Presentation on theme: "Fundamentals of Petrochemicals"— Presentation transcript:
1 Fundamentals of Petrochemicals Presented by Umar Raja th May 2011NOTES:
2 Introduction Mr Umar Raja, Principal Process Engineer Umar has over 20 years experience in developing concept and detail design with an ability to see them through start-up, operations and operations management.The goal of today's workshop is to quickly and effectively bring you up to speed with the language, concepts and key issues in the petrochemical industry. It has been designed for managers, engineers, graduates, operators and other personnel who are new or are requiring insight into the Refining and Petrochemicals industry.The workshop will provide an excellent overview for people from technical, non-technical and commercial backgrounds, who have limited experience and wish to improve their familiarity with some of the systems and technologies involved.NOTES:
3 Summary Chemical Industry Oil Refineries & Petrochemical Refineries Feed Stocks & ProductsBasic Building Block ChemicalsProcess Flow ConfigurationHands-on Session - Constructing simplified flow-schemesMajor Processes: Separation, Reaction, Equipment and EnvironmentThe Petrochem business?Role of EngineersChallenges in the Chemical IndustryWhere can I get more informationWorkshop Summary & QuestionsNOTES:
4 The Chemical IndustryChemical products made from gas and crude oil (~70000 products)End products include plastics, soaps, detergents, solvents, paints, drugs, fertilizer, pesticides, explosives, synthetic textile fibres and rubbers, flooring and insulating materials and much more.The largest petrochemical manufacturing industries are to be found in the United States, Western Europe, Asia and the Middle East.In 2007, 2,980 operating plants worldwide10 Million direct employees, 50 million indirect employeesAnnual growth rate 2.4 %. Global enterprise valued at $2.2 Trillion …… and growing!NOTES:
6 Petrochemical Refinery THE PURPOSE OF A PETROCHEM REFINERY IS TO TRANSFORM RELATIVELY LOW VALUE PRODUCTS FROM OIL REFINERY INTO HIGH VALUE PRODUCTS AS EFFICIENTLY, PROFITABLY AND ENVIRONMENTALLY SOUND A WAY AS POSSIBLENOTES:
10 Basic Building BlocksThe term ‘aromatics’ is typically used to describeBenzeneTolueneXylenesThese are commonly referred to as BTX aromatics and are produced in a refinery or petrochemicals complexThe term ‘olefins’ is used to describe molecules with a C double bondEthylenePropyleneButenes or ButadieneThese are commonly referred to as light olefins and are also produced in a refinery or petrochemicals complexOlefins and aromatics are very high-value productsPrices have reached over 1,000 $ / tonne for Paraxylene and benzene Ethylene and propylene. Compared to naphtha at 40-60% of this valueNOTES:
11 Basic Building Blocks- Aromatics Benzene, C6H6 , colourless and highly flammable liquidCarcinogen, additive in gasoline now limitedBuilding block for over 250 productse.g.. Ethyl benzene (for styrene), Cumene (for phenol), CyclohexaneNOTES:
13 Basic Building Blocks- Aromatics Toluene (Methylbenzene), C7H8 or C6H5CH3, is a clear, water-insoluble liquidProduces benzene and xylenesToluene for toluene diisocyanate (TDI), manufactures polyurethaneProduces phenol, caprolactam, nitrobenzene, benzoic acid .Octane booster in gasoline50% produces benzene and xylenes, 25% in solvents and 10% in the TDI. Around 15% of demand is by gasoline.NOTES:
14 Basic Building Blocks- Aromatics Paraxylene (p-Xylene), C8H10, is colourless and a flammable liquidIsomers are O-xylene and M-xyleneOne of the fastest growing petrochemicalsp-Xylene is used for PTA, DMT and PET for polyesterHigh purity needed for polymerisation processNOTES:
16 Basic Building Blocks - Olefins Ethylene, C2H4, is a gaseous organic compoundSimplest Olefin Chemical feedstockMost produced organic compound90% used to produce three chemical compoundsethylene oxideethylene dichlorideethylbenzenepolyethyleneNOTES:
18 Basic Building Blocks - Olefins LDPE produces containers, dispensing bottles, tubing, plastic bags. Other products made from it include:Food storage and laboratory containersParts that require flexibility, for which it serves very wellParts of computer hardware, such as hard disk drives, screen cards, and optical disc drivesNOTES:
19 Basic Building Blocks - Olefins HDPE is resistant to solvents and has a wide variety of applications, including:Plastic lumberFolding tables/chairsStorage shedsChemical-resistant piping systemsWater pipes, for domestic water supplyRefillable bottlesBottle CapsNOTES:
20 Basic Building Blocks - Olefins Butadiene, C4H6Main intermediate for polymer productionProduct of steam crackingLight feeds, give primarily ethylene and heavier feeds form heavier olefins, butadiene, and aromatic hydrocarbons.Most butadiene is used in styrene-butadiene rubber (BDR) production for the tyre industry (~28%)Other polymers include Polybutadiene (PB), styrene-butadiene latex (SBL), acrylonitrile-butadiene-styrene (ABS)NOTES:
21 Basic Building Blocks - Olefins shoe heels and soles, gaskets and even chewing gum.NOTES:Musical instruments golf club heads (due to its good shock absorbance), automotive trim components, automotive bumper bars, enclosures for electrical and electronic assemblies, protective headgear, whitewater canoes, buffer edging for furniture and joinery panels, luggage, small kitchen appliances, and toys, eg. Lego bricks
22 Basic Building Blocks - Olefins Propylene, C3H6Converts to acetone and phenol via the cumene processProduces isopropanol (propan-2-ol), acrylonitrile.Separated by distillation from hydrocarbon mixtures.Products include plastic items for medical/laboratory, kettles, food containers, clear bags and ropes.NOTES:
24 Major Processes – Aromatics Complex & Naphtha Cracker • Catalytic reformer for aromatics̶ Feeds are heavy naphtha̶ % yield of aromatics̶ Up to 5% benzene, more in dedicated ‘benzene reformers’• Steam cracker for olefins̶ Feeds are ethane, propane, C4s, naphtha̶ % yield of olefins, 2–13% yield of BTXToluene0 KtaParaxylene1400 KtaBenzene932 KtaAromaticsComplexHeavy Aromatics26 KtaMedium/HeavyNaphtha2923 KtaTail Gas85 KtaPropylene720 KtaDeC5’d Pygas440 KtaNaphthaCrackerEthylene1440 KtaC2/C3 Cut KtaLPG KtaL.t Naphtha 308 KtaButene 154 KtaLight Naphtha3489 KtaNOTES:MTBE185 KtaH2 92 KtaH2 35 KtaButadiene200 KtaH2 Export 127 Kta
25 Aromatics Complex - Overview The following processes recover aromatic compounds from mixtureDistillationExtractionPurificationThe following processes convert lower-value aromatics into higher value aromaticsXylene isomerisationToluene conversionC9+ aromatics conversionNOTES:
26 Aromatics Complex - Overview Distillation won’t separate aromatics from non-aromatics due to the similar boiling pointsAromatic are extracted from non-aromatic using eitherSolvent extraction (liquid-liquid extraction)Extractive distillationHybrid extraction (combination of the two)Purification of paraxylene from other C8 aromatics when not achieved by distillation uses following two techniquesCrystallisation exploits wide differences in freezing pointsAdsorption exploits differences in molecular shapesNOTES:
27 Aromatics Complex - Production Processes NOTES:
28 UDEX Process (UOP Dow Extraction) Aromatics Complex - Production ProcessesCatalytic Reformer Operation with high catalyst activity to increase reformate aromatic yields from 50% to 75%UDEX Process (UOP Dow Extraction)Aromatic rich feed with solvent removes non Aromatics in raffinate stream and aromatics in extract stream.SulfolaneTM Process similar to the UDEX but uses internal recycle streams to enhance separation and aromatic recoverySulfolane by Shell Oil Company in the early 1960s is still the most efficient solvent available for the recovery of aromatics.NOTES:
30 Aromatics Complex - Chemical Transformations Toluene conversion into xylenes or benzene can be classified into 3 categories depending on the feed:100% toluene feedToluene together with C9 and heavier aromaticsToluene plus methanolToluene Hydrodemethylation to convert toluene to benzeneHighly exothermic, hydrogen atmosphere to suppress coke formationDemethylation of occurs at about 650°F and 82bargNOTES:
31 Aromatics Complex - Chemical Transformations Toluene hydro de-alkylationToluene methylation: Toluene and methanol+benzeneCH4H2+P-xyleneH2OCH3OHNOTES:
32 Aromatics Complex - Chemical Transformations NOTES:
33 Aromatics Complex - Chemical Transformations Toluene Disproportionation to convert toluene to benzene and xylene2 moles of toluene into 1 mole of benzene and 1 mole of xyleneCatalyst transfers methyl group from one methylbenzene ring to another methylbenzene ringExpensive than hydrodemethylation.Involves hydrogen as reaction mixture is equilibrium limited.2+Mixed xyleneBenzeneNOTES:
34 Aromatics Complex - Chemical Transformations NOTES:
35 Aromatics Complex - Chemical Transformations Process in which mixed C8 aromatics depleted in paraxylene are isomerised to produce more paraxyleneThere are two types of xylene isomerisationEthylbenzene (EB) isomerisationEthylbenzene (EB) dealkylationThe reaction path is dependent on catalyst usedC2H5H2Mixed xylenesC2H5NOTES:+ C2H6+ H2Benzene
36 Aromatics Complex - Chemical Transformations Xylene Isomerisation ProcessFeed and hydrogen are preheated to reaction temperatureIsomerisation reactor is a fixed bed down flow vessel operating at temperatures of 450C and 31bargDeheptanizer separates isomerised product as the bottoms streamNOTES:
37 Aromatics Complex – Selective Adsorption Parex process to separate Paraxylene from Xylene mixturesIsomers boil closely and conventional distillation is not practical.Parex process simulates a moving bed of adsorbentSeparation takes place in the adsorbent chambers.99.9 wt-% pure para-xylene at 97 wt-% recovery per passNOTES:
38 Naphtha Steam Cracking – olefins The feedstock is heated to the point that the energy transfer from heat is enough to ’crack’ the molecule into two or more smaller molecules.High heat inputMixture HC and steam passed through tubes inside a furnaceVery Short Residence Time <1sRapid Quench of reaction followed by distillation.50-80% yield of olefins, 2–13% yield of BTXNOTES:
40 Hands on SessionThe petrochemicals may be olefins or their precursors, or various types of ________ petrochemicals.2) An ________ _______ is a combination of process units which are used to convert _________, from a variety of sources, and ___________ into the basic petrochemical intermediates: ______, ______, and ______.3) Aromatics can be produced from variety of different feedstocks, including ______, _______, ________, and ___________.4) Fill in the missing components for polystyrene production_____________________________PolystyreneNOTES:
41 Fill in the missing process link Hands on SessionFill in the missing process linkTraditional _________ won’t separate aromatics from non-aromatics due to _____ _____ ______. Aromatic components can be extracted from non-aromatic components using ____ _____ or _______ _______.The two processes used to purify paraxylene from other C8 aromatics are ___________ and ___________._____________ exploits wide differences in freezing points and adsorption exploits differences in _________ ___________.Toluene via ____________ or __________with C9-aromatics can produce _____ and an equilibrium mixture of xylenes.?Naphtha(80-110 C)Ethylene, propylene,Butenes & butadieneNOTES:
42 O-xylene / M-xylene separation Hands on SessionFill in the missing processes and components for the aromatic complex block flow below:??Gas?TolueneTADPSeparation?C9 AromaticsO-xylene / M-xylene separation???NOTES:?MetaxyleneIsomerisationO- xylene
43 Hands on SessionThe petrochemicals may be olefins or their precursors, or various types of ________ petrochemicals.2) An ________ _______ is a combination of process units which are used to convert _________, from a variety of sources, and ___________ into the basic petrochemical intermediates: ______, ______, and ______.3) Aromatics can be produced from variety of different feedstocks, including ______, _______, ________, and ___________.4) Fill in the missing components for polystyrene productionAromaticAromaticsComplexNaphthaPy GasBenzeneTolueneXyleneNaphthaLPGCondensatePy Gas_____________________________PolystyreneNOTES:BenzeneEthylbenzeneStyreneEthylene
44 extraction distillation Hands on SessionFill in the missing process linkTraditional _________ won’t separate aromatics from non-aromatics due to _____ _________. Aromatic components can be extracted from non-aromatic components using ____ _____ or _______ _______.The two processes used to purify paraxylene from other C8 aromatics are ___________ and ___________._____________ exploits wide differences in freezing points and adsorption exploits differences in _______________.Toluene via _____________ or ___________with C9-aromatics can produce _______and an equilibrium mixture of xylenes.Naphtha(80-110 C)crackingEthylene, propylene,Butenes & butadienedistillationsimilarboiling pointssolvent extractionextraction distillationcrystallisationadsorptioncrystallisationmolecularshapesNOTES:disproportionationtransalkylationbenzene
45 Hands on SessionFill in the missing processes and components for the aromatic complex block flow below:naphthaBenzeneGasBenzene Toluene SeparationTolueneTADPSeparationHydrotreatingC9 AromaticsO-xylene / M-xylene separationParaxylene SeparationReformerP-xyleneNOTES:MetaxyleneIsomerisationO- xyleneOrthoxylene Separation
46 - Metabolic Processes in Living Organisms Reaction and ReactorReaction- Process leading to transformation of one set of chemical substances to another.Reactor- Confines within which reaction occurs.Principal is not just confined to industrial reactors; but;- Metabolic Processes in Living Organisms- Atmospheric Chemistry.
47 Ideal, Batch and Flow Reactor Ideal Reactor- has uniform temperature, pressure and composition.- In practice reactor temperature, pressure and composition are not uniform.Batch Reactor- Where reactor mass is not exchanged with surroundingsFlow Reactor- Where reactor mass is exchanged with surroundings.
48 Adiabatic and Isothermal Reactor Adiabatic Reactor- Where Reactor does not exchange heat with surrounding. Isothermal Reactor- Where Reactor has good contact with surrounding but held at constant temperature (in both time and position within reactor).
49 CSTR or MFRCSTR or MFR Continuous Flow Stirred Tank Reactor OR Mixed Flow Reactor. Reaction occurs at constant pressure, constant temperature; and composition inside reactor is assumed to be that of effluent.
50 Tubular ReactorIdeal Tubular or Plug Flow ReactorReactor operating isothermally and at constant pressure and at steady-state with unique residence time. Fluid fills the tube and moves like a plug down the length of the tube. Fluid properties are uniform over cross-section normal to direction of flow.
51 Industrial ReactionWhat is expected from a Reaction?Product of ChoiceWhat is a Catalyst?- Substance that enhances reaction without being consumed
53 Reaction and CatalystHow long should a reaction take?Fast to be economicalWhat is Economical?Good value in relation to money, time andeffortAmmonia is a cheap commodity, so catalyst must be cheap and durable! Lasts longer and produces 2000 times its value.
54 Industrial ReactionIf conversion is less what comes to mind?How to dramatically improve it?What are the factors?- Catalysts- ThermodynamicsWhich of above is a primary Consideration?- Thermo is Primary- Catalyst is Secondary
55 Elementary and Stoichiometric Reaction H2+Br2 2HBr KineticsIdentification of ReactionElementary and Stoichiometric ReactionH2+Br2 2HBrMulti-step arrangement in Network (sequence/intermediates)Br+H2 → HBr + HH+Br2 → HBr + BrBreak or Make a single chemical bond. Must be written the way it takes place.
56 Petrochemical Refinery environmental impacts on Water: Environment - WaterPetrochemical Refinery environmental impacts on Water:process wastewater from desalting, distillation, cracking, and reforming operationsabout 24% of total emissions is released to wastewaterlarge quantities of cooling waterNOTES:
57 Petrochemical Refinery environmental impacts on Air: Environment - AirPetrochemical Refinery environmental impacts on Air:volatile hydrocarbons from crude oilSOx from crude oil and process heatNOx and particulates from process heatH2S from sulfur recovery operationsabout 75% of total emissions by weight are released to airNOTES:
58 Environment – Waste & Global Warming Solid WastePetrochemical plants generate significant amounts of solid waste and sludge , some of which is hazardous because of organics and heavy metals.Contribution to Global warmingenergy-intensive operationmost of the energy is consumed as process heatthus, little prospect for replacement of process energy by renewable or non-CO2-intensive sourcesOf great concern are accidental discharges as a result of abnormal operation.NOTES:
59 Environment - Minimising Pollution Operate Furnaces EfficientlyWaste Material to FlareAvoiding Spills and Accidental ReleasesWater TreatmentNOTES:
60 Petrochemical Business Price and quality of feedstock and products is constantly changing.Government regulations add additional constraints.Not much differential between price of feedstock’s and products.HOW DO I KEEP IN BUSINESS?NOTES:
61 I NEED ENGINEERS! Petrochemical Business I need to design and revamp the plant utilizing the latest technology to be more efficientI need to make the plant more flexible and responsiveI need to operate (control) the plant in the most efficient manner possibleI need to keep the equipment running all the timeI NEED ENGINEERS!NOTES:
62 Operations & Maintenance Engineers Control Systems Engineer Role of EngineersOperations & Maintenance EngineersControl Systems EngineerDesign EngineerHealth & SafetyEnvironmental ImpactsPlanning & SchedulingReliability EngineerPlant ManagerNOTES:
63 Chemical Industry- The Challenges Feedstock availability and increasing costEnvironmental controls e.g. increasing constraints on emissionsEnergy SavingsProcess EfficiencyCatalyst DevelopmentIncreasing demand for productsNOTES:
65 Workshop SummaryPresented only some of the main processes in petrochemicals, others downstream are polymers, plastics, fibres and resins is extensive.A petrochemical refinery is made up of a combination of highly integrated processes such as distillation, extraction, and various separation operations.Olefins and aromatics are the building blocks for a wide range of materials and productsAromatic complexes is a general term for a combination of process units that produce the three basic chemicalsCrackers convert feed-stocks into ethylene, propylene, butane, butadiene via cracking. NOTES:
66 Further Information Books: Speight, James. G , Chemical Process and Design HandbookJohn Wiley & Sons , Wiley Critical Content - Petroleum Technology, Volume 1-2Chenier, P. 2002, Survey of Industrial Chemistry, Third EditionInternet: Google Search, Online Books, ArticlesNOTES:
68 Summary Keywords –Language, Concept, Key Issues Petrochemicals- Petrochemical Refineries are a combination of highly integrated processes involving Reaction, Separation; and ExtractionAromatics Complex- A combination of Process units that converts Naphtha and Pygas into basic chemical intermediates. Simplest configuration produces Benzene, Toluene and Xylene.Basic Building Block Chemicals.Process Flow ConfigurationHands-on Session - Constructing simplified flow-schemesMajor Processes: Separation, Reaction, Equipment and EnvironmentThe Petrochem business?Role of EngineersChallenges in the Chemical IndustryWhere can I get more informationWorkshop Summary & QuestionsNOTES: