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Package 2. Oil refining Refineries, Oil Refining Processes, Crude Oil Distillation Chemical Conversion Processes of Crude Oil Distillates Catalytic Cracking Hydrodesulphurisation Hydrotreating Isomerisation Reforming Hydrocracking Residue Conversion Processes Gasoline Upgrading

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Package 2

Oil refining

Refineries, Oil Refining Processes, Crude Oil Distillation

Chemical Conversion Processes of Crude Oil Distillates

Catalytic Cracking

Hydrodesulphurisation

Hydrotreating

Isomerisation

Reforming

Hydrocracking

Residue Conversion Processes

Gasoline Upgrading

Integrated Refinery Structures

Environmental Protection in Refineries, BAT (Best Available Technique) and BREF (BAT Reference Documents) of Refineries


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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


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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


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Process units in integrated refineries


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Crude oils and products


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Sulfur content of crude oils


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Refining processes: distillation

Task: separation

a) Crude desalter;

b) Crude heater;

c) Main fractionator;

d) Overhead accumulator;

e) Kerosene stripper;

f ) Light gas oil stripper;

g) Heavy gas oil stripper;

h) Vacuum heater;

i) Vacuum flasher


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a) Reactor; b) Stripper;

c) Regenerator; d) Riser; e1) Regenerator standpipe; e2) Stripper standpipe;

f) Cyclone vessel; g) Air blower; h) Flue gas expander; i) Waste-heat boiler;

j) Fractionator; k) Absorber;

l) Debutanizer; m) Depropanizer

Catalytic cracking

Task: lowering molecular weight and boiling point


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Viscosity breaking


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Gasoline hydrotreater

Catalyst composition:

Co Mo Ni W

Active form: sulfided

Task: eliminating sufur content

a) Process heater; b) Reactor; c) High-pressure separator; d) Low-pressure separator; e) Stabilizer; f ) Gasoline splitter


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Hydrodesulfurisation of gas oil

a) Process heater; b) Reactor; c) High-pressure separator; d) Low-pressure separator; e) Gas oil stripper; f ) Gas oil dryer; g) Stripper overhead drum

Task: decreasing sulfur content


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Hydrotreating of pyrolysis gasoline

Task: stabilising the product, desulfurisation

a) First stage reactor; b) First stage separator; c) Depentanizer; d) Gasoline (heart cut) column; e) Second stage reactor; f ) Second stage separator; g) Debutanizer


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Catalytic reforming

  • a) Charge – product heat exchanger;

  • b) Process furnace (charge heating cell, first intermediate heating cell, and second intermediate heating cell);

  • c), d), e) Reforming reactors;

  • f ) Catalyst regeneration section;

  • g) Reactor product separator;

  • h) Stabilizer;

  • Recycle gas compressor;

  • j) Product cooler

Tasks: increase octane number, production of aromatics

Catalyst: Pt on alumina (alloyed with Sn)


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Catalytic reforming

Reactions during catalytic reforming:

Dehydrogenation

Dehydrocyclisation

Dehydroisomerisation

Hydrocracking

Isomerisation


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Hydrocracking

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

a) Hydrogen heater; b) First-stage reactor (hydrotreating); c) Second-stage reactor (hydrocracking); d) High-pressure separator; e) Hydrogen compressor; f ) Low-pressure separator; g) Fractionator


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Residue conversion processes

Task: increase the yield of high value products

„H-in” and „C-out” processes


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Delayed coking (Dunai Finomító)

a) Fractionator; b) Furnace; c) Coke drums; d) Gas oil stripper; e) Overhead accumulator

In most advanced refinery structures:

hydroprocessing + [ coking, deasphalting, hydrocracking ] + partial oxidation


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The atmospheric residue feed is introduced to the fractionator (a) where it condenses some of the cracked vapors. The fractionator bottom product is heated in a tube furnace (b) to ca. 490 °C, and the cracked furnace effluent flows through one of the coke drums (c) in which coke is being formed and deposited. The cracked vapors from the coke drum are separated further in the fractionator. In a 24 h cycle, one of the coke drums is in use while the other is emptied by means of a hydraulic coke removal procedure.

The introduction of the fluid coking process brought the advantage of continuous operation, thus avoiding alternate use of the coke drums. The cracking reactions occur at 500 – 550 °C in the reactor in a fluid bed of coke particles into which the residue feed is injected. Coke fines are removed from the cracked vapors in cyclone separators before fractionation. The coke formed in the reactor flows continuously to the heater, where it is heated up to 600 – 650 °C by partial combustion in a fluid bed. The heated coke particles are returned to the reactor, from where the net coke production is withdrawn.


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Gasoline upgrading processes

Task: producing better fuel, high octane number, no health risk, environmentally more friendly

Processes: alkylation, polymerisation, isomerisation

) Reactor; b) Settler; c) Isostripper; d) Depropanizer; e) HF stripper


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Integrated refinery structures

Hydroskimming


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Integrated refinery structures

Catalytic cracking--visbreaking


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Integrated refinery structures

Hydrocracking—catalytic cracking


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Integrated refinery structures

Hydrocracking--coking


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Yield structures of refinery conversion schemes for Arabian light crude processing


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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 !!!)


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Main air pollutants emitted by a refinery


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Energy consumption in refineries


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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.


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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


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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.


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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.


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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.


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Emission free loading of gasoline

a) Storage tank with floating roof; b) Exhaust gas washes (gasoline); c) Fine purification (adsorption); d) Low-temperature cooling (to – 40 °C)


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Reduction of hydrocarbon emission

A) Vapor recovery at the service station;

B) Large carbon filter in the motor vehicle

a) Gas displacement pipe;

b) Vent; c) Gas venting valve

actuated by filling nozzle;

d) Gas – liquid separator; e) Gas

line; f ) Magnetic valve and

regeneration control orifice;

g) Standard gas vent and

overturn protection; h) Outlet;

i) Fuel tank; j) Liquid seal in

filling tube (reduces escape of

gases); k) Activated carbon filter

with 4.5 L capacity (traps gases)


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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


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Waste generation

  • Oily sludges and materials

  • Spent catalysts, other materials

  • Drums and containers

  • Spent chemicals

  • Mixed wastes


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Example of specific emissions and consumptions found in European refineries


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