Overview of the gas and oil industry Professor Antal Tungler 2004

Topics of the module Exploration of gas and oil Oil refining Origin, Exploration, Reservoir Engineering, Forecasts, Deep Drilling and Production Engineering Composition and Classification of Crude Oil and Natural Gas Transportation and Storage of Crude Oil and Natural Gas Oil refining Crude oil distillation Chemical conversion processes in refineries Integrated refinery structures Environmental protection in refineries Modern fuels, high-tech lubricants, utilisation of refinery products, alternative fuels Automotive exhaust gas purification catalysts, hybrid drive, fuel cells

1. Exploration of gas and oil Occurence, composition, origin, reserves, exploration, recovery, production engineering of oil and gas, natural gas purification, LPG

Definition Crude oil is the name given to all organic compounds which are liquid under reservoir conditions. Petroleum composition: - hydrocarbons -S, O, N, P compounds -metal compounds (V, Ni, Cu, Co, Mo, Pb, Cr, As) H2S and water Elementary composition: C 79,5-88,5%, H 10-15,5%

Constituents of petroleum Alkanes Naphtenes Aromatics

Classification of crude oils Paraffin based -found in deeper zones Naphtene or asphalt based –found in upper level Mixed-based –found in middle zones Composition on worldwide basis: ~30% paraffins, 40% naphtenes, 25% aromatics

Natural Gas Dry and wet natural gases Components: methane, higher hydrocarbons, nitrogen, carbondioxid, hydrogen sulfide, helium Associated gas, closely connected to crude oil Natural gas---non-associated

Formation of crude oil predominantly of organic origin Petroleum source rock-deposits in sedimentary basin contain organic residues of terrestrial, limnic, fluvial and marine origin-conversion under anaerobic conditions-resulting in bitumen or kerogen Source rock should contain 0,5% TOC Anoxic zones: nonmarine lakess (lake Tanganyika), closed inland seas with positive water balance (Black Sea deep zones), ascent of marine current from greater depths (Benguela current Africa, Humboldt current, Peru), open ocean (global climatic warming with large transgressions in Jurassic and middle Cretaceous period) Crude oil formation from phytoplankton, bacteria-in the Silurian—Devonian period Formation: organic material in sapropels is decomposed, decayed by anaerobic bacteria, organic material adsorbed onto fine clay particles, which sink to the sea floor. Sedimentation condition in Pliocene were similar to that of novadays in the offshore regions of the sea.

Hydrocarbon formation Diagenesis, Catagenesis, (at depths of 1000-5000 m and 175 oC) Metagenesis

Migration of oil droplets from argillaceous source rocks into porous reservoir rocks Lateral migration through capillary paths Vertical migration- fine fissures During migration occurs separation from water, gravitational separation: gas-oil-water Chemical degradation leads to smaller and more stable compounds Maturation process concludes with the conversion to methane

Reservoir rocks and trap structures Fluvial sand, Beach and barrier sand, Wind-blown sand, Marine platform sand Deep water sand, Reefs, Reef limestone debris, Chalk

Occurences

Production and reserves

Production and reserves

Oil exploration preliminary exploration, exploratory wells Geological exploration Satellite images Examination of rock samples Stratigraphic investigations Geophysical investigation Magnetic measurements Gravimetric measurements Geoelectric measurements Seismic methods Refraction Reflection methods 3D method Geochemical investigation Exploratory drilling

The entire exploration-to-production chain was reviewed and adapted to greater water depths: The development and use of (3D) seismic was intensified. Innovative drilling and production structures were designed. Because these structures could not be installed on the seabed at such great depths, FPSO (Floating Production Storage and Offloading) and TLP (Tension Leg Platform) systems were developed. Efforts were made to come up with new materials for the flexibles (able to withstand high pressures at great water depths, etc.). Horizontal and multibranch wells came into general use, reducing the number of wells.

Estimated proved crude oil reserves in the world (A)

Liquid petroleum consumed in the United States during the past 50 years came from three sources

Main parameters for Conventional oil Measurement Measure Produced-to-date 873 Gb Reserves 928 Discovered-to-date 1801 Yet-to-Find 149 Yet-to-Produce 1077 Ultimate recovery 1950 Current consumption (2001) 22 Gb/y Current discovery rate 6 Gb/y Current depletion rate (ann. prod. as % of Yet-to-Produce) 2%

Peak Oil. It truly is a turning point for mankind Conventional oil - and that will be defined - provides most of the oil produced today, and is responsible for about 95% all oil that has been produced so far. It will continue to dominate supply for a long time to come. It is what matters most. Its discovery peaked in the 1960s. We now find one barrel for every four we consume. Middle East share of production is set to rise. The rest of the world peaked in 1997, and is therefore in terminal decline. Non-conventional oil delays peak only a few years, but will ameliorate the subsequent decline. Gas, which is less depleted than oil, will likely peak around 2020. Capacity limits were breached late in 2000, causing prices to soar leading to world recession. The recession may be permanent because any recovery would lead to new oil demand until the limits were again breached which would lead to new price shocks re-imposing recession in a vicious circle. World peak may prove to have been passed in 2000, if demand is curtailed by recession. Prices may remain weak in such circumstances but since demand is not infinitely elastic they must again rise from supply constraints when essential needs are affected

Oil price of today:

Crude Oil, Gasoline and Natural Gas Futures Prices for August 23, 2004 NYMEX Light Sweet Crude -0.67 $47.46.05 IPE Brent -0.51 $43.03 Gasoline NY Harbor -0.0098 $1.2575 Heating Oil NY Harbor -0.0149 $1.2147 NYMEX Natural Gas -0.242 $5.310

Conclusion about reserves Peak oil is a turning point for Mankind, when a hundred years of easy growth ends. The population may be about to peak too for not unrelated reasons. The transition to decline is a period of great tension when priorities shift to self-sufficiency and sustainability. It may end up a better world, freed from the widespread gross excesses of to-day.

Reservoir engineering Porosity Physical properties of the pore saturating fluids: density, compressibility, viscosity Reserves = Resources x Recovery factor Multiphase flow Recovery factors: microscopic, areal, vertical

The oil, gas and water distribution in a pore

Oil recovery efficiency

Modeling of reservoir and production performance Material balances method Reservoir simulation Steady-state flow Unsteady-state flow Decline curve methods: exponential, harmonic, hyperbolic

History of drilling

Deep drilling engineering Rotary drilling Drilling tools: roller bit Drilling mud: thixotropic liquid, contains additives, like bentonite, cellulose, emulsifiers, inhibitors, density is between 1.1 and 1.4 g/cm3 Horizontal drilling with active steering

Mining drilling method Externally and internally smooth drill pipe Greater drilling progress Geophysical borehole measurements: electrical methods, sonic measurements, radioactivity measurements, determination of geophysical fields Productivity tests before casing, short in duration because unstable borehole Samples from the reservoir content, chemical and physical studies

Key deep offshore technologies

Deep Offshore Production Records

Casing and cementation Several concentric strings of casing pipes installed according to geological and engineering requirements partly during drilling. Casing is cemented Loads on casing: Differential pressure Radial component of the formation stress Tensile strength from own weight Bending stress, especially in horizontal holes Thermal stresses Tubing string with packers transports the fluid produced to the surface Cementing Massive bond of casing and formation Isolation of permeable formation Corrosion protection Cement + water + additives = slurry pumped through the borehole into the annulus between casing and formation, at elevated temperatures retarders and antifriction agents must be added.

Production engineering The purpose of the exploitation and production planning of hydrocarbon reservoir is to produce optimum amount of sealable products at minimum cost and with close attention to all aspects of safety and ecology Problems in oil production: Time of water injection, adjust the pressure Dependence of the productivity index on viscosity of the oil and water cut Gas production and availability in the gas lift method Advantages and disadvantages of the artificial lift methods In gas production: Occurence of toxic and problematic substances Heterogeneous multilayer and selective water incursion Avoiding blowouts

General production engineering Completion, Setting up production Wellhead, casing, cementing, tubing strings,bottom hole completion: „wireline equipment”. Two types: open-hole completion, casing on top of producing formation Perforation tubing-coupled perforating, it is a controlled explosion Well and reservoir treatment Well treatment Obstruction can be caused: solids from the mud, water block, swelling of the clay, chemical precipitation, emulsification. Obstructions can be removed by acid treatment (HCl or HF, surfactant) Reservoir bed treatment: pressure acidizing, hydraulic fracturing, injection of oil, water or acid together with viscosity enhancing agent, proppant (fluvial sand) Workover Workover hoist, wireline technique, coiled tubing, diameter 2,54-5,08cm, used at a depth of up to 5500m Horizontal wells: open hole, open hole with slotted or prepacked liner, slotted liner with external casing packers in the open hole, cemented and perforated liner.

Oil production engineering Flowing production Gas lift Centrifugal pumps Piston pumps, sucker rod or hydraulic

Oil production engineering

Collection and treatment of crude oil Gas separation Dewatering and desalting Emulsion breaking: early feeding of demulsifier, moderate heating, separation in a tank Special problems in crude oil production Paraffin precipitation Chemical precipitates Sand: safe production rate, filters, consolidation by resins Corrosion

Natural gas production engineering

Special requirements in natural gas production High pressures and pressure differences Extreme temperature differences Aggressive gas constituents Gastight tubing, special sealing materials Controlled and monitored production Safety at the surface, underground safety valves Deep storage reservoirs

Sour gas well

Treatment of natural gas Sulfur removal Removal of mercury Dehydration Removal of hydrocarbons Removal of carbondioxid and sulfur components

Dehydration and cooling of natural gas

Hydrocarbon removal from natural gas

Physical-chemical scrubbing of natural gas

Liqiud oxidation process Absorption of hydrogensufide Oxidation to sulfur Reoxidation of active component with air Separation of elementary sulfur

Activated charcoal, zeolites Membrane separation of impurities Adsorption processes Activated charcoal, zeolites

Complete natural gas treating plant

Liqiud Natural Gas Liquefied natural gas on low temperature: -160oC Pretreat the gas Refrigeration Storage Transportation: tankers

Underground storage facility for natural gas

European natural gas pipelines

Trans-Alaska pipeline south of Delta Junction Trans-Alaska pipeline south of Delta Junction. The pipeline extends 800 miles from Prudhoe Bay to Valdez. Alaska Range is in the background.

2. Oil refining Purposes, history, crude oils and products, refining processes, integrated refinery structures, environmental protection,

Oil refining: Purposes Fuels for cars, trucks, aeroplanes, ships and other forms of transport Combustion fuels for the energy industry and for households Raw materials for the petrochemical and chemical industry Speciality products, lubricating oils, waxes, bitumen Energy as by-product, heat, electricity

Oil refining History First purpose-drilled oil well 1859 Pennsylvania Continuous distillation 1875 Baku 20th century--- increased demand on gasoline 1920s Thermal cracking 1930s Houdry catalytic cracking 1940s Pt catalysed reforming Desulfurisation 1960s FCC with zeolites Residue conversion technologies

Process units in integrated refineries

Crude oils and products

Sulfur content of crude oils

Refining processes: distillation Task: separation

Task: lowering molecular weight and boiling point Catalytic cracking Task: lowering molecular weight and boiling point

Viscosity breaking

Gasoline hydrotreater Catalyst composition: Co Mo Ni W Active form: sulfided Task: eliminating sufur content

Hydrodesulfurisation of gas oil Task: decreasing sulfur content

Hydrotreating of pyrolysis gasoline Task: stabilising the product, desulfurisation

Catalytic reforming Tasks: increase octane number, production of aromatics Catalyst: Pt on alumina (alloyed with Sn)

Catalytic reforming Reactions during catalytic reforming: Dehydrogenation Dehydrocyclisation Dehydroisomerisation Hydrocracking Isomerisation

Hydrocracking Task: produce better quality distillates Catalysts: Co-Mo, Ni-W, sulfided

Residue conversion processes Task: increase the yield of high value products „H-in” and „C-out” processes

Delayed coking (Dunai Finomító) In most advanced refinery structures: hydroprocessing + [ coking, deasphalting, hydrocracking ] + partial oxidation

Gasoline upgrading processes Task: producing better fuel, high octane number, no health risk, environmentally more friendly Processes: alkylation, polymerisation, isomerisation

Integrated refinery structures Hydroskimming

Integrated refinery structures Catalytic cracking--visbreaking

Integrated refinery structures Hydrocracking—catalytic cracking

Integrated refinery structures Hydrocracking--coking

Yield structures of refinery conversion schemes for Arabian light crude processing

Environmental protection in the oil and gas industry Emissions to the atmosphere, to groundwater, to soil, to the sea Emission during exploration, production, manufacturing, storage and transportation (enormous trasportation distances and quantities !!!)

Main air pollutants emitted by a refinery Sources CO2 Process furnaces, boilers, gas turbines, FCC regenerators, CO boilers, flare systems, incinerators CO Process furnaces, boilers, FCC regenerators, CO boilers, flare systems, incinerators, sulfur recovery units NOx Process furnaces, boilers, gas turbines, FCC regenerators, CO boilers, flare systems, incinerators, coke calciners Particulates includig metals Process furnaces, boilers, gas turbines, FCC regenerators, CO boilers, cke plants, incinerators Sulfur oxides Process furnaces, boilers, gas turbines, FCC regenerators, CO boilers, flare systems, incinerators, sulfur recovery units VOCs Storage and handling facilities, flare systems, gas separation units, oil/water separation units, fugitive emissions (valves, flanges)

Energy consumption in refineries

Article 2(11) goes on to clarify further this definition as follows: The term ‘best available techniques’ BAT is defined in Article 2(11) of the Directive as “the most effective and advanced stage in the development of activities and their methods of operation which indicate the practical suitability of particular techniques for providing in principle the basis for emission limit values designed to prevent and, where that is not practicable, generally to reduce emissions and the impact on the environment as a whole.” Article 2(11) goes on to clarify further this definition as follows: · “techniques” includes both the technology used and the way in which the installation is designed, built, maintained, operated and decommissioned; · “available” techniques are those developed on a scale which allows implementation in the relevant industrial sector, under economically and technically viable conditions, taking into consideration the costs and advantages, whether or not the techniques are used or produced inside the Member State in question, as long as they are reasonably accessible to the operator; · “best” means most effective in achieving a high general level of protection of the environment as a whole.

Techniques to consider in the determination of BAT Close to 600 techniques have been considered in the determination of BAT. Those techniques have been analysed following a consistent scheme. That analysis is reported for each technique with a brief description, the environmental benefits, the cross-media effects, the operational data, the applicability and economics. BREF document for each industrial sector. Amongst the many environmental issues addressed in the BREF, the five that are dealt with below are probably the most important: · increase the energy efficiency · reduce the nitrogen oxide emissions · reduce the sulphur oxide emissions · reduce the volatile organic compounds emissions · reduce the contamination of water

The bubble concept usually refers to air emissions of SO2, but can also be applied to NOx, dust, CO and metals (Ni, V). The bubble concept is a regulatory tool applied in several EU countries. As represented in the picture, the bubble approach for emissions to air reflects a “virtual single stack” for the whole refinery.

Establishing associated emission values in the bubble concept If the bubble concept is to be used as an instrument to enforce the application of BAT in the refinery, then the emission values defined in the refinery bubble should be such that they indeed reflect BAT performance for the refinery as a whole. The most important notion is then to: identify the total fuel use of the refinery; assess the contribution of each of the fuels to the total fuel consumption of the refinery; quantify the emissions from process units implicated in such emissions (e.g. FCC, SRU); review the applicability of BAT to each of these fuels and/or the process units combine this information with the technical and economical constraints in using these techniques.

Good housekeeping/management techniques/tools. BAT is to: implement and adhere to an Environmental Management System (EMS). A good EMS could include: The preparation and publication of an annual environmental performance report. A report will also enable the dissemination of performance improvements to others, and will be a vehicle for information exchange. External verifications may enhance the credibility of the report. The delivery to stakeholders on an annual basis of an environmental performance improvement plan. Continuous improvement is assured by such a plan. The practice of benchmarking on a continuous basis, including energy efficiency and energy conservation activities, emissions to air (SO2, NOx, VOC, and particulates), discharges to water and generation of waste. Benchmarking for energy efficiency should involve an internal system of energy efficiency improvements, or intra- and inter-company energy efficiency benchmarking exercises, aiming for continuous improvements and learning lessons. An annual report of the mass balance data on sulphur input and output via emissions and products (including low-grade and off-spec products and further use and fate). Improve stability of unit operation by applying advanced process control and limiting plant upsets, thereby minimising times with elevated emissions (e.g. shutdowns and startups) Apply good practices for maintenance and cleaning. Implement environmental awareness and include it in training programmes. Implement a monitoring system that allows adequate processing and emission control.

Emission free loading of gasoline

Reduction of hydrocarbon emission

Water pollution During exploration and production under sea level Transportation on waterways Refineries: process water, steam, wash water, cooling water, rain water from production areas, from non-process areas Water pollutants: oil, H2S, NH3, organic chemicals, phenols, CN-, suspended solids

Oily sludges and materials Spent catalysts, other materials Waste generation Oily sludges and materials Spent catalysts, other materials Drums and containers Spent chemicals Mixed wastes

Example of specific emissions and consumptions found in European refineries

3. Modern fuels Gasoline, diesel oil, kerosene, alternative fuels, storage and transportation

Modern fuels: gasoline Otto engines Four-stroke: Intake of fuel-air mixture Compression of the mixture and timed ignition Combustion and expansion (working stroke) Exhaust of combustion gases

Modern fuels: gas oil Diesel engine The fuel-air mixture is heterogeneous, the ignition is thermal Fuel is injected into the heated air shortly before the end of the compression stroke, where it self-ignites.

Quality of gasoline Octane number Determination in comparative measurement, n-heptane has 0 octane number, 2,2,4-trimethyl pentane(iso-octane) has 100 octane number. Measurement in a one-cylinder, four-stroke test engine, it has a mechanically adjustable compression ratio. The compression ratio is increased until „knocking” occurs. The fuel’s octane number is coming from the composition of the n-heptane-iso-octane mixture, which gives the same knock level.

Quality of gasoline Volatility: balanced distillation performance Benzene content Aromatic content Sulfur content

Gasoline components Straight-run gasoline Thermally cracked gasoline Catalytically cracked gasoline Catalytic reformate Isomerizate Alkylate Polymer gasoline Oxygenates (MTBE, ETBE)

Quality of Diesel fuels (gas oil) Ignition quality Cetane number Determination in comparative measurement, methyl-naphtalene has 0 cetane number, cetane(n-hexadecane) has 100 cetane number. Measurement in a one-cylinder, four-stroke test engine, ignition delay can be altered, varying the compression ratio or throttling the qantity of intake air.

Quality of Diesel fuels (gas oil) Density Sulfur content Viscosity Deposit formation Cold flow properties (summer and winter gas oils)

Diesel fuel components Straight-run middle distillate Thermally cracked gas oil Catalytically cracked gas oil Hydrocracked gas oil Synthetic diesel fuel: SMDS (Shell Middle Distillate Synthesis) from natural gas through steam reforming, Fischer-Tropsch synthesis, isomerization, distillation

Fuel additives Gasoline additives Antiknock agents: lead compounds Antioxidants: amines and phenols Metal deactivators Corrosion inhibitors Anti-icing agents Detergents: avoiding deposits on injectors, ensure intake valve cleanliness Additives for combatting combustion chamber deposits Spark aider additives Additives for diesel fuel Ignition improvers (formation of free radicals upon decomposition) Detergent additives Soot suppressors-combustion enhancers Cold-flow additives (avoid wax crystallization) Flow improvers (EVA copolymers) Cloud point depressants Wax antisettling additives Additives for improving lubricity Additives for increasing storage stability Dehazers Biocides Antistatic additives Antifoam additives Reodorants

Fuel standardization and testing DIN and ASTM testing methods Storage and transportation Storage: floating and fixed-roof tanks Transportation: pipelines, tank ships, rail tankers, road tank trucks

Emission-free loading and unloading of gasoline

Route of liquid hydrocarbons from the well to the consumer

Reduction of hydrocarbon emission during refuelling

Alternative fuels

7. Automotive exhaust gas purification catalysts Otto engines Diesel engines

Reactions and products in the engine and in the catalytic converter

Reactions and products in the catalytic converter

Development of automotive catalysts

Hydrocarbon trap

Working of the electrically heated catalyst

Oxygen storage in three way catalysts

New oxygen storage material: ACZ alumina between cerium and zirconium oxide The diffusion barrier concept for ACZ compared with CZ. (a) ACZ: the sintering of CZ is inhibited by Al2O3 particles dispersed among CZ particles; (b) CZ: sinter easily without any dispersal.

The TWC catalyst is not effective in reducing NOx when the engine is operated lean of the stoichiometric air to fuel ratio (λ > 1). Lean operation Fuel reach operation Only for <1 s

Decreasing of sulfur poisoning Combination of TiO2 and -Al2O3 to minimize the amount of SOx deposition, hexagonal cell monolithic substrate to enhance the removal of sulfate, Rh/ZrO2-added catalyst has high activity of hydrogen generation via steam reforming. Photographs of wash-coat layer on square-cell (left) and hexagonal-cell (right) monolithic substrate.

Non-desirable reaction: The catalytic reactions are:

Diesel particulate trap with burner

Catalytic particulate trap

Hybrid driving Gasoline engine - The hybrid car has a gasoline engine much like the one you will find on most cars. However, the engine on a hybrid is smaller and uses advanced technologies to reduce emissions and increase efficiency. Fuel tank - The fuel tank in a hybrid is the energy storage device for the gasoline engine. Gasoline has a much higher energy density than batteries do. For example, it takes about 1,000 pounds of batteries to store as much energy as 1 gallon (7 pounds) of gasoline. Electric motor - The electric motor on a hybrid car is very sophisticated. Advanced electronics allow it to act as a motor as well as a generator. For example, when it needs to, it can draw energy from the batteries to accelerate the car. But acting as a generator, it can slow the car down and return energy to the batteries. Generator - The generator is similar to an electric motor, but it acts only to produce electrical power. It is used mostly on series hybrids. Batteries - The batteries in a hybrid car are the energy storage device for the electric motor. Unlike the gasoline in the fuel tank, which can only power the gasoline engine, the electric motor on a hybrid car can put energy into the batteries as well as draw energy from them. Transmission - The transmission on a hybrid car performs the same basic function as the transmission on a conventional car. Some hybrids, like the Honda Insight, have conventional transmissions. Others, like the Toyota Prius, have radically different ones.