1. Overview of the gas and oil industry
Professor Antal Tungler
2004

2. 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

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

4. 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%

5. Constituents of petroleum
Alkanes
Naphtenes
Aromatics

6. 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

7. 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

10. 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.

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

12. 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

13. 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

14. Occurences

15. Production and reserves

16. Production and reserves

17. 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

18. 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.

19. Estimated proved crude oil reserves in the world (A)

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

22. 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%

23. 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

27. Oil price of today:

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

31. 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.

32. 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

33. The oil, gas and water distribution in a pore

34. Oil recovery efficiency

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

36. History of drilling

37. 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

38. 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

39. Key deep offshore technologies

40. Deep Offshore Production Records

41. 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.

42. 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

43. 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.

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

45. Oil production engineering

46. 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

47. Natural gas production engineering

48. 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

49. Sour gas well

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

51. Dehydration and cooling of natural gas

52. Hydrocarbon removal from natural gas

53. Physical-chemical scrubbing of natural gas

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

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

56. Complete natural gas treating plant

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

60. Underground storage facility for natural gas

61. European natural gas pipelines

62. 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.

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

64. 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

65. 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

67. Process units in integrated refineries

68. Crude oils and products

69. Sulfur content of crude oils

70. Refining processes: distillation
Task: separation

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

74. Viscosity breaking

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

76. Hydrodesulfurisation of gas oil
Task: decreasing sulfur content

77. Hydrotreating of pyrolysis gasoline
Task: stabilising the product, desulfurisation

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

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

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

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

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

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

89. Integrated refinery structures
Hydroskimming

90. Integrated refinery structures
Catalytic cracking--visbreaking

91. Integrated refinery structures
Hydrocracking—catalytic cracking

92. Integrated refinery structures
Hydrocracking--coking

93. Yield structures of refinery conversion schemes for Arabian light crude processing

94. 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 !!!)

95. 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)

101. Energy consumption in refineries

104. 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.

105. 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

106. 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.

107. 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.

110. 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.

111. Emission free loading of gasoline

112. Reduction of hydrocarbon emission

113. 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

114. 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

115. Example of specific emissions and consumptions found in European refineries

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

117. 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

118. 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.

119. 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.

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

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

123. 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.

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

125. 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

126. 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

127. 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

128. Emission-free loading and unloading of gasoline

129. Route of liquid hydrocarbons from the well to the consumer

130. Reduction of hydrocarbon emission during refuelling

131. Alternative fuels

134. 7. Automotive exhaust gas purification catalysts
Otto engines
Diesel engines

135. Reactions and products in the engine and in the catalytic converter

136. Reactions and products in the catalytic converter

139. Development of automotive catalysts

141. Hydrocarbon trap

142. Working of the electrically heated catalyst

147. Oxygen storage in three way catalysts

148. 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.

149. 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

152. 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.

153. Non-desirable reaction:
The catalytic reactions are:

154. Diesel particulate trap with burner

155. Catalytic particulate trap

156. 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.