q
Is there an effective way of cleaning contaminants variables determine the factors to tailor make catalyst
from deasphalted oil so that it can be used as a feed to a systems that meet each refinery’s needs. In an existing
hydrocracker? unit with existing HCU reactors, there would be a
maximum reactor volume available for the demet cata-
A
Deepak RD, Hydrocracking Technical Service Engineer, lysts which then restricts the maximum amount of
[email protected], and Deepak Agarwal, DAO that could be processed in the HCU feed based
Hydrocracking Technical Service Engineer, D.Agarwal@CRI- on the DAO quality. The performance of Criterion’s
Criterion.com, Criterion Catalysts & Technologies demetallisation catalyst system has been the key factor
In order to maximise the margin of upgrading heavy that enables ULSD and high quality jet fuel to be
fuel oil into lighter products, one operation variable produced directly from DAO over economic cycle
that has been leveraged by refiners is the degree of lengths. In addition, Criterion has developed step-out
‘lift’ employed at the deasphalting unit. Further, HDM/HDN/HDCCR catalysts with exceptionally
depending on DAO application and yield require- high HDN and HDCCR activities, good contaminant
ments, SDA (solvent deasphalting) units are designed metals tolerance and excellent stability. Using innova-
with solvents ranging from propane to hexane. The tive manufacturing technology, Criterion has
type of solvent used is based on the contaminant level additionally developed a new type of active site that
and yield of DAO from the unit. For base oil produc- resists metal and coke deactivation. In applications
tion, propane deasphaltene is used to produce high used, it has demonstrated stable activity at high metal
quality and low yield DAO. Normally, C and heavier deposition levels. Metal species compete with each
4
hydrocarbon is used as a solvent when the DAO is other and hence the effective use of customised layer-
processed in a hydrocracker and higher DAO yield is ing of catalysts is vital to sustain effectiveness.
6 PTQ Q4 2014 www.eptq.com
Q&A copy 15.indd 2 10/09/2014 12:36
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ccbbii_.ipntdqd_ 4 q 12014_ad_sep_2014.indd 1 8/13/12001/049 /82:0481:44 2 A11M:35
A
Alex Yoon, Senior Technology Advisor for Advanced require more of these contaminant removal catalysts
Refi ning Technologies, [email protected] which then reduces the reactor volume available for
The solvent deasphalting (SDA) process is itself a way other hydrotreating and hydrocracking catalysts. A
of cleaning contaminants from a portion of vacuum refi ner wishing to extend cycle length can increase
resid – the deasphalted oil (DAO) – to be processed in loading of high macro/mesoporosity catalysts, but this
a hydrocracker. Depending on the severity of SDA reduces the volume of hydrotreating catalysts.
operation (extraction target of DAO), contaminant To alleviate the downside of the trade-off, ART has
levels can vary signifi cantly. The most common also developed and begun deploying next generation
contaminants are Ni and V containing resid molecules. catalysts that exhibit two to three times the relative
These can vary typically from 1 ppm to 30 ppm. There volume activity of conventional catalysts for this type
are also asphaltenes and other high CCR causing mole- of service. With this next generation technology in the
cules which would be considered contaminants in a catalyst load, the reduced hydrotreating catalyst
hydrocracker operation. The former can be as high as volume will exhibit longer cycle length. A refi ner wish-
1000 wppm while the latter can be as high as 13 wt%. ing to process more DAO can also utilise this next
High sulphur, high nitrogen and low API are also typi- generation technology in a similar way to improve
cal characteristics of the DAO. profi tability. An optimum catalyst loading for maxi-
DAO contaminant removal for the hydrocracker is mum performance requires close cooperation of
accomplished within the hydrocracker using appropri- refi nery operating staff and catalyst supplier experts.
ately designed catalysts, typically in the fi rst two beds
A
of the reactor. Advanced Refi ning Technologies utilises George Anderson, Global Hydroprocessing Specialist,
catalysts with high macro- and mesoporosity that have Albemarle Corporation, [email protected]
been successfully used in many vacuum resid process- Deasphalted oil (DAO) tends to contain relatively high
ing units worldwide. These catalysts have successfully amounts of nickel (Ni) and vanadium (V). In addition,
processed various DAOs with up to 12 wt% CCR, 30 depending on the crude source, it may contain catalyst
ppm metals, and up to 75% DAO blended in the feed. poisons (such as arsenic) and may pick up solids (such
These catalysts also have excellent hydrotreating as particulates and iron scale) during its transport to
functionality. However, high contaminant levels can the hydrocracking unit (HCU). Particulates and iron
rapidly reduce their activity and this results in a trade- scale can be removed effectively by fi ltering prior to
off with downstream hydrocracking catalysts. Higher the HCU or by use of appropriate bed grading and
contaminant levels with a given operating target traps at the top of the hydrocracking pretreat (HC-PT)
Our success formula for innovative water and process management
Permanent research and development form the core of our innovative products for chemical water and process management. As a worldwide market
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Phone: [phone] . www.kurita.de
4032_00KU_LY_1_2seitige_Innovation_engl_MS_04062014.indd 1 04.06.14 12:48
8 PTQ Q4 2014 www.eptq.com
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