PROGRESS - Europa...PROGRESS Preface iv July 2013 PB/EIPPCB/REF_Final_Draft the associated monitoring and the costs and the cross-media issues associated with the techniques. Chapter

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Best Available Techniques (BAT) Reference Document for the

Refining of Mineral Oil and Gas

Industrial Emissions Directive 2010/75/EU (Integrated Pollution Prevention and Control)

JOINT RESEARCH CENTRE Institute for Prospective Technological Studies Sustainable Production and Consumption Unit European IPPC Bureau

FINAL DRAFT (July 2013)

Picture: Slovnaft Bratislava, member of the MOL Group

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This document is one from the series of foreseen documents listed below (at the time of writing, not all documents have been drafted): Reference Document on Best Available Techniques Code

Ceramic Manufacturing Industry CER Common Waste Water and Waste Gas Treatment/Management Systems in the Chemical Sector CWW

Emissions from Storage EFS

Energy Efficiency ENE

Ferrous Metals Processing Industry FMP

Food, Drink and Milk Industries FDM

Industrial Cooling Systems ICS

Intensive Rearing of Poultry and Pigs IRPP

Iron and Steel Production IS

Large Combustion Plants LCP

Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers Industries LVIC-AAF

Large Volume Inorganic Chemicals – Solids and Others industry LVIC-S

Large Volume Organic Chemical Industry LVOC

Management of Tailings and Waste-rock in Mining Activities MTWR

Manufacture of Glass GLS

Manufacture of Organic Fine Chemicals OFC

Non Ferrous Metals Industries NFM

Production of Cement, Lime and Magnesium Oxide CLM

Production of Chlor-Alkali CAK

Production of Polymers POL

Production of Pulp, Paper and Board PP

Production of Speciality Inorganic Chemicals SIC

Refining of Mineral Oil and Gas REF

Slaughterhouses and Animals By-products Industries SA

Smitheries and Foundries Industry SF

Surface Treatment of Metals and Plastics STM

Surface Treatment Using Organic Solvents STS

Tanning of Hides and Skins TAN

Textiles Industry TXT

Waste Incineration WI

Waste Treatments Industries WT

Wood and Wood Products Preservation with Chemicals WPC

Wood-based Panels Production WBP

Reference Document

Economics and Cross-media Effects ECM

General Principles of Monitoring MON Electronic versions of draft and finalised documents are publicly available and can be downloaded from http: //eippcb.jrc.es

http://eippcb.jrc.es/

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Preface

PB/EIPPCB/REF_Final_Draft July 2013 iii

PREFACE 1. Status of this document

Unless otherwise stated, references to ‘the Directive’ in this document refer to Directive 2010/75/EU of the European Parliament and the Council on industrial emissions (integrated pollution prevention and control) (Recast).

This document is a working draft of the European IPPC Bureau (of the Commission’s Joint Research Centre). It is not an official publication of the European Union and does not necessarily reflect the position of the European Commission.

The original best available techniques (BAT) reference document (BREF) for the Refining of Mineral Oil and Gas (REF) was adopted by the European Commission in 2003. This document is the result of a review of that BREF. The review commenced in January 2008. This BAT reference document for the Refining of Mineral Oil and Gas forms part of a series presenting the results of an exchange of information between EU Member States, the industries concerned, non-governmental organisations promoting environmental protection and the Commission, to draw up, review, and where necessary, update BAT reference documents as required by Article 13(1) of the Directive. This document is published by the European Commission pursuant to Article 13(6) of the Directive. As set out in Article 13(5) of the Directive, the Commission Implementing Decision [yyyy/xx/EU] on the BAT conclusions contained in Chapter 5 was adopted on [date of decision] and published on [date of publication of decision in OJ + reference to OJ in footnote]1.

2. Participants in the information exchange As required in Article 13(3) of the Directive, the Commission has established a forum to assist the work, which is composed of representatives from Member States, the industries concerned and non-governmental organisations promoting environmental protection (Commission Decision of 16 May 2011 establishing a forum for the exchange of information pursuant to Article 13 of the Directive 2010/75/EU on industrial emissions (2011/C 146/03), OJ C 146, 17.05.2011, p. 3). Forum members have nominated technical experts constituting the technical working group (TWG) that was the main source of information for drafting this document. The work of the TWG was led by the European IPPC Bureau (of the Commission’s Joint Research Centre). 3. Structure and contents of this document Chapters 1 and 2 provide general information on the Refining of Mineral Oil and Gas and on the industrial processes and techniques used within this sector. Chapter 3 provides data and information concerning the environmental performance of installations within the sector in terms of current emissions, consumption and nature of raw materials, water consumption, use of energy and the generation of waste reflecting the situation in installations in operation at the time of writing. Chapter 4 describes in more detail the techniques to prevent or, where this is not practicable, to reduce the environmental impact of installations in this sector that were considered in determining the BAT This information includes, where relevant, the environmental performance levels (e.g. emission and consumption levels) which can be achieved by using the techniques,

1 OJ [series] [number], [dd.mm.yyyy], p. [starting page].

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the associated monitoring and the costs and the cross-media issues associated with the techniques. Chapter 5 presents the BAT conclusions as defined in Article 3(12) of the Directive. Chapter 6 presents information on 'emerging techniques’ as defined in Article 3(14) of the Directive. Concluding remarks and recommendations for future work are presented in Chapter 7. 4. Information sources and the derivation of BAT This document is based on information collected from a number of sources, in particular through the TWG that was established specifically for the exchange of information under Article 13 of the Directive. The information has been collated and assessed by the European IPPC Bureau (of the Commission's Joint Research Centre) who led the work on determining BAT, guided by the principles of technical expertise, transparency and neutrality. The work of the TWG and all other contributors is gratefully acknowledged. The BAT conclusions have been established through an iterative process involving the following steps: • identification of the key environmental issues for the sector; • examination of the techniques most relevant to address these key issues; • identification of the best environmental performance levels, on the basis of the available

data in the European Union and worldwide; • examination of the conditions under which these environmental performance levels were

achieved, such as costs, cross-media effects, and the main driving forces involved in the implementation of the techniques;

• selection of the best available techniques (BAT) their associated emission levels (and other environmental performance levels) and the associated monitoring for this sector according to Article 3(10) of and Annex III to the Directive.

Expert judgement by the European IPPC Bureau and the TWG has played a key role in each of these steps and in the way in which the information is presented here. Where available, economic data have been given together with the descriptions of the techniques presented in Chapter 4. These data give a rough indication of the magnitude of the costs and benefits. However, the actual costs and benefits of applying a technique may depend strongly on the specific situation of the installation concerned, which cannot be evaluated fully in this document. In the absence of data concerning costs, conclusions on the economic viability of techniques are drawn from observations on existing installations. 5. Review of BAT reference documents (BREFs)

BAT is a dynamic concept and so, the review of BREFs is a continuing process. For example, new measures and techniques may emerge, science and technologies are continuously developing and new or emerging processes are being successfully introduced into the industries. In order to reflect such changes and their consequences for BAT, this document will be periodically reviewed and, if necessary, updated accordingly.

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6. Contact information

All comments and suggestions should be made to the European IPPC Bureau at the Institute for Prospective Technological Studies at the following address: European Commission Institute for Prospective Technological Studies European IPPC Bureau Edificio Expo c/Inca Garcilaso, 3 E-41092 Seville, Spain Telephone: +34 95 4488 284 Fax: +34 95 4488 426 E-mail: [email protected]: http: //eippcb.jrc.ec.europa.eu

http://eippcb.jrc.ec.europa.eu/mailto:[email protected]

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July 2013 PB/EIPPCB/REF_Final_Draft vi

Reference Document on Best Available Techniques for the Refining of Mineral Oil and Gas

PREFACE ................................................................................................................................................ III SCOPE.........................................................................................................................................................1 1 GENERAL INFORMATION ...........................................................................................................1

1.1 The purpose of refineries ............................................................................................................1 1.2 Refinery sector in the EU ...........................................................................................................2

1.2.1 General .............................................................................................................................2 1.2.1.1 Oil refining ...............................................................................................................2 1.2.1.2 Natural gas refining ..................................................................................................3

1.2.2 Feedstock..........................................................................................................................3 1.2.2.1 Crude oil feedstock ...................................................................................................3 1.2.2.2 Biofuels feedstock growth ........................................................................................5 1.2.2.3 Natural gas feedstock................................................................................................8

1.2.3 Europe refining capacity...................................................................................................9 1.2.3.1 European oil refining capacity..................................................................................9 1.2.3.2 European natural gas refining capacity...................................................................10

1.2.4 Product market................................................................................................................14 1.2.4.1 Petroleum products .................................................................................................14 1.2.4.2 Natural gas..............................................................................................................17

1.3 European refineries...................................................................................................................19 1.3.1 Oil refineries...................................................................................................................19 1.3.2 Gas refineries..................................................................................................................19 1.3.3 Technical characteristics of European refineries ............................................................22 1.3.4 Employment in the European refinery sector .................................................................25

1.4 Main environmental issues in the refining sector .....................................................................26 1.4.1 Emissions to the atmosphere ..........................................................................................26 1.4.2 Emissions to water..........................................................................................................28 1.4.3 Waste generation ............................................................................................................30 1.4.4 Soil and groundwater contamination ..............................................................................32 1.4.5 Other environmental issues ............................................................................................32

2 APPLIED PROCESSES AND TECHNIQUES .............................................................................35 2.1 General overview of refinery processes....................................................................................36 2.2 Alkylation .................................................................................................................................40 2.3 Base oil production ...................................................................................................................43 2.4 Bitumen production ..................................................................................................................48 2.5 Catalytic cracking .....................................................................................................................50 2.6 Catalytic reforming...................................................................................................................54 2.7 Coking processes ......................................................................................................................57 2.8 Cooling systems........................................................................................................................60 2.9 Desalting...................................................................................................................................62 2.10 Energy system...........................................................................................................................64 2.11 Etherification ............................................................................................................................71 2.12 Gas separation processes ..........................................................................................................74 2.13 Hydrogen-consuming processes ...............................................................................................76 2.14 Hydrogen production ................................................................................................................86 2.15 Integrated refinery management ...............................................................................................90 2.16 Isomerisation ............................................................................................................................92 2.17 Natural gas plants .....................................................................................................................94 2.18 Polymerisation ..........................................................................................................................97 2.19 Primary distillation units...........................................................................................................99 2.20 Product treatments ..................................................................................................................102 2.21 Storage and handling of refinery materials .............................................................................105 2.22 Visbreaking and other thermal conversions............................................................................108

2.22.1 Visbreaking...................................................................................................................108 2.22.2 Thermal gas oil unit......................................................................................................109

2.23 New high conversion techniques ............................................................................................110 2.24 Techniques for the elimination and the valorisation of external waste used as a secondary raw

material ...................................................................................................................................111

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2.25 Techniques for the abatement of emissions............................................................................ 113 3 CURRENT EMISSION AND CONSUMPTION LEVELS ....................................................... 115

3.1 Current emission and consumption levels in refineries as a whole ........................................ 116 3.1.1 Present consumption levels in refineries ...................................................................... 117

3.1.1.1 Energy .................................................................................................................. 117 3.1.1.2 Water.................................................................................................................... 122

3.1.2 Emissions to air............................................................................................................ 125 3.1.2.1 Carbon dioxide emissions .................................................................................... 125 3.1.2.2 Nitrogen oxides emissions ................................................................................... 126 3.1.2.3 Particulate emissions ............................................................................................ 130 3.1.2.4 Sulphur oxides emissions ..................................................................................... 131 3.1.2.5 Volatile organic compounds emissions ................................................................ 139 3.1.2.6 Other emissions to air........................................................................................... 142 3.1.2.7 Expression of full or partial site air emissions using ‘bubbles’............................ 143

3.1.3 Emissions to water ....................................................................................................... 149 3.2 Alkylation............................................................................................................................... 156 3.3 Base oil production ................................................................................................................ 158

3.3.1 Deasphalting ................................................................................................................ 158 3.3.2 Aromatic extraction...................................................................................................... 158 3.3.3 High pressure hydrogenation unit ................................................................................ 159 3.3.4 Solvent dewaxing......................................................................................................... 159 3.3.5 Hydrofinishing ............................................................................................................. 160

3.4 Bitumen production................................................................................................................ 161 3.5 Catalytic cracking................................................................................................................... 162

3.5.1 Consumptions .............................................................................................................. 162 3.5.2 Emissions ..................................................................................................................... 162

3.5.2.1 Air emissions........................................................................................................ 162 3.5.2.2 Waste water emissions ......................................................................................... 168 3.5.2.3 Solid wastes.......................................................................................................... 168

3.6 Catalytic reforming ................................................................................................................ 169 3.7 Coking processes.................................................................................................................... 171 3.8 Cooling systems ..................................................................................................................... 173 3.9 Desalting ................................................................................................................................ 175 3.10 Energy system ........................................................................................................................ 177

3.10.1 Energy management..................................................................................................... 177 3.10.2 Energy capacity and consumptions .............................................................................. 178 3.10.3 Emissions ..................................................................................................................... 180

3.10.3.1 Air emissions........................................................................................................ 180 3.10.3.2 Waste water.......................................................................................................... 186 3.10.3.3 Solid wastes generated ......................................................................................... 187

3.11 Etherification.......................................................................................................................... 188 3.12 Gas separation processes........................................................................................................ 189 3.13 Hydrogen-consuming processes............................................................................................. 190

3.13.1 Hydrotreatments........................................................................................................... 190 3.13.2 Hydrocracking.............................................................................................................. 192

3.14 Hydrogen production ............................................................................................................. 194 3.15 Integrated refinery management............................................................................................. 197 3.16 Isomerisation.......................................................................................................................... 199 3.17 Natural gas plants................................................................................................................... 201 3.18 Polymerisation ....................................................................................................................... 204 3.19 Primary distillation units ........................................................................................................ 205 3.20 Product treatments.................................................................................................................. 207 3.21 Storage and handling of refinery materials ............................................................................ 209 3.22 Visbreaking and other thermal conversions ........................................................................... 212

3.22.1 Visbreaking .................................................................................................................. 212 3.22.2 Thermal gas oil units (TGU) ........................................................................................ 213

3.23 Emissions from waste gas treatment techniques .................................................................... 214 3.23.1 Sour gas treatments ...................................................................................................... 214 3.23.2 Sulphur recovery units (SRU)...................................................................................... 214 3.23.3 Flares............................................................................................................................ 215

3.24 Emissions from waste water treatment techniques................................................................. 217 3.25 Waste generation.................................................................................................................... 220

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3.26 Monitoring ..............................................................................................................................222 3.26.1 Monitoring of emissions to air......................................................................................222

3.26.1.1 Sulphur monitoring...............................................................................................223 3.26.1.2 Emissions from combustion processes .................................................................223 3.26.1.3 Diffuse VOC monitoring ......................................................................................224 3.26.1.4 Odour monitoring .................................................................................................233

3.26.1.4.1 Dynamic olfactometry with human assessors ...............................................234 3.26.1.4.2 Odour surveys by a committee of residents ..................................................235

3.26.2 Monitoring of releases to water ....................................................................................238 3.26.3 Monitoring solid wastes................................................................................................238 3.26.4 Soil and groundwater monitoring .................................................................................239

4 TECHNIQUES TO CONSIDER IN THE DETERMINATION OF BAT ................................240 4.1 General overview....................................................................................................................243 4.2 Alkylation ...............................................................................................................................244

4.2.1 Hydrofluoric acid alkylation process............................................................................244 4.2.2 Sulphuric acid alkylation process .................................................................................246 4.2.3 Upgrade feedstock by selective hydrogenation or isomerisation..................................248

4.3 Base oil production .................................................................................................................249 4.3.1 Multiple-effect extraction process ................................................................................249 4.3.2 Conversion of a solvent extraction unit (from Furfural or Phenol to NMP).................251 4.3.3 Solvent recovery from dewaxing units .........................................................................254 4.3.4 Wax reprocessing unit ..................................................................................................255 4.3.5 Storage and benchmarking of solvents .........................................................................256 4.3.6 Sulphur treatment from hydrogenation units ................................................................256 4.3.7 Stripping of waste water from aromatic extraction.......................................................257 4.3.8 Energy use and integration ...........................................................................................257 4.3.9 Catalytic processes based on hydrogenation ................................................................258 4.3.10 Improved solvent based plants with lower loss of containment ...................................258

4.4 Bitumen production ................................................................................................................260 4.4.1 Storage of bitumen products.........................................................................................260 4.4.2 Techniques to control emissions to the air....................................................................261

4.4.2.1 Treatment of the gaseous overheads .....................................................................261 4.4.2.2 Use the heat from incondensable products and condensates.................................261 4.4.2.3 Treatment of vents from the storage and handling of bitumen materials..............262 4.4.2.4 Sulphur dioxide abatement and sulphur recovery units ........................................262

4.4.3 Waste water pretreatment techniques ...........................................................................263 4.4.4 Hot oil system...............................................................................................................263

4.5 Catalytic cracking ...................................................................................................................264 4.5.1 Hydrotreatment of feed to the catalytic cracker............................................................264 4.5.2 Waste heat boiler and expander applied to the flue-gas from the FCC regenerator .....267 4.5.3 Catalyst selection..........................................................................................................269 4.5.4 Nitrogen oxides abatement techniques .........................................................................272

4.5.4.1 Selective catalytic reduction (SCR) ......................................................................272 4.5.4.2 Selective non-catalytic reduction (SNCR)............................................................276 4.5.4.3 Low-NOx CO oxidation promoters.......................................................................279 4.5.4.4 Specific additives for NOX reduction....................................................................281 4.5.4.5 Low-temperature oxidation (SNERT process/LoTOX technology) ......................285 4.5.4.6 Process optimisation .............................................................................................287

4.5.5 Particulate abatement techniques..................................................................................288 4.5.5.1 Third-stage cyclone separators .............................................................................288 4.5.5.2 Electrostatic precipitators (ESPs) .........................................................................290 4.5.5.3 Other filters...........................................................................................................296

4.5.6 Sulphur oxides abatement techniques...........................................................................298 4.5.6.1 SOx-reducing catalyst additives ............................................................................298 4.5.6.2 Wet scrubbing.......................................................................................................306 4.5.6.3 Dry and semi-dry scrubbers..................................................................................310 4.5.6.4 Seawater scrubbing...............................................................................................311

4.5.7 FCCU abatement techniques performances and emissions variability .........................312 4.5.8 Waste management techniques.....................................................................................317

4.6 Catalytic reforming.................................................................................................................318 4.6.1 Reduction and/or substitution of catalyst promoter (chlorine precursor) .....................318 4.6.2 Cleaning of the regeneration flue-gas...........................................................................318

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4.6.3 Electrostatic precipitator in the regeneration flue-gas.................................................. 319 4.6.4 Reduction of PCDD/F emissions from catalytic reforming ......................................... 319

4.7 Coking processes.................................................................................................................... 321 4.7.1 Techniques to prevent emissions from delayed coking................................................ 321 4.7.2 Techniques to prevent emissions from fluid coking .................................................... 322 4.7.3 Techniques to prevent emissions from the calcination process.................................... 323 4.7.4 Flexicoking .................................................................................................................. 326 4.7.5 Use of oily sludges and/or waste as coker feedstock ................................................... 327 4.7.6 Water use in the cooling/cutting process...................................................................... 328 4.7.7 Handling and storage of the coke................................................................................. 329 4.7.8 Techniques to reduce air emissions.............................................................................. 330

4.7.8.1 Particulate abatement in coking processes ........................................................... 330 4.7.8.2 SO2 abatement techniques .................................................................................... 331 4.7.8.3 NOx abatement techniques ................................................................................... 332 4.7.8.4 Cleaning of the coking gas ................................................................................... 332

4.7.9 Techniques to prevent emissions to water.................................................................... 333 4.7.9.1 Treatment of the waste water ............................................................................... 333 4.7.9.2 Separation of the oil/coke fines from the coke-cutting water............................... 333

4.7.10 Techniques to reduce soil contamination ..................................................................... 334 4.7.10.1 Control and reuse of coke fines............................................................................ 334

4.8 Cooling systems ..................................................................................................................... 335 4.8.1 Segregation of cooling and process waters .................................................................. 335 4.8.2 Air cooling ................................................................................................................... 336 4.8.3 Prevention of oil leakages into cooling water .............................................................. 336

4.9 Desalting ................................................................................................................................ 337 4.9.1 Good desalting practices .............................................................................................. 337 4.9.2 Enhance the oil/water separation before discharge to the waste water treatment plant 337 4.9.3 Enhance the solid/water-oil separation ........................................................................ 338 4.9.4 Reuse of water for the desalter..................................................................................... 339 4.9.5 Stripping of the desalter brine ...................................................................................... 340

4.10 Energy system ........................................................................................................................ 341 4.10.1 Energy management..................................................................................................... 342

4.10.1.1 Energy efficiency management ............................................................................ 342 4.10.1.1.1 Increasing energy efficiency ........................................................................ 342

4.10.1.2 Heat integration/recovery techniques ................................................................... 343 4.10.1.2.1 Design techniques ........................................................................................ 343 4.10.1.2.2 Process control and maintenance techniques................................................ 344

4.10.1.2.2.1 Steam Management and reduction of steam consumption .................. 344 4.10.1.2.2.2 Other techniques.................................................................................. 345

4.10.2 Refinery fuels: types and cleaning ............................................................................... 346 4.10.2.1 Increase the use of gas.......................................................................................... 346 4.10.2.2 Cleaning of refinery fuel gas ................................................................................ 351 4.10.2.3 Hydrotreatment of liquid refinery fuels................................................................ 352

4.10.3 Energy production techniques...................................................................................... 354 4.10.3.1 Furnaces and boilers............................................................................................. 354 4.10.3.2 Gas turbines.......................................................................................................... 357 4.10.3.3 Cogeneration plants (CHP) .................................................................................. 360 4.10.3.4 Gasification of heavy oils or coke (IGCC)........................................................... 361 4.10.3.5 Fluidised-bed boiler ............................................................................................. 362

4.10.4 Nitrogen oxide control and abatement techniques ....................................................... 363 4.10.4.1 Low-NOX burners and ultra-low-NOX burners .................................................... 363 4.10.4.2 Dry low-NOx combustors..................................................................................... 370 4.10.4.3 Flue-gas recirculation........................................................................................... 371 4.10.4.4 Diluent injection................................................................................................... 371 4.10.4.5 Fuel staging (reburning) ....................................................................................... 372 4.10.4.6 Selective non-catalytic reduction (SNCR) ........................................................... 373 4.10.4.7 Selective catalytic reduction (SCR) ..................................................................... 377 4.10.4.8 Low temperature oxidation .................................................................................. 380 4.10.4.9 Catalytic reduction of CO and NOx...................................................................... 381

4.10.5 Particulate abatement techniques ................................................................................. 384 4.10.5.1 Switching to low-ash content fuels ...................................................................... 384 4.10.5.2 Steam atomisation for liquid fuel ......................................................................... 384 4.10.5.3 Electrostatic precipitator (ESP)............................................................................ 384

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4.10.6 Sulphur oxides abatement techniques...........................................................................385 4.10.6.1 Additives to fuels..................................................................................................385 4.10.6.2 Flue-gas desulphurisation processes .....................................................................386

4.10.7 Combustion units abatement techniques performance and emissions variability.........387 4.11 Etherification ..........................................................................................................................393

4.11.1 Catalytic distillation......................................................................................................393 4.11.2 Prevention of upsets in the waste water biotreater........................................................393 4.11.3 Prevention of leaking of water-soluble compounds......................................................394

4.12 Gas separation processes ........................................................................................................395 4.12.1 Fugitive emissions reduction ........................................................................................395 4.12.2 Prevention of emissions of LPG odorant......................................................................395

4.13 Hydrogen-consuming processes .............................................................................................396 4.13.1 Hydrodesulphurisation processes .................................................................................396 4.13.2 Catalytic distillation......................................................................................................397 4.13.3 On-stream catalyst replacement technology for processing high-metal feeds ..............397 4.13.4 Hydrogenation of light dienes ......................................................................................398

4.14 Hydrogen production ..............................................................................................................399 4.14.1 Steam methane reforming.............................................................................................399 4.14.2 Gas Heated Reforming (GHR) .....................................................................................401 4.14.3 Partial oxidation............................................................................................................402 4.14.4 Purification of hydrogen...............................................................................................404

4.15 Integrated refinery management .............................................................................................405 4.15.1 Environmental management tools ................................................................................405

4.15.1.1 Environmental management system .....................................................................405 4.15.1.2 Energy conservation techniques ...........................................................................407

4.15.2 Production planning and control...................................................................................408 4.15.3 Safety management ......................................................................................................408 4.15.4 Water management .......................................................................................................408

4.15.4.1 Water stream integration (WSI)............................................................................408 4.15.4.2 Water and drainage system...................................................................................411 4.15.4.3 Rainwater..............................................................................................................413 4.15.4.4 Ballast water .........................................................................................................414 4.15.4.5 Firefighting water .................................................................................................414 4.15.4.6 Priority substance-driven management.................................................................414 4.15.4.7 Site-level management of air emissions: the 'bubble approach'............................416 4.15.4.8 Anticipation and adaptation to unfavourable meteorological conditions..............421

4.16 Isomerisation ..........................................................................................................................424 4.16.1 Active chloride promoted catalyst isomerisation process.............................................424 4.16.2 Zeolitic isomerisation process ......................................................................................424

4.17 Natural gas plants ...................................................................................................................426 4.17.1 Amine sweetening of natural gas..................................................................................426 4.17.2 Sulphur recovery unit ...................................................................................................427 4.17.3 Techniques to reduce VOC emissions ..........................................................................427 4.17.4 Techniques to reduce NOx emissions ...........................................................................427 4.17.5 Techniques to reduce water emissions..........................................................................427 4.17.6 Techniques to reduce waste generation ........................................................................428

4.18 Polymerisation ........................................................................................................................429 4.18.1 Reduction of emission and use of catalyst within the process ......................................429 4.18.2 Management and reuse of the catalyst..........................................................................430

4.19 Primary distillation units.........................................................................................................431 4.19.1 Progressive distillation unit ..........................................................................................431 4.19.2 Heat integration of crude distillation units ...................................................................433 4.19.3 Heat integration of the vacuum distillation units ..........................................................433 4.19.4 Use of vacuum pumps and surface condensers.............................................................434 4.19.5 Reduction of the vacuum pressure in the vacuum distillation unit ...............................435 4.19.6 Treatment of non-condensables from the vacuum ejector set condenser......................435 4.19.7 Waste water treatment and reuse ..................................................................................436 4.19.8 Other techniques to consider in the atmospheric units .................................................437

4.20 Product treatments ..................................................................................................................438 4.20.1 Cascading of caustic solutions......................................................................................438 4.20.2 Management of the spent caustic..................................................................................438 4.20.3 Replace clay filtration with hydrotreating ....................................................................440 4.20.4 Catalytic dewaxing .......................................................................................................441

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4.21 Storage and handling of materials .......................................................................................... 442 4.21.1 Underground caverns ................................................................................................... 442 4.21.2 Internal floating roof tanks........................................................................................... 442 4.21.3 Fixed-roof tanks ........................................................................................................... 444 4.21.4 External floating roofs ................................................................................................. 445 4.21.5 Pressurised vessels ....................................................................................................... 448 4.21.6 External floating roof seal systems .............................................................................. 448 4.21.7 Storage strategy............................................................................................................ 449 4.21.8 Prevention of leakage through tank bottoms................................................................ 450

4.21.8.1 Double bottoms tank ............................................................................................ 450 4.21.8.2 Impervious membrane liners ................................................................................ 451 4.21.8.3 Leak detection ...................................................................................................... 453 4.21.8.4 Cathodic protection .............................................................................................. 453

4.21.9 Tank farm bund containment ....................................................................................... 454 4.21.10 Reduction of the generation of tank bottoms ............................................................... 455 4.21.11 Tank cleaning procedures ............................................................................................ 455 4.21.12 Colour of tanks............................................................................................................. 457 4.21.13 Other good storage practices........................................................................................ 457 4.21.14 In-line blending............................................................................................................ 459 4.21.15 Batch blending ............................................................................................................. 460 4.21.16 Vapour balancing during loading processes................................................................. 460 4.21.17 Bottom loading measures............................................................................................. 461 4.21.18 Tightly sealed floors..................................................................................................... 461

4.22 Visbreaking and other thermal conversions ........................................................................... 462 4.22.1 Visbreaking .................................................................................................................. 462

4.22.1.1 Hydrovisbreaking................................................................................................. 462 4.22.1.2 Soaker visbreakers ............................................................................................... 462

4.22.2 Thermal gas oil unit (TGU).......................................................................................... 463 4.22.3 Sour gas and waste water management........................................................................ 463 4.22.4 Reduction of coke formation in visbreakers................................................................. 464

4.23 Waste gas minimisation and treatments ................................................................................. 465 4.23.1 CO-abatement techniques ............................................................................................ 465 4.23.2 CO2 emission control options ....................................................................................... 465 4.23.3 NOx-abatement techniques........................................................................................... 466

4.23.3.1 Low-temperature NOx oxidation .......................................................................... 466 4.23.3.2 Selective non-catalytic reduction (SNCR) ........................................................... 468 4.23.3.3 Selective catalytic reduction (SCR) ..................................................................... 469

4.23.4 Particulates................................................................................................................... 472 4.23.4.1 Cyclones............................................................................................................... 472 4.23.4.2 Electrostatic precipitator (ESP)............................................................................ 473 4.23.4.3 Filtration............................................................................................................... 474 4.23.4.4 Wet scrubbers....................................................................................................... 475 4.23.4.5 Other wet techniques............................................................................................ 476 4.23.4.6 Combination of particulate abatement techniques................................................ 476

4.23.5 Techniques for sulphur recovery and SO2 abatement .................................................. 477 4.23.5.1 Amine-treating ..................................................................................................... 478 4.23.5.2 Sulphur recovery units (SRU) .............................................................................. 481

4.23.5.2.1 Increased efficiency of the Claus Process .................................................... 481 4.23.5.2.2 Tail gas treatment units (TGTUs)................................................................. 485

4.23.5.2.2.1 Direct oxidation to sulphur .................................................................. 485 4.23.5.2.2.2 Continuation of the Claus reaction ...................................................... 485 4.23.5.2.2.3 Reduction to H2S and recovering sulphur from H2S ........................... 486 4.23.5.2.2.4 Oxidation to SO2 and recovery of sulphur from SO2........................... 487

4.23.5.2.3 Wet gas scrubbing of the SRU off-gas ......................................................... 494 4.23.5.2.4 Stored sulphur degassing.............................................................................. 495

4.23.5.3 Hydrogen sulphide and light mercaptan removal................................................. 496 4.23.5.4 Sulphur dioxide abatement techniques................................................................. 496 4.23.5.5 Sulphur recovery units performances and variability........................................... 504

4.23.6 VOC abatement techniques.......................................................................................... 507 4.23.6.1 Techniques for the prevention, detection and control of VOC fugitive emissions

.............................................................................................................................. 507 4.23.6.1.1 Techniques to prevent/reduce VOC emissions related to the process and plant

design ........................................................................................................... 507

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4.23.6.1.2 Techniques to prevent/reduce VOC emissions related to plant installation and commissioning ..............................................................................................509

4.23.6.1.3 Programme for the prevention, detection and control of VOC fugitive emissions.......................................................................................................510

4.23.6.2 Vapour recovery units (VRU)...............................................................................512 4.23.6.3 Vapour destruction (VD) ......................................................................................522

4.23.7 Flares ............................................................................................................................524 4.23.8 The SNOx combined technique to abate air pollutants .................................................530 4.23.9 Odour pollution preventing and control techniques......................................................534

4.24 Waste water treatments...........................................................................................................536 4.24.1 Management of waste water within a refinery..............................................................539 4.24.2 Sour water stripping (SWS)..........................................................................................540 4.24.3 Reduction and recovery of hydrocarbons from waste water at source .........................544 4.24.4 Primary treatment - Removal of insoluble substances..................................................545

4.24.4.1 Step 1 – Oil removal .............................................................................................546 4.24.4.2 Step 2 - Further oil/water/solid separation............................................................548 4.24.4.3 Step 3 – Biological treatment................................................................................550

4.24.5 Additional treatments ...................................................................................................555 4.24.6 Global refinery waste water treatments performance ...................................................556 4.24.7 Reduction of odours .....................................................................................................571

4.24.7.1 Reduction of odours from WWTP........................................................................571 4.24.7.2 Reduction of odours from water buffer tanks .......................................................572

4.25 Waste management.................................................................................................................574 4.25.1 Establishment of a waste management programme......................................................574 4.25.2 Sludge management and treatment ...............................................................................575 4.25.3 Spent solid catalyst management..................................................................................577

4.25.3.1 Control and reuse of the catalyst fines..................................................................579 4.25.3.2 Removal of catalyst from slurry decant oil...........................................................579

4.25.4 Recycling and re-using waste .......................................................................................580 4.25.4.1 Treatment of heavy residues .................................................................................580 4.25.4.2 Improving the recovery of oils from oily sludges.................................................581 4.25.4.3 Regenerate or eliminate filtration clay..................................................................581 4.25.4.4 Reprocessing off-specification products...............................................................581 4.25.4.5 Recycle/Reuse outside the installation..................................................................581 4.25.4.6 Reuse of waste lubes.............................................................................................582 4.25.4.7 Recycle lab samples..............................................................................................582

4.25.5 Biodegradation of wastes..............................................................................................582 4.25.6 Waste storage................................................................................................................583

5 BEST AVAILABLE TECHNIQUES (BAT) CONCLUSIONS..................................................585 Definitions ............................................................................................................................................586 General considerations..........................................................................................................................588 Averaging periods and reference conditions for emissions to air .........................................................588 Conversion of emissions concentration to reference oxygen level .......................................................588 Reference conditions for emissions to water ........................................................................................589 Averaging periods for emissions to water.............................................................................................589 5.1 General BAT conclusions for the refining of mineral oil and gas ..........................................590

5.1.1 Environmental management systems ...........................................................................590 5.1.2 Energy efficiency..........................................................................................................591 5.1.3 Solid materials storage and handling ............................................................................591 5.1.4 Monitoring of emissions to air and key process parameters .........................................592 5.1.5 Operation of waste gas treatment systems....................................................................593 5.1.6 Monitoring of emissions to water .................................................................................594 5.1.7 Emissions to water........................................................................................................595 5.1.8 Waste generation and management ..............................................................................597 5.1.9 Noise.............................................................................................................................597 5.1.10 BAT conclusions for integrated refinery management .................................................598

5.2 BAT conclusions for alkylation process .................................................................................599 5.2.1 Hydrofluoric acid alkylation process............................................................................599 5.2.2 Sulphuric acid alkylation process .................................................................................599

5.3 BAT conclusions for base oil production process ..................................................................600 5.4 BAT conclusions for the bitumen production process............................................................600 5.5 BAT conclusions for the fluid catalytic cracking process ......................................................601

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5.6 BAT conclusions for the catalytic reforming process ............................................................ 606 5.7 BAT conclusions for the coking process................................................................................ 607 5.8 BAT conclusions for the desalting process ............................................................................ 609 5.9 BAT conclusions for the combustion units ............................................................................ 610 5.10 BAT conclusions for the etherification process ..................................................................... 616 5.11 BAT conclusions for the isomerisation process ..................................................................... 616 5.12 BAT conclusions for the natural gas refinery......................................................................... 616 5.13 BAT conclusions for the distillation process.......................................................................... 617 5.14 BAT conclusions for the products treatment process............................................................. 617 5.15 BAT conclusions for storage and handling processes ............................................................ 618 5.16 BAT conclusions for visbreaking and other thermal processes.............................................. 619 5.17 BAT conclusions for waste gas sulphur treatment ................................................................. 620 5.18 BAT conclusions for flares .................................................................................................... 621 5.19 Description of techniques for the prevention and control of emissions to air ........................ 622

5.19.1 Dust .............................................................................................................................. 622 5.19.2 Nitrogen oxides (NOX)................................................................................................. 623 5.19.3 Sulphur oxides (SOX)................................................................................................... 624 5.19.4 Carbone monoxide (CO) .............................................................................................. 625 5.19.5 Combined air pollutants emissions prevention and control ......................................... 626 5.19.6 Volatile organic compound (VOC) emissions prevention and control ........................ 626 5.19.7 Other air emissions prevention and control.................................................................. 628

5.20 Description of techniques for prevention and control of emissions to water ......................... 629 5.20.1 Waste water pre-treatment ........................................................................................... 629 5.20.2 Waste water treatment.................................................................................................. 629

5.21 Description of techniques for the prevention of waste generation and the management of waste................................................................................................................................................ 629

6 EMERGING TECHNIQUES ....................................................................................................... 630 6.1 Refinery activities overview................................................................................................... 630 6.2 Alkylation............................................................................................................................... 631

6.2.1 Alkylation of parafines................................................................................................. 631 6.2.1.1 Sulphuric acid process.......................................................................................... 631 6.2.1.2 Hydrofluric acid (HF) process.............................................................................. 631 6.2.1.3 Solid-acid technology........................................................................................... 631 6.2.1.4 Ionic liquids (IL) .................................................................................................. 635

6.2.2 Alkylation aiming to reduce benzene content in gasoline............................................ 635 6.3 Base oil production ................................................................................................................ 636 6.4 Catalytic cracking................................................................................................................... 636 6.5 Catalytic reforming ................................................................................................................ 636 6.6 Coking.................................................................................................................................... 636 6.7 Energy system ........................................................................................................................ 636 6.8 Etherification.......................................................................................................................... 636 6.9 Hydrogen production ............................................................................................................. 637 6.10 Hydrogen-consuming processes............................................................................................. 637 6.11 Hydrocracking........................................................................................................................ 638 6.12 Isomerisation.......................................................................................................................... 639 6.13 Primary distillation................................................................................................................. 640 6.14 Product treatments.................................................................................................................. 640 6.15 Waste gas treatments.............................................................................................................. 640 6.16 Waste water treatment............................................................................................................ 642

7 CONCLUDING REMARKS AND RECOMMENDATIONS FOR FUTURE WORK .......... 643 8 REFERENCES .............................................................................................................................. 647 GLOSSARY............................................................................................................................................ 657

8.1 ISO country codes .................................................................................................................. 657 8.2 Monetary units ....................................................................................................................... 658 8.3 Unit prefixes........................................................................................................................... 658 8.4 Units ....................................................................................................................................... 659 8.5 Chemical elements ................................................................................................................. 660 8.6 Chemical formulae commonly used in this document ........................................................... 661 8.7 Acronyms and technical definitions ....................................................................................... 662

9 ANNEXES ...................................................................................................................................... 667

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9.1 Refinery configurations ..........................................................................................................667 9.1.1 Configuration 1: hydroskimming + isomerisation unit.................................................668 9.1.2 Configuration 2: catalytic cracker configuration ..........................................................669 9.1.3 Configuration 3: hydrocracker configuration ...............................................................670 9.1.4 Configuration 4: complex refinery with hydroconversion and IGCC ..........................671

9.2 Refinery feedstock, intermediates and products .....................................................................673 9.2.1 Crude oil .......................................................................................................................673 9.2.2 Refinery intermediates and products ............................................................................675

9.3 Cost effectiveness of implementation of some techniques .....................................................678 9.3.1 Basic concepts for cost effectiveness analysis..............................................................678 9.3.2 Basic hypothesis and assumptions used in the REF BREF for economics...................678

9.4 Description of zeolites ............................................................................................................679 9.5 Soil and groundwater monitoring – An example ....................................................................680 9.6 Air emissions –The 'Bubble approach': a methodology..........................................................685

9.6.1 APPENDIX A ON ‘GOOD PRACTICES’ FOR THE IDENTIFICATION AND MAPPING OF ALL INCLUDED SOURCES .............................................................687

9.6.2 APPENDIX B ON VOLUMETRIC GAS ESTIMATION...........................................688 9.6.3 APPENDIX C ON MASS/LOAD EMISSION ESTIMATION...................................699 9.6.4 APPENDIX D BUBBLE MONITORING ...................................................................701

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List of figures Figure 1.1: Refinery sulphur balance trend up to 2010 ............................................................................ 5 Figure 1.2: Percentage of biofuel blend (Source: Biodiesel EurObserv’er) ............................................. 5 Figure 1.3: World bioethanol fuel production.......................................................................................... 7 Figure 1.4: World biodiesel fuel production (European Biodiesel Board, EU Barometer, Biofuels

Global Potentials 2007) ......................................................................................................... 7 Figure 1.5: Global oil refining throughputs............................................................................................ 10 Figure 1.6: Major gasoline and diesel trade to and from the EU............................................................ 15 Figure 1.7: Geographical distribution of the European refineries .......................................................... 20 Figure 1.8: Capacity of the various processes in the EU-27 refineries (O&GJ 2011)............................ 24 Figure 1.9: Nelson complexity index dispersion for some European refineries per country ................. 25 Figure 1.10 Distribution of refineries in the EU+ according Nelson complexity index.......................... 25 Figure 2.1: General scheme of a complex oil refinery ........................................................................... 38 Figure 2.2: Simplified process flow scheme for a HF alkylation unit.................................................... 41 Figure 2.3: Simplified process flow scheme for sulphuric acid alkylation ............................................ 42 Figure 2.4: Block scheme of a lubricating oil manufacturing plant with a combination of process

options units......................................................................................................................... 45 Figure 2.5: Simplified process flow scheme of a bitumen blowing unit ................................................ 49 Figure 2.6: Simplified process flow scheme for a fluid catalytic cracker .............................................. 53 Figure 2.7: Simplified process flow scheme for a continuous catalytic reformer .................................. 55 Figure 2.8: Simplified process flow scheme for a delayed coking unit.................................................. 58 Figure 2.9: Simplified process flow scheme for a flexicoker................................................................. 59 Figure 2.10: Simplified diagrams of the cooling systems used in refineries............................................ 60 Figure 2.11: Simplified flow diagram of a crude desalter........................................................................ 63 Figure 2.12: Simplified flow diagram of a fuel gas system...................................................................... 65 Figure 2.13: Simplified flow diagram of a heavy fuel oil system ............................................................ 66 Figure 2.14: Block flow scheme for an IGCC process............................................................................. 68 Figure 2.15: Typical layout of a boiler feed water preparation unit and a steam boiler ........................... 70 Figure 2.16: Simplified process flow scheme of a MTBE production process ........................................ 72 Figure 2.17: Simplified process flow scheme of TAME production........................................................ 73 Figure 2.18: Simplified process flow scheme for a part of a gas plant .................................................... 74 Figure 2.19: Simplified process flow scheme of a distillate hydrodesulphurisation unit ......................... 80 Figure 2.20: Simplified process flow scheme of a hydrocracker (single stage with recycling) ............... 83 Figure 2.21: Simplified process flow scheme of a hydroconversion process (moving bed) .................... 85 Figure 2.22: The four main steps of H2 production by steam methane reforming ................................... 87 Figure 2.23: Simplified process flow scheme of an isomerisation unit.................................................... 92 Figure 2.24: General block diagram of a natural gas plant ...................................................................... 95 Figure 2.25: Condensate separation in a natural gas plant ....................................................................... 96 Figure 2.26: Gas dehydration in a natural gas plant ................................................................................. 96 Figure 2.27: Simplified scheme of a polymerisation unit ........................................................................ 97 Figure 2.28: Simplified process flow diagram of a crude distillation unit ............................................. 100 Figure 2.29: Simplified process flow scheme of a high vacuum distillation unit .................................. 101 Figure 2.30: Simplified process flow diagram of the mercaptan oxidation extraction process.............. 103 Figure 2.31: Simplified process flow diagram of the caustic cascading system (mercaptan oxidation

extraction and sweetening) ................................................................................................ 104 Figure 2.32: Examples of some types of storage tanks .......................................................................... 106 Figure 2.33: Simplified process flow scheme for a visbreaking unit ..................................................... 109 Figure 2.34: Simplified process of a thermal gas oil unit....................................................................... 109 Figure 3.1: Example of specific emissions and consumptions in European refineries......................... 118 Figure 3.2: Estimated primary energy consumption distributed by refining process in the US ........... 119 Figure 3.3: Specific energy consumption compared to CO2 emissions and site complexity for a sample

of EU refineries ................................................................................................................. 121 Figure 3.4: Use of gaseous fuels and emitted part of sulphur input for a sample of EU refineries sorted

by ascending order of specific energy consumption .......................................................... 121 Figure 3.5: Specific water usage data for a selection of European refineries....................................... 122 Figure 3.6: Water specific consumption breakdown for a sample of European refineries................... 125 Figure 3.7: Respective weights of the main NOx-contributing processes for 12 European refineries not

operating an FCC unit as a function of their specific emissions (g/t of feed) .................... 127 Figure 3.8: Respective weights of the main NOx-contributing processes for 24 European refineries

operating an FCC unit as a function of their specific emissions (g/t of feed) .................... 127

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Figure 3.9: Influence of the configuration, complexity and specific energy consumption on NOxemissions ............................................................................................................................128

Figure 3.10: Influence of the gaseous fuels used for energy supply on the site NOx emissions .............129 Figure 3.11: Average sulphur output distribution from a sample of European refineries.......................132 Figure 3.12: Respective weight of main SO2 contributing processes for 12 European refineries not

operating a FCC unit as a function of their sulphur emitted/input ratio .............................137 Figure 3.13: Respective weight of main SO2 contributing processes for 24 European refineries operating

an FCC as a function of their sulphur emitted/input ratio ..................................................137 Figure 3.14: Influence of the configuration, complexity and crude quality on SO2 emissions...............138 Figure 3.15: Influence of the gaseous fuels used for energy supply on the site SO2 emissions..............139 Figure 3.16: VOC specific emission range and breakdown for 39 European refineries.........................141 Figure 3.17: Equivalent concentration of the NOx emissions from the whole energy system, FCC and

SRU units of 24 European refineries..................................................................................146 Figure 3.18: Equivalent concentration of the NOx emissions from the whole energy system and the FCC

unit of 30 European refineries ............................................................................................146 Figure 3.19: Equivalent concentration of the SO2 emissions from the whole energy system and the FCC

and SRU unit of 30 European refineries.............................................................................147 Figure 3.20: Distribution of COD emissions for a sample of 36 European refineries ............................154 Figure 3.21: Distribution of BOD5 emissions for a sample of 29 European refineries...........................154 Figure 3.22: Distribution of TOC emissions for a sample of 21 European refineries ............................154 Figure 3.23: Distribution of suspended solid emissions for a sample of 34 European refineries ...........155 Figure 3.24: Distribution of annual average concentrations of nitrogen compound discharges for a

sample of 26 European refineries.......................................................................................155 Figure 3.25: Distribution of specific emissions of nitrogen compounds for a sample of 27 European

refineries.............................................................................................................................155 Figure 3.26: NOx yearly average concentration from a sample of 21 European FCC units ...................165 Figure 3.27: PM yearly average concentration from a sample of 20 European FCC units.....................166 Figure 3.28: SO2 yearly average concentrations from a sample of European FCC units ......................167 Figure 3.29: Energy Intensity Index and specific energy consumption for 41 EU refineries .................178 Figure 3.30: Sulphur and nitrogen contents in HFO (vacuum residues) according to their geographical

origin ..................................................................................................................................180 Figure 3.31: Large combustion plants in refineries 2009 reporting of Member States to the Commission

............................................................................................................................................182 Figure 3.32 Emissions to air from LCP in refineries: loads and associated concentrations ..................182 Figure 3.33: Distribution of NOx yearly average equivalent concentrations from the energy system of a

sample of European refineries............................................................................................184 Figure 3.34: Distribution of SO2 yearly average equivalent concentrations from the energy system of a

sample of European refineries............................................................................................186 Figure 3.35: Petroleum coke commercial process ..................................................................................195 Figure 3.36: Sulphur recovery yield range of SRUs operated in a sample of 47 European sites............215 Figure 3.37: Leak concentration measurement .......................................................................................226 Figure 3.38: Bagging of a leaking valve .................................................................................................226 Figure 3.39: An OGI videocamera .........................................................................................................227 Figure 3.40: Typical visualisation of gas leak ........................................................................................227 Figure 3.41: Scheme of the DIAL process..............................................................................................227 Figure 3.42: Typical DIAL concentration map obtained with DIAL measuring system........................229 Figure 3.43: Overall shape of alkane emissions from an oil refinery as measured with SOF ................230 Figure 3.44: Detection of high leaking storages within a refinery tank farm using SOF........................230 Figure 3.45: References used in a methodology for odour profile identification ...................................236 Figure 3.46: Olfactory profile of the ExxonMobil refinery in Port Jérôme (France) .............................237 Figure 4.1: Evolution of the feed S content and SO2 emissions after FCC feed hydrotreatment..........265 Figure 4.2: Monthly average SO2 emissions after FCC feed hydrotreatment.......................................266 Figure 4.3: Waste heat boiler and expander applied to the regenerator flue-gas of a catalytic cracker 268