petroleum technology quaterly

7/28/2019 PETROLEUM TECHNOLOGY QUATERLY

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special features

Heat management

carbon capture

refining

gas processing

petrocHemicals

petroleum technology quarterly

Q2 2010


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2010. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rightsreserved. 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 Quarterlythe publisher cannot be held responsible for anystatements, opinions or views or for any inaccuracies.

5 Geographical trade-offs ChrisCunningham

7 Processing Trends

11 ptq&a 15 Anode-grade coke from traditional crudes MitraMotaghi,KanuShreeandSujathaKrishnamurthyKBR Technology

21 Catalytic reforming options and practices TomZhouFluor Enterprises FrederikBaarsFluor BV

27 Planning for carbon capture SuzanneFergusonFoster Wheeler

35 Online cleaning and decontamination of a butadiene unit DinoPolveriniandCosimoCucinelliPolimeri Europa

MarcelloFerrara ITW

41 Optimisation of product yield and coke formation in a RFCC unit

SepehrSadighi,SeyyedRezaSeifMohaddecy,OmidGhabouli andMehdiRashidzadehResearch Institute of Petroleum Industry47 Optimising steam systems: part I

IanFlemingSpirax Sarco

55 Calculating column relief loads HaribabuChittibabu,AmudhaValliandVineetKhannaBechtel india PVE Ltd DipanjanBhattacharyaBechtel Corporation

67 Crude oil selection: optimisation by weight or by volume? MDPawdeandSachinSinghHindustan Petroleum Corporation Ltd (HPCL)

75 Designing for sulphur removal and storage: part 1 ShamimGandhi,WayneChungandKrishNangiaFluor Corporation

87 When MTBE outscores ETBE for bioenergy contentEelcoDekkerBioMCN95 Microchannel reactors in fuel production

DerekAtkinsonOxford CatalystsJeffMcDanielVelocys

101 Hydrotreating in the production of green diesel RasmusEgeberg,NielsMichaelsen,LarsSkyumandPerZeuthenHaldor Topse

115 Selecting technologies for onshore LNG production SaeidMokhatabTehran Raymand Consulting Engineers

121 Estimation of heat losses from process piping and equipment AlirezaBahadoriandHariBVuthaluruCurtin University of Technology

124 Industry News

127 New Products

KBRsROSEsolventdeasphaltingprocessatNavajoReningCompanys75,000bpdreneryinArtesia,NewMexico.On

p15,KBRauthorsdiscussacombinationofsolventdeasphaltinganddelayedcokingtominimisefueloilproductionandproduceanodegradecoke. Photo: KBR

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The European Union has arguably

been the global leader in biodiesel

production and use, with overall

biodiesel production increasing from 1.9

million tonnes in 2004 to nearly 10.3 million

tonnes in 2007. Biodiesel production in the

US has also increased dramatically in the

past few years from 2 million gallons in 2000

to approximately 450 million gallons in 2007.

According to the National Biodiesel Board,

171 companies own biodiesel manufacturing

plants and are actively marketing biodiesel.1.

The global biodiesel market is estimated

to reach 37 billion gallons by 2016, with an

average annual growth rate of 42%. Europe

will continue to be the major biodiesel

market for the next decade, followed closely

by the US market.

Although high energy prices,

increasing global demand, drought andother factors are the primary driversfor higher food prices, food competitivefeedstocks have long been and willcontinue to be a major concern for thedevelopment of biofuels. To compete,the industry has responded bydeveloping methods to increase processefciency, utilise or upgrade by-products and operate with lowerquality lipids as feedstocks.

FeedstocksBiodiesel refers to a diesel-equivalentfuel consisting of short-chain alkyl(methyl or ethyl) esters, made by thetransesterication of triglycerides,commonly known as vegetable oils oranimal fats. The most common formuses methanol, the cheapest alcoholavailable, to produce methyl esters.The molecules in biodiesel are primarilyfatty acid methyl esters (FAME),usually created by transestericationbetween fats and methanol. Currently,biodiesel is produced from variousvegetable and plant oils. First-generation food-based feedstocks arestraight vegetable oils such as soybeanoil and animal fats such as tallow, lard,yellow grease, chicken fat and the by-products of the production of Omega-3fatty acids from sh oil. Soybean oiland rapeseeds oil are the commonsource for biodiesel production in theUS and Europe in quantities that canproduce enough biodiesel to be used in

a commercial market with currentlyapplicable technologies.

First-generation feedstocks for

PTQ Q2 2010 5

EditorChris [email protected]

Production EditorRachel [email protected]

Graphics Editor

Mohammed [email protected]

Editorialtel +44 844 5888 773fax +44 844 5888 667

Advertising Sales ManagerPaul [email protected] SalesBob [email protected]

Advertising Sales Ofcetel +44 844 5888 771fax +44 844 5888 662

PublisherNic [email protected]

CirculationJacki [email protected]

Crambeth Allen Publishing Ltd

Hopesay, Craven Arms SY7 8HD, UKtel +44 844 5888 776fax +44 844 5888 667

ISSN 1362-363X

Petroleum Technology Quarterly (USPS 0014-781)is published quarterly plus annual Catalysis editionby Crambeth Allen Publishing Ltd and is distributedin the USA by SPP, 75 Aberdeen Rd, Emigsville, PA17318. Periodicals postage paid at Emigsville PA.Postmaster: send address changes to PetroleumTechnology Quarterly c/o POBox 437, Emigsville, PA 17318-0437Back numbers available from the Publisherat $25 per copy inc postage.

Vol 15 No 3

Q2 (Apr, May, Jun) 2010

Geographicaltrade-offs

If the contents of this editors email inbox and quite possible yours sincethe turn of the year are anything to judge by, the industry debate on emissionstrading and carbon control is generating enough heat for its own signicant

contribution to global warming. Depending on where you are in the world, thenaysayers hold a signicant lead over the doomsayers if number of paragraphspublished is the measure of the argument.

Whatever the level of political combat, and as this issue ofPTQ demonstrates,reners can always be relied upon to take the pragmatic approach and arepressing ahead with practical plans to deal with cap-and-trade, carbon offsets or

whatever else government bodies care to unleash on them. On p27, SuzanneFerguson of Foster Wheeler Energy outlines the practical and economic issuesthat must underlie a decision if any is to be taken to capture producedrenery carbon emissions. Meanwhile, in our Processing Trends pages, beginningon p7, Tom Yeung of Hydrocarbon Publishing outlines his organisations newsurvey of reners actual plans for dealing with greenhouse gas emissions.Sources of the information are a direct survey of rening companies and areview of reners intentions that are already in the public domain.

The table accompanying the Processing Trends article is particularly telling forthe concerted support, or preference, it reveals for a carbon cap-and-tradeapproach over a carbon tax system among Western European reners. Comparethis with the position in North America, where proposals remain in Congressional

limbo. The industry lobbying system in Brussels does not have the cloutof its counterpart in Washington, and there was never any doubt thatcompanies would have to march to the tune of the legislators in matters ofemissions regulation.

Established in 2005, the European Unions Emissions Trading System (ETS)immediately became the worlds largest multi-state emissions trading scheme.According to the system, large emitters of carbon dioxide within the EU mustmonitor and annually report their CO

2emissions, and they are obliged every

year to return an amount of emission allowances to the government that isequivalent to their CO

2emissions in that year.

A signicant provision of the original ETS was the inclusion of allowances, orcarbon offsets. These are effectively credits granted to projects that claim moneyhas been spent to reduce carbon emissions. By potentially easing the burdenimposed by central government, carbon offsets made the ETS more attractive tomajor producers of CO

2, including reners. Since it is difcult to demonstrate

any saving in emissions, unless CO2

is either not produced or is permanentlystored, selecting projects and handing out permits to those whose work justiesthe credits is a major challenge for the Brussels bureaucrats. The estimated valueof carbon offsets by 2012, at current levels of growth, has been reckoned toexceed the EUs total spending on renewable energy projects.

Nonetheless, there are approaches to a system of credit where it is due thatmight work in a more appropriate fashion. For instance, at the European ReneryTechnology Conference held late last year in Berlin, a speaker called for rewardsfor reners within the rules of the ETS. If reners took steps to produce cleanerfuels, albeit producing more CO

2in the process, emissions trading would reect

the improvement in fuel quality rather than the extra greenhouse gas produced.However, since its latest review of the ETS, the EU seems determined to replacethe system of carbon offsets with a more auction-based trading system.

CHRIS CUNNINGHAM

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9/132

Renery CO2

management strategiesTom Yeung, Hydrocarbon Publishing Company

[email protected]

The recent global climate summit in Copenhagen,Denmark, has not produced any clear guidance on whenand how denitive climate legislation will be carried outby many countries, including the worlds two largestGHG emitters: China and the US. Meanwhile, on 23February 2010, the US Environmental Protection Agency(EPA) announced that it will slow down its earlier rulingregarding CO

2emissions from reneries, while also

possibly raising the threshold on these limits. Thesehappenings are indicative of difculties in passing land-mark legislation, which will affect nationalenvironmental policies that tie in to the well-being of

heavy industry and other businesses. Oil companieshave anticipated uncertainties in upcoming climatechange rules that could ultimately impact companysustainability. Therefore, many rms have already initi-ated or implemented programmes throughout theiroperations to address carbon emissions.

Taking these developments into account, HydrocarbonPublishing Company, in its latest strategic report, set outto identify the specic steps and strategies oil companiesare taking to help curb their GHG emissions. The datawere gathered through two methods: a direct surveysent to oil companies (excluding any E&P concerns)

around the globe; and a comprehensive search ofcompany websites and press releases. Both the surveyand information search focused on four key areas:energy efciency improvements, cogeneration, renew-able power sources, carbon capture and sequestration(CCS), and future legislative preferences.

Results of direct survey

The survey, titled Renery CO2

Management Survey,contained roughly 20 questions and was conducted viaemail across the global rening community in thesummer of 2009. A copy can be viewed at www.hydro-carbonpublishing.com/survey.php.

Surveys were sent out to process engineers, mainte-nance engineers, operations managers, unit managers,and others in an attempt to establish what steps renersare actively taking to reduce their carbon footprints. ChiSquare statistical tests were performed on the data todetermine statistical signicance.

The survey focused on the four main topics mentionedabove, along with preferences in carbon legislation forreners. In terms of preferred carbon legislation in pric-ing CO

2emissions, 47% stated that they would prefer a

carbon cap-and-trade (CCT) system, while 26% felt thata carbon tax (CT) would be the best approach. These

preferences may have something to do with how aparticular renery denes carbon management. Carbonmanagement denitions varied among survey

respondents: 34% stated that they dene carbonmanagement as internal emissions and product

consumption plus external power/utility generation;32% agreed with dening carbon management as inter-nal emissions and production consumption, but notexternal power/utility generation; and 28% felt that theentire life cycle needed to be taken into account toderive an accurate denition of carbon management.

With regard to energy management, 64% of renerswho responded are using or have used some type ofenergy management programme at their reneries.Energy efciency benchmarking was almost universallyused (94% of respondents). The use of energy manage-ment programmes and energy efciency benchmarkingappears to be popular, as 70% of respondents stated that

they are seeing both economic and environmental bene-ts from the use of these programmes.

On-site or exclusively associated power generationsystems was another focus area of the survey, with 68%of renery respondents currently utilising on-site orexclusively associated power generation systems. Out ofthe 68%, 42% are using a steam generator with a steamturbine as the systems prime mover, while 44% are util-ising natural gas as the primary combustion fuel.Natural gas may be a popular fuel choice as it is acleaner-burning alternative to other fuels and could helpreduce GHG emissions in a renery.

CCS is seen as a future technology that can help curbGHG emissions from industrial plants, including rener-ies. Of the reners surveyed, 51% are currently involvedor are considering involvement in CCS projects at theirfacilities. Within a renery, the main areas of focus forthese projects appear to be the H

2plant (39%) and the

FCCU (24%). Post-combustion amine absorption (27%),oxycombustion (23%) and pre-combustion steam reform-ing (23%) are viewed as the best future carbon-capturetechnologies, while injecting CO

2into depleted oil or gas

elds and enhanced oil recovery (30%) are the preferredstorage methods for reners.

In a nal summary question, reners were asked toselect purchase carbon credits, implement energymanagement, utilise lower carbon fuels for utility gener-ation, supplement fossil-based energy with renewableenergy or implement CCS as the best way to complywith impending CO

2caps. A majority (70%) feel that the

use of energy management programmes is the best routefor reners with regard to meeting GHG caps, followed

by purchasing carbon credits (15%).Further statistical breakdowns of the survey were

performed by region (North America vs Europe) andtype of oil company (integrated vs independent vsnational). While North American and European

responses were almost identical and matched the globalresponses presented above, major differences were seenin the answers to certain questions when comparing

www.eptq.com PTQ Q2 2010 7

Processing Trends


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An area in which many oil companies appear to differis the use of renewable energy for curbing GHG emis-sions. The direct survey received insignificant responsesto the question of renewable energy use in a refinery. Onthe other hand, a majority of West European oil compa-nies report involvement in renewable energy on theirwebsites and in press releases, which could be due tolarge government subsidies; for instance, $0.133/kWh

for wind electricity in Germany and $0.6053/kWh forphotovoltaic solar electricity in Italy.In contrast to the position taken by US and Canadian

firms, most European and Asian oil companies favourCCT over CT. As expected, many small, independentrefiners and oil concerns, particularly in Africa, providedno climate change position or carbon strategies in anypublic announcements, and their inputs are not includedin Table 1.

What does it mean?

Major oil companies are very proactive in formulatingstrategies and taking steps to comply with future CO

2

cap legislation. In the name of business sustainability,the impact on the bottom line must first be consideredwhen investing in any sort of project to cut carbon emis-sions. This fact may explain why the use of energymanagement and/or energy efficiency programmes issuch a popular method for refiners looking to curb GHGemissions. The direct survey and search of companyclimate change policy announcements led to the sameconclusion. Refiners prefer energy efficiency improve-ment programmes (often referred to as the low-hangingfruit of GHG emissions mitigation options), which theycan obtain easily and recoup investment from quickly

while waiting for clarity on legislation.On the other hand, short- and medium-term concerns,

such as depressed demand, poor margins, marketerosion by biofuels and decreasing consumption indeveloped nations due to higher vehicle fuel efficiency,have not distracted companies from impending regula-tory requirements for GHG emissions, which is whythey are also pursuing other carbon footprint reductionoptions, such as renewable energy (solar and wind) andCCS projects. The next decade could be a very challeng-ing time for refiners, but it could also provideopportunities for well-prepared concerns to expandmarket shares at the expense of many companies, partic-ularly small ones, which lack resources and have nostrategy for tackling and adapting to the not-so-distant,costly climate change legislation as revealed in thesurvey and search. Despite uncertainties, many devel-oped countries and China are expected to slash GHGemissions by 2020, just ten years away.

For further discussions and analyses of the directsurvey and publicly announced company policies, plusthe latest technology advances for improving energyefficiency, cogeneration, renewable energy use andcarbon capture, refer to Hydrocarbon Publishings multi-client strategic report, Refinery CO

2Management

Strategies: Technology Solutions to Reduce Carbon Footprintand Meet Business Sustainability Goals (www.hydrocar-

bonpublishing.com/ReportP/CO2Cap.php), March 2010.

integrated and national oil companies to independentrefiners. Both integrated (59%) and national (83%) oilcompanies prefer CCT, while independent refinersprefer a CT (55%) to regulate GHG emissions. Also,current or future involvement in CCS projects generatedvaried responses. Again, a majority of integrated (70%)and national (83%) oil companies mentioned participa-tion in current and/or future CCS projects, while 80% of

independent refiners indicated no current interest orplan in CCS projects in the future. This distinct differ-ence among these three groups could be due to thecurrently exorbitant costs of CCS projects. Independentrefiners would face sustainability problems if CCS wasrequired by legislation. As to the best way to complywith impending CO

2cap legislation, integrated (66%),

independent (67%) and national oil companies (50%) allprefer energy management programmes.

Company policies from other sources

While the results of the survey presented above weresent in by individual refineries, a search of oil company

websites and press releases was undertaken to deter-mine corporate policies in regard to curbing refineryGHG emissions. Oil companies around the globe seemto be actively engaged in utilising energy efficiencyprogrammes and combined heat and power plants attheir operations. A number of firms are also involved inconsortiums researching the possibilities of using CCS tohelp curb GHG emissions.

8 PTQ Q2 2010 www.eptq.com


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Company Country Energy Combinedheat Renewableenergy Carboncapture Positionincarbonpricing efciency andpower (excludingbiofuels) andstorage(CCS) (CTorCCT)UnitedStatesChevron CTConocoPhillips a CCTb

ExxonMobil CTFlintHillsResources

LyondellBasell

MarathonPetroleum CTValeroEnergy

CanadaHuskyEnergy a

ImperialOil a a CTIrvingoil a

SuncorEnergy a CCTb

LatinAmericaandCaribbeanEcopetrol Colombia Petrobras Brazil a

Pemex Mexico CCTPetroperu Peru

WesternEuropeBP UK CCTCEPSA Spain a

Eni Italy a CCTERG Italy a CCTGalpEnergia Portugal a

HellenicPetroleum Greece MotorOilHellas Greece OMV Austria a CCTRepsolYPF Spain a CCTRoyalDutchShell UK/Netherlands CCTSaras Italy a CCTStatoil Norway CCTTotal France

EasternEurope,CISCzechRening CzechRepublic MOL Hungary a

Rosneft Russia

MiddleEastADNOC(Takreer) UAE a

SaudiAramco SaudiArabia a

Tupras Turkey

Asia-PacicAttockRenery Pakistan CaltexAustralia Australia CCTCosmoOil Japan a CCTCPC Taiwan a

HindustanPetroleum India

IdemitsuKosan Japan IndianOil India JapanEnergy Japan NewZealandRening NewZealand NipponOil Japan Pertamina Indonesia PetroChina China a

Petronas Malaysia Sinopec China SKEnergy SouthKorea a

aNotacommercialcarbon-captureproject,butpartofconsortiumresearchingCCSpossibilities

bNotnalcompanydecision,butleaningtoward

Renersfavouredstrategiesforcarbonreduction

Table1



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vacuum ejectors- and above all,mate these interdependent com-ponents into a fully integratedsystem that reliably and consis-tently maximizes VGO yields lowin microcarbon and vanadium.

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stream compositions. And theperson who runs the simulationsmust always keep in mind thedictum of one of the grand oldmen of refining: "Fluids obey thelaws of physics and not thewhims of the process designer."In these times when every barrelof crude needs to be convertedto highest value products, onemust look to the expertise not

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To learn more about designing andoperating deepcut vacuum units,ask for Technical Papers 185, 199,and 205.

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Q How do I achieve the maximum yield of LCO from the FCCunit with the least possible increase in bottoms yield?

A Yen Yung [email protected]; Alan Kramer [email protected], Albemarle Catalysts

The rst thing the rener should do to maximisedistillate-range product in the renery is to remove alldistillate from the FCCU feed. That means optimisingthe separation in the upstream fractionators to removeall components having an atmospheric boiling rangelower than 370C (700F) from the FCC feedstock.

Traditionally, light cycle oil (LCO) production isenhanced by lowering reaction temperature and/orreducing FCC catalyst activity. As a consequence,conversion and bottoms cracking deteriorate. This can

be circumvented by applying bottoms recycle at theexpense of fresh feed intake.

The major challenge when maximising LCO yield ishence the reduction of conversion without sacricing

bottoms conversion. Therefore, an FCC catalyst isrequired with a high bottoms cracking power and highselectivity to LCO production. Albemarles UpgraderMD, Coral MD and Amber MD are designed to achievea maximum LCO yield. They feature: High accessibility to maximise the diffusion of oilfeed molecules to the active sites for maximum bottomsconversion

The high accessibility enhances the diffusion ofprimary products from the reaction zone and conse-quently minimises the conversion of LCO molecules tosecondary products High matrix-to-zeolite ratio to minimise cracking ofLCO molecules Tailored zeolite activity and selectivity for optimum

bottoms cracking potential Maximum resistance to the deleterious effect of feedcontaminants like nitrogen, carbon residue and metals.

Furthermore, Albemarles BCMT-500 additive lever-ages our catalyst technology and provides extreme

bottoms conversion power in an additive form. This isthe solution for reners faced with challenging situa-tions caused by sudden or short-term yield degradationdue to opportunity feedstocks being sent to the FCCU.

Q What catalyst type, or types, do you recommend forminimum octane loss in FCC gasoline hydrotreaters?

A George Anderson [email protected]; Steve

Mayo [email protected], Albemarle Corporation

Octane loss incurred across FCC gasoline hydrotreatersis primarily a result of olens saturation. The goal ofthis operation is to achieve sufcient removal of

sulphur (and nitrogen) from the FCC naphtha streamwhile minimising the saturation of olenic molecules.

If the renery is planning to hydrotreat full-rangeFCC naphtha, it is generally preferable to utilise alicensed selective naphtha HDS process. Theseprocesses use operating conditions and catalystsdesigned to minimise olen saturation reactions whilemaximising desulphurisation reactions. Gasoline prod-uct specs with total ((R+M)/2) road octane loss of 3octane numbers can typically be achieved. The cata-lysts used in these processes are proprietary.

If the renery is planning to post-treat the FCCnaphtha using conventional naphtha hydrotreatingtechnology, it is going to face some tough business andtechnical choices. Conventional hydrotreating of full-

range FCC naphtha is generally uneconomic in termsof octane loss and hydrogen consumption, regardlessof the type of catalyst used. Typical loss of road octanewill be on the order of 57 octane numbers, at best. Inthis case, the renery is best served by taking advan-tage of the fact that olens are most predominant in


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the light naphtha fractions, while sulphur, nitrogenand aromatics are most predominant in the heaviernaphtha fractions.

Caustic treating processes can be used to removesulphur from the light naphtha fraction while main-taining most of the olens. The heavy fraction can befully hydrotreated to remove sulphur, nitrogen andolens, accepting the resultant octane loss. The octane

loss may be limited to 35 road octane numbers usingthis strategy. CoMo catalyst is recommended for fullyhydrotreating the heavy naphtha fraction.

A further optimisation of this strategy may beachieved by separating an additional, mid-range cutwith naphtha hydrotreating followed by naphthareforming. CoMo or NiMo catalyst can be used tohydrotreat the mid-range naphtha fraction, dependingon the nitrogen content. All of these conventionalhydrotreating options require sweet FCC naphtha (ie,pretreated FCCU feed) to successfully control octaneloss. These strategies also require that the rener havethe exibility to continually optimise the light/heavy/

mid splits to meet the product specs and minimiseoctane loss.

Q Can you recommend a strategy for the best possibleproduction of transportation fuels from heavy vacuum residue

in a new-build renery?

A Hiroshi Toshima [email protected]; SteveMayo, Albemarle Catalysts

The strategy for achieving clean distillate production

from vacuum residue is a crucial issue for a new ren-ery. The strategy is even more important in light of thetrend toward heavier and more sour feeds, increasingenvironmental legislation in many countries and future

bunker fuel regulations. The representative VR conver-sion processes commercially applied are coking andebullated-bed hydrocracking. There are many cokingprojects ongoing globally; however, coking produces a

low-value coke and provides a limited increase indistillate production. Secondary hydrotreating of thecoker products requires more intensity due to the highsulphur, nitrogen and aromatics content. E-bedprocesses, with improved sediment reduction catalysttechnology, offer the opportunity to increase the distil-late yield much more than earlier generation catalysttechnology. In many cases, this enables E-bed processeconomics to be even more attractive than cokingeconomics.

Another technology for VR-to-distillate processing isa solvent deasphalting (SDA) unit, replacing thevacuum tower. The asphaltenes in VR are the mole-

cules that accelerate catalyst deactivation andcreate instability in the products. Deasphalted oil(DAO) can be used as the feed for a hydrocrackingprocess thatmaximises distillate production. Using SDAto replace the vacuum tower and either DAO hydro-cracking, DAO xed-bed hydrotreating or DAO E-bedhydrocracking processes may be one of the best solu-tions for a new renery to increase distillateproduction.

Finally, slurry-bed hydrocracking (SHC) is an emerg-ing technology. Several technology providers aredeveloping commercial slurry bed conversion

processes. Secondary upgrading of the SHC productscan be integrated in a high-pressure loop for improvedperformance and economics. Depending on the time-frame for design of the new renery, SHC may be aviable conversion technology for maximum distillateproduction.

A Yen Yung, Albemarle CatalystsThe FCC process is the premier conversion process toconvert residual feedstocks such as vacuum gas oil andresidues to transportation fuels. Modern design canhandle heavily contaminated feedstocks, thanks toimprovements in equipment design, such as feednozzles and catalysts coolers, and advancement in FCCcatalysts. Modern FCC catalysts are resistant tometal contamination, which is encountered whenprocessing heavy vacuum residue. The process is veryselective for the production of gasoline and has theexibility to produce high amounts of propylene orLCO, a diesel blending component. All major processlicensors offer a FCC design capable of cracking resid-ual feedstocks for maximum gasoline, maximum LCOor maximum propylene. Albemarle catalysts arerenowned for maximising the intake of residualfeedstocks to the FCCU, and the company champions

the continuous development of resid uidcracking catalysts, the latest being our Upgradercatalyst family.



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Upon completion of the HSSX Process, your amine or glycol system will exhibit improved performance with:

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The HSSX Process can take a slipstream from your system and clean the solution on-line, or it can clean the

solution off-line while the system is down. The HSSX Process may also be used to clean spent amine or glycol

from storage tanks.

MPR Services has cleaned over 4 million gallons of amine and glycols f or many of the major oil companies,gas plants, ammonia plants, and coal gasi cation plants. MPR provides all necessary personnel and specialized

equipment to perform their services at the plant.

MPR also offers full analytica l laboratory services to support job planning, as well as support on-site to jobs in

ro ress.

MPR Services can help you moni tor and optimize the operation of your amine/glycol treating uni ts!Contact us today!

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ConocoPhillips is comm itted to oering environmentally

riendly delayed coking technology all over the w orld. We

design and implement industry- leading systems that m eet

stringent environmental emissions standards globally.

Our advanced closed blowdow n system, an essential

part o the ConocoPhillips delayed coking process, saely

condenses the steam and hydrocarbon vapors during the

coke drum steaming and w ater quench operations. This

system saely recovers heavy hydrocarbons and inerts

released rom the coke drums dur ing upset conditions.

The coke storage area is comprised o high w alls to reduce

wind- borne dust, and the coke is handled by overhead

crane. The ThruPlus design meets rigorous environmental

guidelines or venting the coke drum ater quenching the

coke. The processing o oil bearing solid w aste recovers

solids and oily solids rom the ref nery. The oil is contained

with in the coker process and converted to valuable

ref ned products.

ConocoPhillips Billings ref nery was awarded theClean Air Act Excellence Award in 2006 and the EPAEnergy Star Aw ard in 2006 and 2007.

At ConocoPhillips, we believe we are

def ned by what we pass on to the next

generati on. Our ThruPlus Delayed Coking

Technology oers sae, clean, proven

and prof table coking units or several

generations in the uture. Sae. Clean.

Proven. Prof table. All over the w orld.

ConocoPhillips. Energy or tomorrow.

Turning heavy cr ude into high value

Sae. Clean. Proven. Prof table.

For help solving your delayed

coking challenges, contact

us via our Web site at

www.ThruPlus.com.www.ptqenquiry.comfor further information
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Anode-grade coke from traditional crudes

In an era of economic and politi-cal uncertainties, renerymargins will continue to be

dictated by processing heavier,sourer crudes. The dramaticincrease in residuum content from

10% in light sweet crudes to 50% inextra-heavy crudes poses interest-ing challenges, while presentingsome unique opportunities. This isespecially true when it comes toproducing high-value productsfrom low-value, bottom-of-the-barrel streams.

According to conventionalwisdom, the residuum is eitherremoved as fuel oil or asphalt, orsubjected to thermal conversion

processes for upgrading. Traditionalresid upgrading methods includeresid uidised catalytic cracking(RFCC), visbreaking (VB) anddelayed coking (DC).

RFCC is a widely used carbonrejection technology to converthigh-boiling, high-molecular-weighthydrocarbon fractions to more valu-able gasoline, olenic gases andother products. However, due tothe nature of the process, it islimited to processing lighter, low-metals, low-sulphur residues.

Visbreakers are essentially ameans of improving the viscosity ofthe residuum so as to minimise theaddition of valuable distillateboiling-range cutter stock to meetfuel oil specications. As worldeconomics seems to be inuencedby the use of natural gas, theproduction of fuel oil has a nega-tive effect on renery product slateand economics. This situation is

expected only to worsen as renersface regulatory pressures rangingfrom new maritime bunker fuel

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KBR Technology

specications to carbon dioxide capand trade and carbon footprintlimitations. This leaves renerieswith the challenge to minimise fueloil production.

Cab ci cicResidues from heavy crude oilscontain high concentrations ofsulphur, complex hydrocarbons andheavy metals such as nickel andvanadium. Due to the nature ofthese residues, delayed coking tech-nology is the most commonly usedcarbon rejection technology. In

addition, it enables the rener tosignicantly reduce production oflow-value fuel oil. Coking is a ther-mal cracking process in which,typically, a low-value residual oil,such as atmospheric or vacuumresidue (VR), is converted into valu-able distillate products and off-gas,leaving behind low-value fuel-gradecoke. High-sulphur petroleum cokeprices are distressed and, as isevident in Canada, coke is justbeing piled up in large quantitieswith no real economic outlet.

On the other hand, anode-gradecoke is in high demand in the elec-

trode industry. The world marketfor anode-grade coke is projected tobe approximately 1720 million tpa.

The high price differential betweenthe two grades, coupled withincreasing demand for anode-gradecoke, creates an unprecedentedneed to nd an alternate path toimprove the economics of coke

production while maintaininghigher renery margins.

Production of anode-grade cokeis greatly inuenced by the sulphurand metal content of the feed or, forall practical purposes, the VR. Thevolume and quality of the residueis essentially determined by thequality of the vacuum gas oil frac-tion and the ability to process thisfraction through conventionalhydroprocessing or catalytic crack-

ing conversion units. In most cases,the limiting factor is the metalscontent or the Conradson carbonresidue (CCR) in the gas oil.

The residue volume and qualityis by balance a reject dened by gasoil quality. Furthermore, not muchattention has been paid to improv-ing the quality of the residue priorto coking, primarily because ofissues associated with the methodsused to improve the residuequality.

One approach to reduce themetals and sulphur content of theresiduum is hydrotreating. Whilehydrotreating addresses the sulphurand metals content of the feed, it isan expensive proposition incurringhigh capital investment due to highoperating pressures and highhydrogen consumption with poorcatalyst cycle length. In addition,hydrotreating increases the level ofsaturates in the residuum, which

may make it unsuitable for anodecoke production because otherphysical requirements, such as


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18/132

volatile carbonaceous materialcontent, bulk density and grindabil-ity, may no longer be met. So, inreality, hydrotreating is not aneconomic option for residuumupgrading for anode coke produc-tion, and is therefore not widelypractised.

Three-product ROSEThe solution to obtaining anode-grade coke from traditional crudes,therefore, lies in alternative low-sulphur, low-metals content feedoptions to the coker unit. Theoptions become obvious whenanalysing the residuum at themolecular level, where it is clearthat the undesirable impurities inthe coke are essentially asphaltenicin nature and can be separated bysolubility-driven processes.

The solution involves the use of a

proven solubility-based physicalseparation process solvent deas-phalting in which a parafnic


solvent preferentially extractsparafnic and resinic molecules,leaving behind asphaltenic prod-ucts. While solvent deasphalting isprimarily an aromatics rejectionprocess, it is also a metals and CCRrejection process. The aromaticmolecules that are rejected contain

the majority of the metals and CCR,thereby producing a deasphaltedoil (DAO) that can be processed indownstream units directly or afterthe removal of resins.

While DAO has been traditionallyhydrotreated and/or catalyticallycracked owing to its higher valuemolecules, the resin that isproduced has so far been used onlyfor production of fuel oil or roadasphalt. The resin product is a rela-tively low-metal, low-sulphurresiduum that is high in asphaltene-

free CCR. Due to thesecharacteristics, resin is very goodfor producing higher quality coke,

and an excellent feedstock for theproduction of anode-grade coke.

Inherent in the solvent deasphalt-ing process is the ability to drawout the resinic molecules and toadjust the volume and quality ofthe resin. The operating conditionsof the asphaltene separator can be

adjusted to lift the resinic moleculesin the DAO. The resinic moleculesare then recovered from the DAOby partially expanding the solventunder supercritical conditions. Thisarrangement provides the exibilityto balance the streams to down-stream processing needs, whileconsistently meeting the requiredDAO quality and exercising otherdisposition options for the interme-diate resin streams.

While this addresses the issue of

providing low-sulphur, low-metalsfeed to the coker, the issue of deal-ing with streams used to make fueloil remains. While the higher valuedistillate products used for cutterstock can be used as saleable prod-ucts, streams of much poorerquality, such as the claried slurryoil (CSO) from the FCCU, nowrequire an alternative outlet. Theslurry oil is a highly aromatic rejectfrom the FCCU. Being denser than

water, transporting the CSO by seais not easy either. However, theCSO, despite being a reject from theFCCU, has low sulphur primarilybecause of the hydrotreated feed tothe FCCU.

So while the CSO may not havethe superior quality required forproducing high-value distillateproducts, it can still be blendedwith the resin from the three-product ROSE (residuum oilsupercritical extraction) process tobe used as feedstock for productionof anode-grade coke. In fact, anoptimum feed to the delayed cokerto produce anode-grade coke wouldbe a blend of the resin from theROSE process, the CSO from theFCCU and the required amount ofVR to compensate for any qualitygiveaway. In effect, what this givesthe rener is the ability to insulatethe coke grade from uctuations inthe quality of the crude and hence

always produce anode coke, irre-spective of the quality of the crude.Furthermore, the use of ROSE resin

Resin

separator

Asphaltene

separator

DAO

separator

Resinstripper

Asphaltene

stripper

DAOstripper

ROSEexchanger

Startresiduum

Resinheater

Hot oil

Hotoil

Solventcirculation

Asphalteneheater

Staticmixer

DAOheater

Solventstorage

Condensor

Asphaltene DAO

SteamSteam

Resin

Cooler

Steam

Hot oil

ROSEexchanger

Solventrecycle

Figure 1 Three-product ROSE


19/132

along with the available CSO willsubstantially moderate the varia-tions in VR quality that the renerymay see with changing crude slates,thereby enhancing the exibilityand reliability of the anode-gradecoker.

Although ROSE offers an excel-

lent feedstock for anode cokeproduction, it introduces the issueof disposal of the asphaltenesproduced. While the resin cut canbe utilised for making anode-gradecoke, the asphaltenic moleculesremain. These asphaltenes can besubjected to coking too but, owingto their high impurity levels, willonly produce low-quality high-sulphur fuel-grade cokes. However,delayed coking can only tolerate aCCR of 3438%. Therefore, the

amount of resin extracted dependson the quality of the remainingpitch or, in other words, only somuch resin is drawn out so that theCCR of the pitch remains withinthe limits of the delayed cokingunit. As a result, the renery willproduce a xed amount of anode-grade coke and the balance will bea lower amount of poorer qualityfuel-grade coke.

If the CCR of the asphaltenes is

too high for delayed coking, anotheralternate would be to divert thesemolecules away from the reneryto industries or end users outsidethe rening business who have anincentive to process these streams.The major challenge here is in thehandling and transportation ofthese molecules. The asphalteneproduct is a high-viscosity liquidthat solidies at ambient tempera-ture. A low-cost, high-capacity solidpelletisation technology such asKBRs Aquaform is an obvioussolution. This will help reners toeconomically store and move theserejects to a more desirable end use,such as solid fuel for cement kilns,the steel industry or the utilityindustries.

Delayed cokingIn its simplest form, delayed cokingis a semi-continuous process, irre-spective of the type of coke

produced. Although the cokingprocess is continuous, coke removal,handling and disposal are carried

out in a batch manner. The feed isheated to the reaction temperaturein a direct-red heater and subse-quently transferred to the cokedrums. The coking reaction isdelayed until the heated feed is

transferred into the coke drums,where the residence time is longenough for the coking reactions togo to completion. Coke is depositedin the drum and the cracked vapourproduct exits the drum from thetop, then enters the downstreamfractionator. Coke is removed fromthe drum by taking the drum off-line. In order to achieve nearsteady-state unit operation, the cokedrums operate in pairs, so that one

drum is in lling mode, while theother is off-line for decoking. Thechemistry of coking is similar to asevere thermal cracking process,wherein the larger molecules suchas parafns and parafnic sidechains are cracked into smallermolecules, which then polymeriseand condense to form coke.

Depending on feed quality andthe operating conditions of thecoker, the quality of coke producedmay vary from fuel-grade andanode-grade to needle-grade coke.Fuel-grade coke is used primarilyin power and cement plants as fuel;anode-grade coke is widely used inthe aluminium industry for the


manufacture of electrodes; andhigh-grade needle coke is apremium coke used to manufactureelectrodes for the steel industry.Table 1 shows typical specicationsfor three grades of coke.

The operating conditions of thecoker unit are selected according tothe quality of the feedstock and theprocess objectives. The threeprimary operating variables thataffect product yield and coke qual-ity are coke drum pressure, recycleratio and coke drum temperature.Table 2 shows commercial datapublished by a US rener to illus-trate the typical range of cokeroperating conditions for producing

different grades of coke.Most modern coker units are

designed and operated at low pres-sure, low temperature and lowrecycle ratios to maximise the yieldof distillate products and henceproduce fuel-grade coke as abyproduct. Cokers producinganode-grade and needle-grade cokeneed to be subjected to more severeconditions of temperature and pres-sure, along with a high recycleratio. Increasing the recycle ratiomeans increasing the hydrauliccapacity of the coker. This meansthat the fresh feed to the cokerneeds to be reduced to stay withinthe limitations of the hydraulic

Property Fuel coke Calcined anode coke Calcined needle cokeBulk density, kg/m3 880 720800 670720

Sulphur, wt% 3.57.5 1.03.5 0.20.5

Nitrogen, ppmw 6000 50

Nickel, ppmw 489 200 57

Vanadium, ppmw 141 350 Volatile combustible material, wt% 12 0.5 0.5

Ash content, wt% 0.35 0.4 0.1Moisture content, wt% 812 0.3 0.1

HGI 3570+ 60100

Coefcient of thermal expansion, x 10-7C 15

Specications for three grades of coke

Table 1

Fuel grade Anode coke Needle cokeDrum pressure, bar 1.01.5 1.53.0 4.07.0

Recycle ratio, vol% 510 2530 5080

Drum temperature, C 435440 440445 450455

Typical range of coker operating conditions for producing different grades of coke

Table 2


20/132

solution economically unattractive.In an attempt to improve the coke

quality, several combinations of VRand CSO from the FCCU weretested, conrming that the produc-tion of anode-grade coke from theexisting crude slate was not viable.Changing the crude slate was notan option, and an economic analy-

sis indicated that the production ofanode-grade coke would have asignicant and positive impact onrenery margins.

In an effort to reduce overall fueloil production, the renery is alsoconsidering the implementation ofa traditional two-product solventdeasphalting unit as a low-capitaloption to separate sufcientvolumes of high-quality DAO to besent to the FCCU, while rejecting

the pitch to fuel oil.The option to use a three-product

solvent deasphalting unit toproduce a DAO stream for feed tothe FCCU, a pitch stream for fueland an intermediate resin streamfor use as a coker blend stock wasevaluated. The three potential feedstreams VR, ROSE resin andCSO for testing in a delayed coker are shown in Table 3.

Several combinations of VR, CSOand ROSE resin were tested forcoke quality. The results (see Table4) indicate that a combination ofresin and CSO will produce high-grade anode coke. This is primarilybecause of the ability of the ROSEunit to sufciently improve the

sulphur, metals and C7 insolublescontent in the resin stream to allowfor the production of anode-gradecoke.

The use of ROSE resin along withthe available CSO will also substan-tially moderate the variations in VRquality that a renery may see withchanging crude slates, therebyenhancing the exibility and relia-bility of the anode-grade coker.

Conclusion

Anode coke production can be real-ised from traditional crudes byadopting a technology solution thatinvolves the integration of acommercially proven niche versionof the ROSE process and FCC slurryoil to custom blend feed for anodecoke production.

The combination of solvent deas-phalting and niche-delayed cokingrepresents an economic solution tominimise fuel oil production and

produce anode-grade coke, whichcan be implemented at a fraction ofthe cost of other resid processingoptions.

Mitra Motaghi is an Associate with the

KBR rening technology business unit in

Houston, with specic focus on resid and

hydroprocessing technologies. She holds an

MS degree in chemical engineering from Texas

A&M, Kingsville, Texas.

Kanu Shree is an Associate with the KBR

rening technology business unit in New

Delhi, with specic focus on resid and

hydroprocessing technologies. She holds a BS

degree in chemical engineering from the Indian

Institute of Technology.

Sujatha Krishnamurthy is an Associate with

the KBR rening technology business unit in

New Delhi, with specic focus on resid and

hydroprocessing technologies. She holds a BSdegree in chemical engineering from Anna

University, Chennai, India.


capacity of the original coker unit.Hence, three-product solvent deas-phalting becomes the obviouschoice to cut down the amount oforiginal feed to the unit, whereinthe extracted resinic molecules,along with the stranded streamsfrom the renery such as CSO andbalance VR, become a reduced fresh

feed to the coker unit. The balancecapacity can be met by increasingthe recycle ratio, which, in fact,favours anode coke production.

Renery case studyIn this example, an FCC-basedrenery is processing heavy crudesand has no bottoms processingcapability. Under the current oper-ating scenario, the VR is cut withdistillates and sold as high-sulphur

fuel oil.The quality of VR is too high in

sulphur and metals content, suchthat the addition of a delayed cokerprocessing the entire VR streamwould result in the production oflow-grade petroleum coke. Whenprocessing the entire VR stream, thelarge size of the coker and the lackof an economic outlet for the high-sulphur petroleum coke made this

Vacuum residue Slurry oil Resin

SG @60F 1.0279 1.0926 1.017

API gravity 6.2 -2.0 7.6

Sulphur, wt% 3.9 0.9 3.5CCR, wt% 20.3 9.9 17.6

Nickel, wppm 47 1 20

Vanadium, wppm 163 1 65

Three potential feed streams

Table 3

Coke specs 20/80 CSO/VR 40/60 CSO/VR CSO+ resin

Dry gas, wt% 4.2 4.2 4.2C

3+ liquid, lv% 61.8 59.9 60.7

Coke, wt% 33.0 35.3 34.4

Coke quality

Capacity, bpsd 20 000 20 000 20 000Coke, MT/D 1090 1177 1144

Sulphur, wt%


21/132

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Catalytic reforming options and practices

Reners throughout the worldutilise catalytic reforming toproduce high-octane reformate

for gasoline blending and high-value aromatics (benzene, tolueneand xylene, BTX) for petrochemical

use. Reforming is also a majorsource of renery-based hydrogen.

Reforming operations continue tobe challenged in the context oflowering gasoline pool aromatic/

benzene content; however, the cata-lytic reforming unit is still amainstay of renery operations.The recent upward trend in hydro-treatment needs has put even moreemphasis on reformer hydrogenproduction. The main differences in

technology among the variousreforming processes are discussedin this article, and special attentionis given to chloride control andcorrosion management.

FdtcThe standard feed to a catalyticreforming unit (CRU) is hydro-treated straight-run naphtha (SRN),typically containing C

6through C

11

parafns, naphthenes and aromat-ics. Naphtha from different sourcesvaries greatly in its ease of reform-ing. Most naphthenes react rapidlyand efciently to form aromatics.This is the basic reaction of reform-ing. Parafns are the most difcultcompounds to convert. A richnaphtha (lower parafn, highernaphthene content) makes the oper-ation much easier and moreefcient. The types of naphtha usedas feed to the CRU can impact theoperation of the unit, activity of the

catalyst and product properties.When catalytic reforming is usedmainly for BTX production, a C

6-C

8

Dgn nd prctc n ctlytc rfrng vlvng t t rnry cllng,

ncldng lwr gln pl bnzn cntnt nd ncrd dnd fr ydrgn

Tom Zhou Fluor Enterprises

FReDeRik BaaRs Fluor BV

cut (initial and nal boiling pointsIBP-FBP 60140C), rich in C

6, is

usually employed. For pro

petroleum technology quaterly

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