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ptqQ1 2012

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2012. 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 the publisher cannot be held responsible for any statements, opinions or views or for any inaccuracies.

3 All at sea ChrisCunningham

5 Outlook 15 ptq&a 21 Catalysts for maximising middle distillates RubenMiravallesandTamaraGalindoRepsol

27 Using cold boiler feed water for energy recovery AliSanDoGanTurkish Petroleum Refineries Corporation

33 Cost estimating for turnarounds GordonLawrence Asset Performance Networks

45 Abatement of hydrogen sulphide in asphalt JenniferDraperandJosephStarkBaker Hughes

51 Oxygen enrichment in desulphurisation ShivanAhamparamandStephenHarrisonLinde

55 Green retarder technology for the styrene industry LishengXu,JavierFlorencio,VincentLewisandChristopherMorrison Nalco AnaGuzman,CarmenMonfortandAnaOlivares Repsol Qumica Tarragona

65 Energy recovery with compact heat exchangers MarcosMatsufugiAlfa Laval

71 Low rare earth catalysts for FCC operations YenYungandKenBruno Albemarle Corporation

81 Catalyst additives reduce rare earth costs RayFletcher Intercat

85 Consolidation of refinery control rooms EricJanKwekkeboomYokogawa Europe & Africa

93 Integrated monitoring for optimising crude distillation GregoryShahnovsky,TalCohenandRonnyMcMurrayModcon-Systems Ltd

102 Crude oil vapour pressure testing HannesPichlerandKlausHense Grabner Instruments, a subsidiary of Ametek

105 Optimised hydrogen production by steam reforming: part I SankeRajyalakshmi,KedarPatwardhanandPVBalaramakrishna Larsen and Toubro

111 Improved catalytic reforming AnthonyPoparad,BeatrixEllis,BryanGloverandStephenMetro UOP LLC, A Honeywell Company

119 New crude oil basket for hydrogen savings RajeevKumar,PrashantPariharandRaviKVoolapalli Corporate R&D Centre, Bharat Petroleum Corporation Ltd

125 Industry News

126 Technology in Action

Covercaption:JettoweratSuncorsSarniarefinery,Ontario,Canada Photo:Suncor

Q1 (Jan, Feb, Mar) 2012www.eptq.com

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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 and other factors are the primary drivers for higher food prices, food competitive feedstocks have long been and will continue to be a major concern for the development of biofu-els. To compete, the industry has responded by developing methods to increase process efficiency, utilise or upgrade by-products and operate with lower quality lipids as feedstocks.

Feedstocks Biodiesel refers to a diesel-equivalent fuel consisting of short-chain alkyl (methyl or ethyl) esters, made by the transesterification of triglycerides, commonly known as vegetable oils or animal fats. The most common form uses methanol, the cheapest alcohol available, to produce methyl esters. The molecules in biodiesel are pri-marily fatty acid methyl esters (FAME), usually created by trans-esterification between fats and metha-nol. Currently, biodiesel is produced from various vegetable and plant oils. First-generation food-based feedstocks are straight vegetable oils such as soybean oil and animal fats such as tallow, lard, yellow grease, chicken fat and the by-products of the production of Omega-3 fatty acids from fish oil. Soybean oil and rapeseeds oil are the common source for biodiesel produc-tion in the US and Europe in quanti-ties that can produce enough biodie-sel to be used in a commercial market with currently applicable

PTQ Q1 2012 3

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Petroleum Technology Quarterly (USPS 0014-781) is published quarterly plus annual Catalysis edition by Crambeth Allen Publishing Ltd and is distributed in the USA by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. Periodicals postage paid at Emigsville PA.Postmaster: send address changes to Petroleum Technology Quarterly c/o POBox 437, Emigsville, PA 17318-0437Back numbers available from the Publisher at $30 per copy inc postage.

Vol 1 No 1

Q1 (Jan, Feb, Mar) 2012

All at sea

It being that time of the year, this issue of PTQ features our annual Outlook section, which leads off with a concise appraisal of the state of the global refining industry from the IEAs Executive Director, Maria van der Hoeven (see p5). The story, not unexpectedly, can be distilled to: lots more capacity on the way, with pressure building on more established centres of over-capacity.

A key image of the industry in years gone by was of crude carriers waiting offshore the worlds refining hubs for the best pricing opportunities to unload. In recent years, refiners have become major exporters and the picture is of shiploads of petroleum products chasing each other around the worlds oceans competing for markets.

In the first nine months of 2012, according to the Energy Information Administration, the US exported 655 million barrels of finished petroleum products, including 121 million barrels of gasoline. At the same time, the country imported 264 million barrels of finished petroleum products, includ-ing 32 million barrels of gasoline. Whether or not it is a long-term trend, Americans are driving less. No refiner wants to deal with the economics of running a plant under capacity, so export markets are the means to shore up production levels. This in turn means that quantities of crude oil imports, and therefore prices, have held up.

How long refiners in North America and Europe can hold onto those mar-kets is a matter for some conjecture. A couple of examples from fast-growing centres of refining may help to illustrate. According to Indias oil minister, in a statement in December, the nations annual oil refining capacity will rise by over 60% to 310 million tonnes by 201617 after new refineries in the states of Orissa and Punjab are commissioned. At present, the refining capacity of Indian refineries is around 190 million tonnes. India currently has enough refining capacity for its local markets, with fuel demand at 140 million tonnes in 201011. Domestic demand is projected to rise by 45% per annum up to 2017, which is some way short of accounting for a 60% increase in capacity.

In the far smaller but energy-rich United Arab Emirates, developments are, proportionately, just as significant. Forty years ago, there were no refineries in the UAE and the country depended on imports of petroleum products to meet demand. The first, 15 000 b/d refinery opened in 1976, but the recent completion of the Ruwais expansion takes the Emirates refining capacity to 774 000 b/d. Significantly, current refining capacity is not geared simply to local markets. Fuel oil production is being kept to a minimum and product specifications are geared to international markets. Sulphur levels in gasoline and diesel produced at Ruwais will be as low as those in Europe and other developed countries. Total refining capacity will grow by another 200 000 b/d when the $3 billion Fujairah refinery is completed in 2016. The outcome of the UAEs fast-paced developments will be a combined total of 500 000 b/d of petroleum products, of which close to 200 000 b/d is slated for addi-tion to the global export market.

The IEAs contribution to Outlook points out the inevitable consequences of capacity additions across Asia and the Middle East: over-capacity in Europe and North America is likely to bend under the strain imposed by more, and more modern, refineries pouring products into the global export pool. The least competitive refineries will succumb.

CHRIS CUNNINGHAM

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Maria van der HoevenExecutive DirectorIEA

The story of refining is one of two divergent trends. Huge and modern capacity increases are being built in key emerging markets, and particularly in Asia. But in developed OECD markets, refiners are seeing their already low operating rates and profitability squeezed further by the newer additions. What will be the end game? The simple answer is that we expect significant excess refining capacity for at least another several years, pushing many European and other OECD refineries to close up shop.

Following the economic recession of 2008-2009, and maturing OECD oil demand relative to the rapid growth seen in the non-OECD, the OECD oil refining sector has come under intense economic and operational pressure. The new refining capacity in emerging countries is often developed with high complexity, and is sometimes built more for strategic than purely economic reasons. This new capacity will place further pressure on OECD refiners not only because it is more efficient and of a larger scale, but also because the differentiation between environmental standards places OECD operators at a further cost disadvantage.

As highlighted in the IEAs Medium Term Oil and Gas Markets 2011, the world will add an additional 9.7 million b/d of crude distillation capacity post-2010, to reach a total of 103 million b/d in 2016. This compares to forecast demand growth of some 7 million b/d in the period, of which an increasing share will be met by non-refined supplies, such as biofuels, gas and coal to liquids, NGLs and condensates, which bypass the refining system.

Some 95% of additions are planned in the non-OECD, and most notably in Asia. China alone is expected to account for a third of global capacity growth, or 3.3 million b/d. That is largely in line with demand growth estimates. While project uncertainty here is ever present, the governments strategy seems to balance concerns over surplus capacity and increased product import requirements. Projects scheduled for the tail end of the forecast are therefore likely to be managed in line with evolving demand prospects. The rest of Asia will see a further 1.3 million b/d added in the period, or 13% of

P

global growth, while significant investments are also taking place in the Middle East and Latin America.

In contrast with Chinas caution, India is expanding its refining industry strategically, to establish itself as a key product exporter in the Asia Pacific region. India is already exporting high-quality products to the US, Latin America and Europe since the opening of Reliances huge new Jamnagar export plant in 2009. The country is likely to further increase product surpluses as refinery capacity is expanded by more than 1 million b/d by 2016. In the Middle East, Saudi Aramco has revived its ambitious refinery expansion plan, which was temporarily put on hold during the recession. It seems that three of the four proposed mega-projects will now come to fruition, with two 400 000 b/d projects likely before 2016. Elsewhere in the region, the UAEs 400 000 b/d Ruwais project is expected in 2014. Latin American expansions are dominated by Brazil, which is likely to add 1 million b/d of capacity by 2016 through several greenfields projects.

Emerging market plans seem to be driven by various objectives. Some major consumers wish for greater product self-sufficiency, while others are positioning themselves as regional hubs. At the same time, some erstwhile crude exporters are trying to shift to the export of higher value-added products. Most are driven by a mix of these goals.

OECD refining offers a stark contrast to this booming picture. Since the economic downturn, a total of 1.8 million b/d of crude distillation capacity has been shut (or is firmly committed to shut) in the coming years. That is the result of two things: structurally declining demand and increased competition from the non-OECD.

The picture looks particularly bleak in Europe, where seven refineries have already closed. Furthermore, several plants have lately been sold to cash-rich upstream non-OECD interests (Rosneft, CNPC and Essar, among others). The US sector is interesting, as the country is transforming into a significant product exporter - a major turnaround from its position as a net importer of more than 2 million b/d only a few years ago. Diverging markets also exist within the country, with those enjoying access to now very cheap crude from the US Midwest at a great advantage, especially compared to those in the difficult East Coast refinery market. With lower US gasoline import needs, European refiners face further pressure, as they are structurally inclined towards gasoline production (and less towards distillates). In the OECD Pacific, industry rationalisation also continues apace, with Japan accounting for the

www.eptq.com PTQ Q1 2012 5

Outlook for 2012

What are the important trends affecting the downstream processing industry this year? Executives and experts forecast challenges and prospects that could affect profitability

outlook copy.indd 1 13/12/11 10:58:35

brunt. By 2014, Japanese refiners face tough choices of closing capacity or investing heavily in upgrading units. As in the rest of the OECD, further capacity rationalisation, over and above that already announced, is likely before the market finds a new equilibrium.

The global refining market is seeing a contrast between developed and emerging economies, which is familiar in so many areas of global economic activity. The story is one of booming growth versus stagnation or contraction compounded by technologically superior and larger-scale competition. Given the short- to medium-term economic picture and resulting demand uncertainties, refiners would be wise to maximise the flexibility of their capacity plans, and to see what 2012 will bring. Some will not have that luxury.

Umberto della SalaPresident & Chief Operating OfficerFoster Wheeler

We are certainly seeing robust activity in all of the hydrocarbon-related business sectors in which Foster Wheelers Global Engineering and Construction Group operates: onshore and offshore upstream oil and gas, midstream/LNG, refining, chemicals, pharmaceuticals, metals and mining and power.

Certainly, we have a good prospects pipeline, although it is true that clients are in some cases taking longer to reach final investment decision or are releasing projects in phases. We have a number of projects that are going through the final investment decision-making process and for which we believe we are well positioned. And we are seeing new opportunities continuing to emerge, particularly in Asia, the Middle East and South America.

Looking forward into 2012, we see three key themes, which are in many ways the same three that we saw at the start of 2011, but these are now coming into even sharper focus. First is local service delivery. This has always been important to us and is becoming an even stronger area of focus for us and for our clients. We have made further strides forward this year, for example in Saudi Arabia and in Azerbaijan, by developing our own resources and by building relationships with local or regional client and/or contractors to enable us to deliver the Foster Wheeler product locally and competitively to our clients, for the long-term, in line with local content requirements and our clients preferences.

Second, the emphasis is on upstream. We are seeing clients splitting their organisations into separate upstream and downstream companies, and many of international oil companies are focusing more of their planned capital spend on the upstream sector (many include LNG in this category). The offshore and onshore upstream sector remains a strategically important market for us and one in which we are further developing our skills, service portfolio and geographic presence.

The third theme relates to the size and complexity of projects. Large projects are getting even larger and more complex; for example, the scope and scale of some of the planned investments in the Middle East, South America and Asia. In a number of these regions, new approaches are required, including bringing sources of external financing, leveraging local partnerships and developing innovative execution strategies, such as smart cloning for fast-track delivery, or employing a modular design and build approach in areas where resources are constrained. Size and complexity play to our strength, and we are now leveraging our skills and experience in delivering these complex hydrocarbons projects into the metals and mining sector.

As we have said before, competition remains strong everywhere. We are focusing on those opportunities where we believe we have differentiators, such as our technologies, our know-how, our client relationships, our global presence and our ability to work with clients from the earliest phases of projects to help them shape their investment, and our proven track record of safely delivering technically complex and very large projects.

Leon de BruynManaging Director Chevron Lummus Global

Fear of change is a natural human emotion and especially felt in todays tough economic market. As daily crises are announced, the energy industry is reeling from the challenges that could cause our industry to fall farther and farther behind in meeting the worlds increasing energy demands.

Actually, the energy industry is currently in a period of technical innovation that is quietly, yet surely, improving the future of energy for generations to come. We now expect to produce a more diverse supply of cleaner energy products available globally with extended lifecycles. Here are a few examples that were considered major world crisis problems only a few years ago, while now they are viewed as challenges that lead us to innovations that help make positive changes: The anxiety over the inevitable onslaught of peak oil that had been discussed and argued for years The competition for scarce energy causing future wars, famine, destruction of wildlife habitat and global warming as carbon heavy fuels were consumed more and more rapidly The future of energy expected to be particularly tough for the developing world that needs it to decrease poverty and develop their countries potential in a brutal market The environmental goals that were always viewed to be in conflict with world economic growth.

And in the US, the Energy Policy will force consumers to pay higher and higher prices for transportation fuels

6 PTQ Q1 2012 www.eptq.com




cbi.indd 1 8/12/11 22:05:08

as carbon gets taxed, coal mines are shut, petroleum supplies shrink and where bio-derived fuels, wind and solar power are mandated and subsidised. In each and every one of these areas, investments in R&D are steadily changing in direction from negative to positive in coal, shale, petroleum, biofuels, wind and solar. It is with such advanced, innovative technologies that we are able to discover new unconventional resources to produce products for our future.

The continuous search for energy efficiency at all levels in our industry, whether driven by emissions and carbon footprint reduction, energy utilisation or economic optimisation, continues to propel research and development breakthroughs. We continue to see new materials in catalysis and higher performance catalysts, manufacturing improvements, process innovations and equipment design advancements, and we are even rethinking our basic assumptions and conventional wisdoms, among others. This relentless search at Chevron Lummus Global has resulted in new-generation Isocracking applications, such as integrating hydrocracking for fuels and lubes, integrating hydrocracking and hydrotreating functions, and optimised partial conversion. The first of these new-generation Isocracking units that we designed were started successfully in the last couple of years.

Heavy oil development continues to be economic and highly attractive in North and South America. Horizontal drilling and multistage fracking will eventually unlock trillions of dollars of new oil and gas shale reserves in the Americas, Europe and Asia. These technologies will continue to improve the useful life of these reserves, which are estimated to last multiple decades.

Our latest heavy oil catalyst technologies allow the production of light clean transport fuels while still reducing the overall carbon intensity of the combined process. Catalyst innovation continues as a platform for greater R&D investment for Chevron Lummus Global. We have a great history and continue to develop and commercialise lower cost, higher performance hydrotreating and hydrocracking catalysts that are fit for purpose to convert heavy oil fractions to high-value, salable products.

Heavy oil recovery and upgrading will move well above 2 Million b/d as improved thermal technologies make their application economic at crude oil prices as low as $50/bbl. We also anticipate a technology push into the subsurface areas of heavy oil production, where in-situ upgrading may prove feasible and economic in the next few years. Subsurface upgrading technology is an area that could prove as revolutionary as the recent shale technologies have been in unlocking previously unrecoverable oil assets.

Recovered heavy oils such as bitumen are being converted in LC-Fining complexes in Canada and elsewhere to synthetic crude or finished products. We have furthered the LC-Fining technology and integrated it in upgrading schemes with other proven processes such as solvent deasphalting and delayed coking. As a result, recovery of heavy oil and conversion to transport


fuels has become more economically attractive, unlocking resources.

Bio-derived fuels are not doomed to causing inflation by driving up food prices. Non-food crops will prove to be cost-effective sources of biofuel feedstocks in the near future as our latest R&D investments come on line. Chevron Lummus Global is now working in partnership with ARA to bring our first dedicated demonstration biorefinery on line by 2014.

Maybe we will always continue to fear change in our energy industry, but here we must recognise that a new generation of engineers, scientists and investors are coming behind us to meet the energy and environmental goals of a growing population.

Charles DrevnaPresidentNational Petrochemical & Refiners Association(American Fuel & Petrochemical Manufacturers as of 25January 2012)

Political and regulatory uncertainty abounds for petroleum refiners and petrochemical manufacturers in the US in 2012, making it impossible to predict with certainty what changes lie ahead. 2012 also brings one change I can predict for the 110-year-old trade association I represent: NPRA, the National Petrochemical & Refiners Association. On 25 January, we will change our name to AFPM, the American Fuel & Petrochemical Manufacturers. We are adopting this new name because it better describes who we are and what we do.

Regarding the outlook for our industries in 2012, much depends on actions by Congress, President Obama, the US Environmental Protection Agency and the courts. President Obama, his EPA and the Senate majority remain focused on increasing over-regulation and increasing taxes on companies that produce oil and natural gas and that manufacture fuels and petrochemicals. The policies they advocate are part of an anti-fossil fuels agenda that would raise the cost of petroleum fuels and petrochemicals in an effort to make so-called alternatives that receive billions of dollars in taxpayer subsidies more competitive.

The majority in the House of Representatives is seeking to rein in over-regulation by EPA. The environmental agency wants to require fuel and petrochemical manufacturers to spend billions of dollars to reduce emissions, even though these reductions would bring little or no environmental benefit and would increase energy costs, trigger job losses, and harm US economic and national security.

At the same time, the outcome of lawsuits will determine how far EPA can go in some of its regulation of fuel and petrochemical manufacturers. One major case before the US Court of Appeals for the District of Columbia Circuit challenges EPAs endangerment


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finding. This finding concluded that greenhouse gas emissions threaten the environment and public health, and is the foundation of EPAs greenhouse gas regulations. My trade association has joined with other groups to argue that since the Clean Air Act never authorised greenhouse gas regulation, the only way to impose such a regulation would be for Congress to pass a new law.

AFPM will continue to support sensible and beneficial environmental regulation. But we believe that Americas national interest would best be served by comprehensive and objective cost-benefit analyses of regulations to determine which make sense and which do more harm than good.

We will continue to make our case in 2012 that EPA should not have unchecked power to take any action it wants without specific authorisation by Congress in the single-minded pursuit of unrealistic and harmful overregulation. It is time for higher consumer costs, lost jobs, and damage to Americas economic and national security to be considered as relevant factors in weighing whether ever-more stringent regulations are beneficial.

Eric BenazziMarketing DirectorAxens

T he main trends that will dominate the market for refinery products over the next 20 years are now well known. World demand for oil products or their equivalents is likely to increase at an average rate of a little less than 1% per year up to 2030 when it will represent about 104 million b/d of oil equivalent. However, this growth will not be distributed evenly around the world. Growth in road diesel, currently at 1.8% per year, will continue at a higher rate than that of gasoline (0.8% per year) for which new demand will be mainly located in emerging countries. Whereas, in the OECD developed countries demand will drop by an average of 0.8% per year, generating refining overcapacity.

Demand for refinery products will also be influenced by legislation that will impose the incorporation of increasing quantities of biofuels, notably those derived from recycling lignocellulosic biomass. The situation is different in emerging countries. These countries whose GDP is growing at a fast rate have populations who aspire to greater mobility. Therefore, demand for oil products in these regions is due to rise at the rate of 1.6% per year over the coming years and will represent 65% of world demand by 2030.

Demand for natural gas will also continue to increase in all the regions of the world, driven by the production of electricity and the needs of industry. In Europe, its use represents one of the best compromises for combining economic competitiveness with the reduction of greenhouse gases. In North America, the exploitation of

unconventional gas sources is a game changer that will have lasting repercussions in the energy, refining and petrochemical sectors.

While these contrasting trends offer opportunities for development, there are also negative aspects. Worries and risks are present, linked to the financial crisis that is shaking Europe and which could, if the European governments do not restore confidence quickly, plunge the rest of the world into a deep financial crisis.

The fact is that emerging countries continue to rely on the spending of richer countries to fuel their growth needs; this is especially true for China. In 2010, Chinese consumer spending represented only 34% of GDP compared to 60% within OECD countries.

Nevertheless, due to the growing influence of emerging countries in the world, they will need to shift their economies to concentrate more on domestic consumption. This will mean that the organisation of entire industries will have to change. Higher wages will be required for this kind of rebalancing and the population will claim a higher level of social security and welfare. As a result, the catching up of developing markets will provide opportunities for developed countries.

In 2012, the magic words will be: Flexibility and revamping of existing units to reduce the gasoline/diesel imbalance Integration between refining and petrochemicals will be part of the solution to recover valuable products such as propylene from low-value heavy feeds Squeezing the most from the bottom of the barrel will be required to take advantage of lower priced heavy crudes and to maximise motor fuel yields Tightening of fuel quality specifications will persist worldwide, requiring catalysts that perform even better.

Innovation in both technology and catalysts will continue to be the best tools to respond to market changes and to maximise profitability.

Colin ChapmanPresidentEuro Petroleum Consultants

In the refining and petrochemical Industry, it is true to say that the only constant in the industry is change. Over the past decades, refiners and petrochemical companies have had to meet challenges posed by legislation: Refiners: to continuously improve product qualities for transportation fuels Petrochemical producers: to produce higher valued products to differentiate from competitors.

In the gas sector, the introduction of shale gas on the global horizon is having a major impact on the future global gas markets and, in particular, in the Middle East and Russia. To meet these challenges, technology improvements have played a key role. We have seen




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upsets from water slugs andother unpredictable situationsthat have damaged internals,resulting in diluent losses andhigh vacuum unit overhead con-densable oil. Diluent is neithercheap nor plentiful, and highvacuum column operating pres-sure will reduce overall liquidvolume yields. And if the designof the delayed coker fractionatoris based on todays experiencewith conventional heavy feed-stocks you will be lucky to runsix months.What all this means is thatspecial process and equipmentdesigns are needed to satisfythe special demands of pro-cessing oil sands crudes. Suchprocesses are not generated bycomputer based designers whohave little or no experience andnever leave the office. They aredeveloped only by engineerswith know-how who have realexperience wearing Nomex suitsand measuring true unit per-formance in Northern Alberta.Shouldnt this be kept in mindby those considering long termsupply agreements?

Oil Sands Crude Profits andProblems?Canadian bitumen productioncurrently runs about 1 MMbpd,with some being sold as Synbitand Dilbit. Over the next 10-12years output is expected toincrease to 3.5 MMbpd and morerefiners will begin investing toprocess it and come to dependon the Synbit and Dilbit for asignificant part of their supply.Few today, however, have everprocessed these feeds at highblend ratios, and are unawarethat conventional process andequipment designs are not upto the job. Canadian oil sands

feedstocks are extremely hardto desalt, difficult to vaporize,thermally unstable, corrosive, andproduce high di-olefin productfrom the coker. If you intend tolock into a long-term supply,therefore, it is imperative that youconsider reliability and run lengthfrom a particular design.Too low tube velocity in thevacuum heater tubes will lead toprecipitation of asphaltenes. Toofast a flow rate will erode thetube bends. If coil layout, burnerconfiguration and steam rate arenot correct, run length will bemeasured in months, not years.Diluent recovery unit designsmust take into account possibleFor a discussion of factorsinvolved in designing refinery unitsto process difficult oil sands feed-stocks, ask for Technical Papers#234 and 238.

10 PTQ 01:10 01 PC PTQ 0107 ADF 10/19/07 4:42 PM Page 1

ad copy 2.indt 1 8/12/11 21:19:00

significant improvements in catalysts, plant designs and equipment.

This overview will focus on the Middle East gas and petrochemicals markets and their impact on the global markets. As the Middle East region looks to produce and export more refined products, predominantly ultra-low-sulphur diesel (ULSD), that meet the latest environmental specifications, radical changes are taking place in the established refining infrastructure and also produce more higher valued speciality products in the petrochemical sector, instead of commodity products.

Investment for new refineries and petrochemical facilities and new process technologies are being reconsidered as the economic climate has changed drastically in the last few years. Middle East producers are taking a fresh look at their existing assets and the options open to them to meet the increased production and product quality demands for the future. Projects are being scaled back to meet the new global situation.

However, we have recently seen an announcement on a project for the largest integrated refinery petrochemical complex in the world. The Sadara complex will benefit from low-cost ethane and propane feedstock from the adjacent Satcorp Complex and also from economy of scale. The complex will produce a variety of propylene-based products and aromatics. The project is estimated to cost $20 billion. About 45% of the products are destined for the Asian markets and 25% for other countries in the Middle East.

Sadara is the reincarnation of the $28 billion Dow/Aramco Ras Tanura Integrated Project (RTIP). The project was abandoned in 2010 due to escalating costs and a lack of agreement between the parties. Nearer term, Petro Rabighs $10 billion expansion on the Red Sea is being reconfigured from its original plan to produce 17 products in a $6.7 billion investment. Major quantities of speciality liquid chemicals will still feature. And in the immediate future, there is the $10 billion Saudi Kayan complex. Kayan has been producing major quantities of liquids and polymers for some time and will eventually manufacture 18 products.

These projects are based on low-cost feedstock and benefit from economies of scale. Middle East prices are usually fixed at favourable rates. The Saudi price for

natural gas, the dominant feedstock for the petrochemical industry in the Middle East, is $0.75/million Btu. This compares with much higher prices in other regions, which can vary from $310/million Btu.

The objective of the low Saudi price level was to guarantee very attractive internal rates of return for the potential international partners whose technology was required to develop the petrochemical sector. The price level has been fixed for decades. However, the price is due to be revised at the end of 2011 and is the subject of much debate in the region and beyond.

Saudi Arabia is in the leader of the move towards differentiated, higher valued speciality liquid chemicals. Other countries in the region are also moving into speciality liquid chemicals. The move to downstream speciality liquids is a strategy to stimulate economic diversification in the country, leading to greater employment prospects by creating locally available chemical and polymer building blocks for local conversion industries. This enables added value to be captured in the region. Why ship acetone from the Middle East to China, where it is converted into acrylic glass, and then ship it all the way back to the Middle East for use in signs and windows?

So more changes are on the horizon in the refining petrochemicals and gas sectors in the Middle East. Many of these topics will be presented and debated at our upcoming ME-TECH 2012 in Dubai, 1314 February.This overview was prepared with assistance from Leslie McCune,

Managing Director of Chemical Management Resources.

Rajeev GautamPresident & CEOUOP LLC, A Honeywell Company

This past year was an exciting one for UOP and across the refining, petrochemical, natural gas and biofuels industries where we work. We have high expectations for 2012 and continue to dedicate ourselves to developing and delivering unique solutions




that will address key trends in distillate production growth, novel refining technologies that will allow refiners to get more valuable product from every barrel of oil and the growing use of non-fossil feedstock sources.

There will be a continued emphasis on hydrocracking technology, catalysts and equipment for on-spec distillate production, especially in emerging regions like the Middle East, Asia and India, where capacity growth will be the strongest. This shift in product mix is a long-term trend, and we have committed significant resources to driving technology enhancements, new products and improvements in hydrogen management and energy efficiency to improve yields and profitability. Additionally, heavy crude is becoming a larger feedstock resource, and a refiners ability to process these heavier sources can offer a boost in margins. Our recently commercialised Uniflex process delivers 90% conversion to transport fuels while minimising by-products.

Another emerging trend that offers a great deal of opportunity for our customers is the continued growth in petrochemicals demand worldwide and the increased return on investment that producers can achieve by integrating their refineries and petrochemical complexes. UOP offers a number of novel approaches that can maximise production efficiency and leverage low-cost feedstocks.

Our latest innovation in FCC technology, the UOP

RxPro process, can achieve more than 20 wt% propylene yield from an FCC utilising advanced reactor technology and configurations found in our conventional FCC designs. In aromatics, technology and catalyst innovations are driving a significant increase in throughput at existing facilities along with step-change enhancements in energy efficiency. Additionally, we expect that the demand for solutions that produce propylene at high efficiency from cost- advantaged feeds, such as our own Oleflex technology, will remain an attractive option, especially as the shale gas boom drives LPG economics and availability.

We have seen the renewable fuels industry make some important steps forward over the last year, including the ASTM International approval of natural oil-based biofuels for commercial passenger flight and an impressive number of certification tests on military platforms. More and more global customers and governments are realising the importance of alternative options and that there are viable technologies available today. Renewable feedstocks have an enormous potential to contribute to our hydrocarbon supply and we expect to see the momentum for these technologies grow. The first UOP Ecofining unit for green diesel production will come online by the end of 2012.

Looking into 2012, we understand that our customers must focus on getting the highest return on their investments, maximising the yield on every single barrel of oil that they process.


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Q There are so many catalyst/process options for maximising the LCO yield. What delivers the maximum yield at a competitive cost?

A Yen Yung, Global Technical Specialist, Albemarle, [email protected] Ken Bruno, Global Applications Technology Manager, FCC, Albemarle, [email protected] amount of light cycle oil (LCO) for blending to diesel from the fluid catalytic cracking (FCC) unit can be increased by adopting the following operation strategy: Sharper fractionation of the FCC feed to minimise the amount of material boiling below 370C, the so-called diesel-range fraction of the FCC feed Minimise the initial boiling point of the LCO as much as possible while respecting the specifications for diesel, such as the flash point. The LCO yield will then increase at the expense of gasoline. This recommenda-tion applies to all columns in which diesel-range fractions are separated from gasoline. Some units have been able to minimise the LCO initial boiling point to about 165C Maximise the end point of LCO at the expense of the initial boiling point of heavy cycle oil while taking care that the specifications for diesel for example, density and viscosity are not exceeded.

The above reflect the first points the refinery operator should take care of before taking any other measures. In addition, an optimal FCC catalyst has to be selected based on the following considerations.

Most FCC units have been designed for operation in the LCO overcracking mode for the sake of high gaso-line yields. Nonetheless, a substantial increase in LCO in the 3040 wt% range can be obtained. An obstacle to overcome is the potential loss in bottoms conversion. The actual yield of gasoline and LCO will depend on operating severity, feed type and quality, and catalyst. The challenge is to selectively crack the large slurry molecules to LCO, while keeping down the coke yield and avoiding overcracking of LCO molecules into lighter products. This means increasing the reaction rates of the LCO-producing reactions while decreasing the rates of the LCO-consuming reactions to gasoline and to coke. It is generally accepted that mesopore and macropore activity, the so-called alumina matrix activ-ity, favours bottoms cracking, while zeolite provides for higher LPG and gasoline selectivity. Therefore, middle distillate production is generally favoured by higher matrix cracking (as evidenced by a higher meso

surface area) and reduced zeolite cracking. In other words, middle distillate production increases as the zeolite-to-matrix ratio (Z/M) decreases.

For greatest bottoms conversion, the feed molecules need to reach the active sites quickly. Conversion of the desirable products in the diesel boiling range and other secondary reactions, such as hydrogen transfer, aroma-tisation and condensation, must be avoided. This is achieved by increasing the accessibility of the catalyst. Accessibility, related to mass transfer, is the property that allows the feed molecules to rapidly reach the active sites and primary products to escape promptly, prior to any deleterious secondary reactions. Outstanding performance of highly accessible catalysts, as measured by our internally developed Albemarle Accessibility Index (AAI) method, has been confirmed in several applications.

Albemarle has a full line of MD catalysts. Amber MD

and especially Upgrader MD feature the highest matrix cracking and AAI in industry. Amber MD is recom-mended for gasoil feed applications, and the Upgrader catalyst family is recommended for cracking residual feedstocks. For applications requiring flexibility, our bottoms conversion additive BCMT-500 is recom-mended for all types of feedstock. In addition, Albemarles technical specialists have special tools for selecting the proper FCC catalysts grades, including low rare earth (LRT) technology alternatives, and opti-mising unit operations.

The two examples below show that a very high LCO yield can be achieved. The first example concerns an FCC unit processing vacuum gasoil with a typical API of 23 and a sulphur content of about 1 wt%. The cata-lyst used is Amber MD, the unit riser outlet temperature was 518C, the combined feed tempera-ture 226C and the cat-to-oil ratio 7.0 kg/kg. The special unit feature is that the gasoline endpoint is minimised to an ASTM D-86 endpoint of 149C, while the LCO endpoint is very high at an ASTM D-86 endpoint of 379C. Thanks to these cutpoints and the


ptq&a

Additional Q&A can be found at www.eptq.com/QandA

Mesopore and macropore activity favours bottoms cracking, while zeolite provides for higher LPG and gasoline selectivity

Q&A copy 9.indd 1 9/12/11 09:55:39

use of Amber MD, a yield of 44 wt% LCO is obtained, having a typical cetane index of 34. This unit applies no bottoms recycle.

The second example is an Amber MD application processing vacuum gasoil. The severity is very low: low reaction temperature (499C), high combined feed temperature (368C) and low catalyst-to-oil ratio (4.0 kg/kg). Bottoms recycle (the recycle rate/fresh feed ratio varied between 0.51.0 vol/vol) is applied to enhance the production of LCO. Note that the volume of recycle can be as high as the fresh feed intake. In this example, gasoline endpoint is also minimised. LCO yield and cetane index are very high: 42.4 wt% and 34, respectively.

A Ray Fletcher, Senior Technologist, Intercat, [email protected] are several options for maximising LCO produc-tion on the FCC unit. Since increasing LCO yield is achieved by reducing conversion, there will be a corre-sponding increase in slurry yield. The profitability achieved in a maximum LCO operation is directly related to the ability to prevent or limit this increase in slurry yield. Another important consideration that is typically overlooked is the anticipated duration of favourable diesel market economics.

Achieving desired yield selectivities is rarely the result of a single variable optimisation. It is very

unlikely to be able to maximise LCO yield entirely through catalyst reformulation. Intercat strongly recommends that the FCC operator works closely with their chosen catalyst supplier to optimise the catalyst formulation. However, it must not be overlooked that the catalyst supplier will rarely be able to meet tran-sient LCO market opportunities adroitly.

This is due to the fact that there are often large volumes of catalyst within the manufacturers strategic stocks held in reserve for the refiner, catalyst shipments

in transit plus fresh catalyst within the catalyst hopper. In addition, the unit must be 3540% changed out before the refiner can begin to see selectivity differ-ences. The typical time frame for the refiner from the point of decision until the unit begins to see selectivity changes will often be at least two to three months.

This long lag time has been sufficient to prevent most refiners from attempting to profit from market shifts. Intercat offers an alternative solution that will enable the refiner to profit from both short- and long-term market diesel demand.

The first step to maximising the LCO yield1 on the FCC unit is to ensure that the unit independent vari-ables have been optimised (see Figures 1 to 8). Note that the absolute value and slope for each independent variable will vary unit by unit. These standard shifts for maximum LCO are provided below. Reduce riser outlet temperature (+0.75 wt% for -10F) Increase preheat temperature (+0.15 wt% for +10F) Reduce gasoline and point (+1.7 wt% for -10F) Recycle slurry (LCO ~3040% of conversion) Increase CRC for partial-burn units (~12 wt%) Reduce catalyst activity (0.25 wt% for -1 wt%).

The most typical variable shifts for maximum LCO include reduced riser outlet, reduced gasoline end point, reduced catalyst activity via lower catalyst addi-tions, recycling slurry up to the unit constraints (typically main air blower or wet gas compressor) plus optimisation of catalyst circulation rate via preheat temperature.

The catalytic variables for LCO maximisation include: Decrease zeolite concentration Decrease rare earth on zeolite Increase matrix composition (acid sites residing in pores greater than 8 ) Optimised catalyst architecture. This may be defined as pore volume or accessibility, depending on your catalyst supplier.

The standard catalyst formulation for maximum diesel includes a reduction in zeolite content plus rare earth on zeolite, and an increase in active alumina with



The first step to maximising the LCO yield on the FCC unit is to ensure the unit independent variables have been optimised

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Q&A copy 9.indd 3 9/12/11 09:56:04

optimisation of catalyst particle diffusional characteris-tics. The most successful catalyst reformulations feature a reduction in the zeolite-to-matrix (Z-to-M) ratio. These formulation changes are worth consideration if

optimal diesel market conditions are expected to last more than four to six months.

An alternative approach to LCO maximisation for those refiners operating in dynamic diesel markets is to apply an additive approach (see Figures 9 and 10). Intercat has successfully applied its bottoms cracking additive (BCA) in over 41 FCC units globally. The aver-age LCO yield increase in these applications has exceeded 2.0 wt% (see Tables 1 and 2). This approach employs a reduction in the circulating inventory Z-to-M. Empirical observation has shown that the main air blower and wet gas compressor loadings have been unaffected in every application. This enables refiners to base load BCA into their FCC units without negatively impacting throughput. Intercat further enables refiners a swift return to typical Z-to-M levels in the circulating inventory via injection of Hi-Y, which is an additive containing very high levels of zeolite.

This approach has been commercially proven in multiple FCC units to swiftly increase LCO yields. Its primary advantage is to enable refiners to optimise the Z-to-M level of the circulating inventory in response to actual market demand. Intercat supplies state-of-the-art loading systems without charge to those refiners inter-ested in using this approach.1 Fletcher R P, Opportunities for On-Demand LCO Maximization, AM-09-69,

2009 NPRA Annual Meeting.

Figure 9 BCA-105 performance

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Design criteria Charge Base btms Additions Yield selectivitiesRegion Design Supplier API CCR Yield API Cat, tpd BCA, % Dry gas LPG Gaso LCO Slurry CokeEurope UOPSBS Albemarle 23.1 0.82 6.0 0.5 6.5 -0.60 0.0 1.0 5.0 -1.5NAmerica KelloggUltra Grace 22.5 2.28 17.8 10.0 10.0 10.0 0.00 0.00 3.3 -3.3 -3.3 0.0Asia Kellogg CCIC 26.6 3.7 9.6 8.1 7.3 8.0 -0.05 -1.2 -1.2 3.3 -0.5 -0.9NAmerica KelloggF IMP 24.1 8.8 -0.5 4.5 -0.05 0.0 -0.8 2.9 -1.0 -0.4NAmerica Sinclair Albemarle 23.3 2.3 4.5 10.6 9.0 0.8 2.7 -2.0Europe UOPSBS Albemarle 20.0 4.7 10.5 3.0 5.0 12.0 -0.10 0.0 2.0 2.0 -3.9 0.0NAmerica UOPStack Grace 24.4 0.2 14.3 2.0 6.5 0.00 0.4 2.0 -3.5 0.0NAmerica KelloggF Grace 26.3 8.8 3.0 2.9 -0.90 0.9 -1.0 1.8 0.0 -0.2Asia UOPSBS 20.7 0.3 13.0 13.2 1.5 3.0 -0.05 0.0 -0.2 1.7 -1.7 0.0NAmerica KelloggUltra IMP 24.7 5.8 4.6 1.4 -0.24 1.5 2.0 1.5 -1.4 -0.8Asia R2R 21.7 2.39 12.0 -1.7 5.0 6.9 1.3 -1.3Asia R2R Grace 20.0 4.9 16.0 -1.5 6.5 1.0 -1.0NAmerica UOPSBS Grace 22.7 0.29 9.8 -2.0 3.0 10.0 0.00 0.0 0.0 1.0 -1.0 0.0

Overview of BCA performance in LCO mode

Table 1

Minimum Average MaximumFeed qualityGravity 20.0 23.1 26.6Sulphur 0.20 1.20 2.30CCR 0.20 2.19 4.90Nitrogen 200 729 1390OperationsReactor temp 919 966 993Regenerator temp 1216 1303 1360Catalyst adds, tpd 1.4 4.3 10.0BCA conc, % 3.0 7.8 12.0Equilibrium catalystMAT 61 67 71Ni 355 2287 5700V 693 2396 7500Yield selectivitiesDry gas -0.9 -0.2 0.0LPG -1.2 0.2 1.5Gasoline -1.2 0.3 2.0LCO 1.0 2.3 5.0Slurry -3.9 -1.7 0.0

Typical yields of BCA in LCO mode

Table 2

Q&A copy 9.indd 4 9/12/11 16:52:25

Q Are low rare earth catalyst additives for SOx reduction

available?

A Alan Kramer, Global FCC Additives Specialist, Albemarle, [email protected] Yes, Albemarles SOxMaster is a zero rare earth SOx reduction additive that has been in use since 2005. Albemarle originally developed SOxMaster in response to the known negative effects of cerium in partial- combustion FCC units. As rare earth prices escalated, refiners operating in full combustion have turned to SOxMaster to control both SOx emissions and rare earth costs. It has been used by over 20 refineries around the world.

Switching SOxMaster requires special attention due to the differences in performance characteristics between SOxMaster and cerium-containing SOx reduc-tion additives. Albemarle has collected the best practices and lessons learned from the multitude of additive trials our technical service teams have performed globally. We have condensed this information into an efficient trial execution template, designed to keep the refinery in compliance with its SOx emissions regulations, while becoming acquainted with the new additive. This template consists of four main components: prerequisite data gathering and analysis, baseline establishment, SOxMaster transition, and the ongoing demonstration of performance.

In conclusion, refiners should not have to settle for new low rare earth SOx additives when non-rare earth alternatives are already available.

A Ray Fletcher, Senior Technologist, Intercat, [email protected] plays a significant role in additives for SOx reduction. Reducing the additive cost by simply drop-ping the cerium oxide concentration will work up to a certain point. However, exceeding this point will result in loss of SOx-reducing activity, leading to substantially increased additive injection rates.

Intercat has developed a low-cerium SOx-reducing additive, Super SOxGetter-II, in which the cerium oxide content has been reduced by 50%. The activity of this additive has been observed to be at least equal to the benchmark SOx-reducing additive, SOxGetter, which contains twofold more cerium oxide. Over 38 FCC units are now continuously injecting SOx Getter-II with-out any loss in SOx absorption efficiency. This technology enables refiners faced with stringent SOx emissions standards to reduce their operating budget without compromising effectiveness. Additional R&D work is currently under way to further reduce this cerium level; it is expected that SOxGetter-III will shortly become available with much lower cerium content.

Intercat has developed a rare earth-free SOx-reducing additive, Cat-Aid. This additive is effective where ultra-low levels of SOx reduction are not required. This additive is lower in cost but requires higher concentrations in the circulating inventory. It has

the side benefit of passivating vanadium and absorbing feed nitrogen, leading to enhanced conver-sion together with a reduction in fresh catalyst additions. This additive provides add-on features for refiners who do not yet require reductions in SOx to ultra-low levels.

Q Is it possible to predict desalter performance accurately when switching between crude blends?

A Sam Lordo, Marketing Manager-Process NA, Nalco Energy Services, [email protected] without a lot of testing and knowledge of the indi-vidual crudes that comprise the blend. Even after that the models used are not accurate enough to fully predict impacts on desalination, dehydration and oil undercarry.

cheap crudes and supplemental feedstocks drive plan-ning decisions. The task at hand is to decide how to prepare and protect your hydrocracker or hydrotreater from silica and other contaminants that will force you into an early shutdown. No-one wants to turn an oper-ating unit around prior to a planned event, as the cost and disruption to the entire facility are enormous. Todays refiners have competing forces at play: inex-pensive, opportunity feeds containing high levels of contaminants combined with the need to keep the unit operating until the next scheduled turnaround or longer.

Innovative technology solutions can help address this issue. CLG has catalyst systems available to handle silica and other contaminants. Our catalysts are capable of handling high levels of silica and can be designed to handle specific contaminants as well as optimised for particular operating conditions and expectations. We offer a complete line of guard systems and catalysts to protect your investment, as well as to allow you to opti-mise your refinery and operate it at its full potential.

: EZnkZ DZ]e^\% M^ \agheh`r FZgZ`^k _hk Ahg^rpêelNHIAr]khikh\^llbgÌkhc^\mM^ \agheh`r@khniSilicon is a contaminant that is present in all delayed coker-derived feedstocks and also observed in straight-run gas oils derived from certain crudes. Catalyst loading strategies are available to manage silicon in the feed while maintaining the desired catalyst cycle life.

The first bed in a hydroprocessing unit reactor includes a graded bed consisting of several layers of different materials, with the objective of protecting the down-stream catalyst from plugging due to particulates and/or deactivation due to metals, sodium, silicon or other contaminants.

If the unit feedstock contains silicon, one of the materials utilised in the graded bed would be a cata-lyst optimised for silicon uptake. A high surface area catalyst is recommended to provide high silicon removal capacity without significantly impacting cata-lyst activity. UOP specifies catalysts manufactured by our alliance partner Albemarle, which are well suited to silicon removal. The specific materials are selected based on the nature of the unit feedstock (naphtha or distillate vs heavy gas oils) and the processing objectives.

It is not required that all silicon in the feed be trapped in the graded bed, since the main hydrotreat-ing catalyst typically retains a reasonable activity even when loaded with some silicon. The graded bed volume may be limited by the need to maintain a certain volume of active treating catalyst. In this case, there will be some breakthrough of silicon from the graded bed into the main catalyst as the cycle progresses. However, by optimising the proportion of silicon trap versus active catalyst, sufficient activity may be retained to reach the desired cycle length. It should be noted that sulphur breakthrough into the main catalyst will prevent the catalyst from being regenerated and reused, since silicon is not removed during a catalyst regeneration.

: @^hk`^:g]^klhg%@eh[ZeAr]khikh\^llbg`Li^\bZeblm%:e[^fZke^%`^hk`^'Zg]^klhg9Ze[^fZke^'\hfLmô^g FZrh% @eh[Ze FZgZ`^k Ar]khikh\^llbg`:iieb\Zmbhgl%:e[^fZke^%lmô^g'fZrh9Ze[^fZke^'\hfThe good news is that silicon is a relatively mild poison for hydrotreating catalyst. It can come into the hydrotreater as a solid (eg, sand particulates) or as a dissolved organic material. If silica (SiO2) comes into the unit as a particulate, it will tend to build up the pressure drop in the unit by filling in void space in the

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Q&A copy 8.indd 3 13/9/11 12:03:34

www.eptq.com PTQ Q1 2012 19www.ptqenquiry.com for further information

Reducing the additive cost by simply dropping the cerium oxide concentration will work up to a certain point

Q&A copy 9.indd 5 9/12/11 09:56:27

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grace.indd 1 8/12/11 21:10:12

Catalysts for maximising middle distillates

Increasing middle distillates consumption in Europe is a trend that began in the 1990s and is expected to continue in the future, while at the same time gasoline demand is decreasing. This has resulted in an imbalance between demand and supply for middle distillates and gasoline in Europe, meaning that refiners face an important challenge of increasing the gasoil-to-gasoline ratio in the refinery. There are many options by which refiners can raise the produc-tion of middle distillates at the expense of gasoline. For example, refineries can operate their FCC units in maximum distillates mode.

The Repsol Puertollano refinery is an inland refinery located in the centre of Spain. The refinery proc-esses heavy crudes with a deep conversion scheme, which includes a delayed coker and FCC and mild hydrocracker (MHC) units. The complex also includes an ethyl tert-butyl ether (ETBE) and a hydrofluoric acid alkylation unit, which process the C4 fraction from the FCC unit. The FCC unit is a 40 500 b/d Exxon Flexicracker, which was started up in 1983. In 2004, an Axens MHC was installed for FCC feedstock pretreatment, in order to adapt product quality to the more stringent regulations of maximum sulphur in fuels. Since then, 9095% of the feedstock proc-essed by the FCC unit is mild hydrocracker residue (RMHC), with the other 510% being a heavy feed-stock, such as atmospheric residue, which is necessary to close the unit heat balance.

The main objective at the Puertollano FCC unit is the maxim-

Collaboration in catalyst development and application, from laboratory scale to commercial operation, enabled a refiner to achieve production objectives

Ruben MIRavalles and TaMaRa GalIndoRepsol

isation of middle distillates production. Other unit objectives include a reduction in light naphtha yield, maximum olefin content and a minimum motor octane number (MON) value required. To achieve these objectives, the unit operates at very low severity (low riser temper-ature, cat-to-oil ratio and e-cat activity), with maximum slurry recycle. Producing maximum middle distillates in the Puertollano FCC unit case is a difficult chal-lenge. The severely hydrotreated

RMHC feedstock is highly crackable with a very poor selectivity to middle distillates. In addition, the coke-making tendency of the RMHC feed is very low. Therefore, processing this feedstock at low severity requires maximum slurry recycle and the simultaneous processing of a certain amount of heavy feedstock, such as atmos-pheric residue, in order to close the heat balance.

Processing of atmospheric residue in this unit has several disadvan-tages. For example, low-sulphur atmospheric residues must be proc-

essed in the FCC unit in order not to penalise the sulphur balance. Therefore, light crudes, which are not the optimum feedstock in the refinery scheme, must be distilled to feed the FCC unit. Processing of atmospheric residue in the FCC unit also results in high metals contamination on the e-cat, with a subsequent increase in catalyst consumption.

Collaboration projectGrace Davison has been the FCC catalyst supplier for the Puertollano FCC unit for several years. Grace has continually made innovations in catalyst technology, which has allowed the Puertollano FCC unit to better adapt to the changing production scenarios. Before the start-up of the MHC unit, the Goal catalyst from Grace Davison was used. After the start-up of the FCC pretreatment and in order to adapt to the significant feed quality change and operating conditions in the FCC unit, the Goal catalyst was replaced by the Nomus-100 catalyst based on first-generation EnhanceR technology.

Later, Grace Davison developed the Nomus-Dmax catalyst, which is a second-generation EnhanceR cata-lyst for increased middle distillates yields, and this catalyst was also successfully applied to the Puertollano FCC unit operation. In order to fully optimise the challeng-ing Puertollano operation, Grace Davison and Repsol decided to start a joint collaboration project to develop a new generation of cata-lysts for middle distillates maximisation in hydrotreated feed-stock scenarios.


Increasing middle distillates consumption in europe is expected to continue, while at the same time gasoline demand is decreasing

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formulations and tested them on a laboratory scale in an ACE (advanced catalyst evaluation) unit.

A total of 19 catalysts were evalu-ated in the first round to select the best zeolite, matrix and post- treatments, and six of the highest performing catalysts were fine-tuned and tested again in a second round of trials. Upon completion, the top four catalysts were selected for the following phase of the project, which consisted of an eval-uation in the Repsol DCR-II pilot plant unit. Process modelling with FCCSim was used to translate pilot plant results to the commercial unit, to check unit constraints and to optimise operating conditions for the new catalysts. The catalyst that showed the best performance in both a high and low metals scenario, the DieseliseR-Sol 16 cata-lyst, was manufactured by Grace Davison on an industrial scale and the results from its commercial use in Puertollanos refinery will now be discussed.

Commercial application of DieseliseRThe DieseliseR-SOL 16 catalyst trial began in September 2009. During the catalyst turnover, the feed rate in the commercial unit was variable, with alternating operations at a minimum feed rate during the end of 2009 and early 2010 with periods of high throughput. Independently of the total feed rate, the improve-ment in heat balance closure achieved with the new DieseliseR-SOL 16 catalyst has allowed a desired progressive reduction in the low-sulphur atmospheric residue (AR) processing (see Figure 1).

Due to the reduction in the amount of atmospheric residue needed to close the heat balance, contaminant metals on e-cat have been significantly reduced, in particular by deactivating metals such as vanadium and sodium. The periods of low feed rate have also contributed to lower contaminant metals levels on e-cat. Consequently, the catalyst addition rate has been progressively decreased until it reached the minimum technically needed to maintain levels in the regenerator and stripper (see Figure 2).

Two different scenarios were defined for the development of the new catalyst: a high metals scenario, corresponding to atmospheric resi-due processing and high metals on

e-cat; and a low metals scenario, with no atmospheric residue proc-essed and low metals on e-cat. In the first phase of the project, Grace Davison developed several catalyst

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Figure 3 Middle distillates (140380C) production

repsol.indd 2 9/12/11 16:56:32

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During the catalyst turnover, a continuous increase in middle distil-lates (140380C) was recorded in the unit (see Figure 3), thus achiev-ing a significant improvement in the main production objective.

Reduction in light naphtha production using the DieseliseR-SOL 16 catalyst is also clear (see Figure 4), although in this case the comparison is not so straightfor-ward because the level of olefins promoter in the inventory has not been constant. Due to lower propyl-ene demand, olefins promoter usage was stopped during the DieseliseR-SOL 16 catalyst period, as can be seen in the graphic of P2O5 on e-cat (see Figure 5). This factor must be taken into account because it is necessary to discount the olefins promoter effect for the comparison of the two catalysts.

Shifts in commercial yields with the new catalyst are detailed in Table 1. The deltas have been obtained as the difference between average values from several test runs performed in the commercial units with the Nomus-Dmax 121 catalyst, before catalyst substitution, and the DieseliseR-SOL 16 catalyst at around 60% turnover. Regarding operating conditions, it can be seen that riser temperature and MAT activity have been held constant on average between the two periods. Feed rate was slightly lower during the DieseliseR-SOL 16 catalyst period, whereas slurry recycle was slightly higher.

The main change in operating conditions was the reduction in olefins promoter addition rate due to lower propylene demand. Nevertheless, the effect of olefins promoter on the yields in Table 1 has been corrected. Results show an impressive increase of more than 3 wt% in middle distillates, similar bottoms production and a signifi-cant reduction in light naphtha, thus achieving the desired FCC product yields to better suit market demand. The decrease in propylene production is not an issue in the current situation as a result of low product demand, and in any case LPG production loss could be easily recovered with the addition of ZSM-5 additive.

E-cat comparison Direct comparison of the previous and current catalyst in the industrial unit is difficult. First, feedstock qual-ity has been variable, with atmospheric residue being progres-sively reduced during the catalyst turnover. Second, some of the oper-ating conditions that greatly impact yields and selectivity, such as feed rate (which affects residence time) and olefins promoter addition rate, have been varied during the DieseliseR-SOL 16 catalyst turnover.

For this reason, in order to check the good results observed during the industrial trial, several Nomus-Dmax 121 and DieseliseR-SOL 16 e-cat samples collected from the commercial FCC unit were tested in the DCR pilot plant at Repsols research and development facilities.

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yield (DR16 - base)Yields: Conversion @ 161C -3.8Fuel gas 0.2C

3 total -1.18

C4 total -1.15

LPG -2.3LCN-L -2.9LCN-M 1.1Gasoline -1.7Middle distillates 3.5DO 0.3Coke 0.0Operating conditions:Feed rate, t/h -24.9RA rate, t/h -6.4Slurry recycle, m3/h 5.8Feed density -0.0042Riser temperature, C 0Preheat temperature, C 11MAT activity, wt% 0Olefins promoter, % e-cat -2.5

Yields and operating data comparison of DieseliseR-SOL 16 vs Nomus-Dmax 121

Table 1

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provided a successful outcome in an area of joint interest. It has been an exemplary project, covering all the stages from research in new catalytic technology to development and testing, first at laboratory scale, followed by pilot plant validation and successful application to commercial production and operation.

EnhanceR, DieseliseR-SOL, NOMUS-DMAX, NOMUS-100 and GOAL are marks of Grace Davison.

Rubn Miravalles works in the Refining Department of Repsols R&D Division where he is in charge of the FCC research project and has acquired broad experience in catalyst characterisation and selection, modelling and process studies. He holds a bachelors degree in chemistry from the University of Burgos, Spain, and a masters in refining, gas and marketing from the Instituto Superior de la Energia. Tamara Galindo is a Process Engineer at Repsols Puertollano refinery, Spain, where she is in charge of several processes. She holds a bachelors degree in chemical engineering from Rey Juan Carlos University, Madrid, and a masters in refining, gas and marketing from the Instituto Superior de la Energia.


For the pilot plant comparison, the e-cat samples were tested at constant operating conditions, which simu-lates operation in the industrial unit, using a representative feed sample collected from the Puertollano unit. The results of pilot plant comparison of both catalysts at constant coke, which are shown in Table 2, confirmed the excellent results observed in the commercial unit.

ConclusionsThe development of a new genera-tion of EnhanceR FCC catalysts for maximising middle distillates has resulted in a significant benefit for the Puertollano refinery. The DieseliseR-SOL 16 catalyst has achieved an improvement in the two main production objectives namely, a significant increase in middle distillates production in a very challenging hydrotreated scenario and a decrease in gasoline production thus allowing the FCC unit product yields to better match the refinerys demand. The optimised catalyst also allows the

FCC units heat balance to be closed without having to process atmos-pheric residue, which provides a reduction in e-cat metals and cata-lyst consumption, and a decrease in the sulphur content of FCC products.

Last, but not least, this project involved close collaboration between Repsol and Grace, which

Table 3

yield (DR16 - base)Yields: Conversion @ 161C -4.4Sulfhydric 0.0Fuel gas 0.1C

3 total -0.47

C4 total -0.50

LPG -1.0LCN-L -2.5LCN-M 1.0Gasoline -3.4Middle distillates 3.0DO 1.2Coke 0.0Total 0.0

DCR pilot plant comparison of e-cats at constant coke

Table 2

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From Engineering Through Fabrication

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Using cold boiler feed water for energy recovery

Steam at different pressure levels is used for many purposes in refineries, includ-ing power production (steam turbines), heating, steam tracing, stripping, atomising and deaeration. Steam is produced from fired utility boilers, cogeneration units (gas turbine HRSGs), furnace waste heat boilers, product rundowns, column refluxes and so on by adding heat to supplied boiler feed water. Boiler feed water is conventionally supplied by deaerators, where steam is used to heat water to saturation conditions at a certain pressure to strip dissolved oxygen, with the aim of preventing corrosion in steam production units. In this article, the benefits of providing cold boiler feed water from membrane deaerators to steam-producing or water-heating waste heat streams will be explained, with some typical examples for an oil

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