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Chapter 13: Environmental Impacts of

Petroleum Refining Processes

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In this chapter, we will briefly study:

The different types of pollutants from petroleum refineries and how they are discharged to environment

Pollutants discharges from major refinery processes

World regulations on pollutants discharges from petroleum refineries

Reduction of pollutants discharges to environment and treatment of wastes

Overview

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Some Important Terminologies

Fugitive Emissions are emissions of gases or vapors from pressurized equipments due to leaks and various other unintended releases of gases, and is not routed to a pollution control device.

Process Vent is a point of emission from a unit operation (e.g., reactor) having a gaseous stream that is discharged to the atmosphere.

Heater Stack Gases are side products of the combustion of fossil fuels used by heaters and furnaces.

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Air Emissions (Air Pollutants) Heater Stack Gas (CO, NOx, SOx)

CO2

Volatile hydrocarbons (e.g., Benzene, Toluene, Xylene, Propane and others)

Solid particulate (e.g., metals and dust)

NH3

H2S

HCl

AIR EMISSIONS

Pollutant Average ratekg/t of crude

Particulate matter 0.8Sulfur oxides 1.3Nitrogen oxides 0.3Benzene, tolueneand xylene (BTX) 0.0025VOC 1

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Combustion Emissions: associated with the burning of fuels in the refinery, including fuels used in the generation of electricity.

Equipment Leak Emissions (Fugitive Emissions): released through leaking valves, pumps, or other process devices. They are primarily composed of volatile compounds such as ammonia, benzene, toluene, propylene, xylene, and others.

Process Vent Emissions: typically include emissions generated during the refining process itself. Gas streams from all refinery processes contain varying amounts of refinery fuel gas , hydrogen sulfide and ammonia.

Sources of Air Emissions

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Water Effluents (Water Pollutants) Oil H2SNH3

PhenolsSuspended and dissolved solidsChloridesMercaptansAlkalinesBOD (Biochemical Oxygen Demand)COD (Chemical Oxygen Demand)CynidesH2SO4

AminesHeavy metals

PollutantAverage ratemg/l ofwastewater

BOD 150-250COD 300-600Phenols 20-200Oil 100-300Benzene 1-100Benzopyrene 1-100Heavy metals 0.1-100Chrome 0.2-10

Approximately 3.5-5 cubic meters of wastewater per ton of crude are generated.

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BOD (Biochemical Oxygen Demand)BOD= amount of oxygen consumed by microorganisms (e.g., bacteria)

to utilize organic wastes as food and/or energy. From BOD we can estimate the amount of organic wastes in wastewater

Example:

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COD (Chemical Oxygen Demand)COD= amount of oxygen required to fully oxidize organic wastes in

wastewater. From COD we can estimate the amount of organic wastes in wastewater

Example:

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Sources and Types of Wastewater Produced in Refineries

Surface Water Runoff: is generated intermittently (either by rainfall or human) and may contain constituents from spills to the surface, leaks in equipment and materials in drains.

Cooling Water: which normally does not come into contact with oil streams and contains less contaminants than process wastewater. It may contain chemical additives used to prevent biological growth in heat exchanger pipes.

Process Wastewater: that has been contaminated by direct contact with oil accounts for a significant portion of total refinery wastewater.

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Solid Wastes

Refineries generate solid wastes and sludges ranging from 3 to 5 kg per ton of crude processed, 80% of this sludges may be considered hazardous because of the presence of harmful organics and heavy metals.

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Most refinery residuals are in the form of sludge, spent caustics, spent process catalysts, and incinerator ash.

Non-hazardous Residuals: are incinerated, landfilled or regenerated to provide products that can be sold off-site or returned for re-use at a refinery.

Hazardous Wastes: Listed hazardous wastes include oily sludge, leads tank bottom corrosion solids and wastes from the cleaning of heat exchanger bundles.

Toxic Chemicals: These are very dangerous materials that require extreme handling care. Many toxic chemicals are produced/used in large quantities by refineries.

These residuals could be classified as follows:

Residual Wastes

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Types and Sources of Residual WastesCrude oil/desalted sludge: Contains iron rust, clay, sand, metals, emulsified oil and wax.

Coke dust: Contains carbon particles and hydrocarbons

Spent catalysts: May contain metals, fine particles, phosphoric acid, and/or alumina silicate.

Neutralized alkylation sludge: Contains sulfuric acid or calcium fluoride and hydrocarbons.

Heat exchanger sludge: Contains oil, metals and suspended solids

Tank bottom sludge: Contains iron rust, clay, sand, metal, emulsified oil and wax.

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DesaltingPurpose of Desalting: remove corrosive salts along with some of the

metals and suspended solids from crude oil before processing.

Environmental impact of Desalting:Air Emissions: CO, SOx, NOx, particulates and fugitive emissions

(hydrocarbons).Effluent to Water: Oil, H2S, NH3, phenol, high levels of suspended solids, dissolved solids and high BOD. Amount of wastewater produced = 2.1 Gal/Bbl crude oil processed. 1 Bbl= 31 GalResidual waste generated: Sludge contains salts, iron rust, clay, sand, metals, emulsified oil and wax.

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Purpose of Distillation: To separate the ingredients of crude oil into several valuable products.

Environmental impact of Distillation:Air Emissions: CO, SOx, NOx, and particulates. Vent and fugitive

emissions (hydrocarbons).

Distillation

Effluent to Water: Oil, H2S, NH3, suspended solids, chlorides, mercaptans, phenol and alkalines. Amount of wastewater produced= 26 Gal/Bbl crude oil processed

Residual waste generated: Typically little or no residual waste generated.

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Purpose of Visbreaking: To produce lighter (more valuable) products from heavy (residual) feedstocks.

Environmental impact of Visbreaking :

Visbreaking

Air Emissions: CO, SOx, NOx, and particulates. Vents and fugitive emissions (hydrocarbons).

Effluent to Water: Oil, H2S, NH3, phenol, suspended solids, alkalines, BOD and COD. Amount of wastewater produced= 2.0 Gal/Bbl crude oil processed

Residual waste generated: Typically little or no residual waste generated.

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Purpose of Coking: To produce distillate naphtha and gas oils from heavy residuum.

Environmental impact of Coking:

Coking

Air Emissions: CO, SOx, NOx, and particulates. Vents and fugitive emissions (hydrocarbons). Decoking emissions (hydrocarbons and particulates).Effluent to Water: H2S, NH3, suspended solids, alkalines and COD. Amount of wastewater produced= 1.0 Gal/Bbl crude oil processed

Residual waste generated: Coke dust (carbon particles and hydrocarbons).

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Purpose of Catalytic Cracking: To upgrade some refinery stocks to more valuable products through catalytic reactions.

Environmental impact of Catalytic Cracking:

Catalytic Cracking

Air Emissions: CO, SOx, NOx, and particulates. Vents and fugitive emissions (hydrocarbons).

Effluent to Water: High levels of oil, H2S, NH3, suspended solids, alkalines, phenols, cyanides, BOD and COD. Amount of wastewater produced= 1.0-2.0 Gal/Bbl crude oil processed

Residual waste generated: Spent catalyst, which may containhydrocarbons, metals and/or solid particles

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Purpose of Alkylation Alkylation is used for the production of higher molecular weight isoparaffins from the reaction of low molecular weight olefins with an isoparaffin in the presence of either sulfuric or hydrofluoric acid.Environmental impact of Alkylation:

Alkylation

Air Emissions: CO, SOx, NOx, and particulates. Vents and fugitive emissions (hydrocarbons).

Effluent to Water: H2S, dissolved and suspended solids, acids (such as sulfuric acid) and COD.

Residual waste generated: Neutralized alkylation sludge (containshydrocarbons, sulfuric acid or calcium chloride).

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Purpose of Isomerization is to convert straight-chain paraffins into isomers that have higher octane numbers.

Environmental impact of Isomerization:

Isomerization

Air Emissions: CO, SOx, NOx, and particulates. Vents and fugitive emissions (hydrocarbons).

Effluent to Water: Chloride salts, caustic wash and relatively low amounts of H2S and NH3

Residual waste generated: Calcium chloride sludge.

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Purpose of Polymerization Polymerization is a catalytic process to convert low-boiling olefins into gasoline blending stocks

Environmental impact of Polymerization:

Polymerization

Air Emissions: H2S from caustic washing.

Effluent to Water: Mercaptans, caustic wash, alkalines, H2S and NH3

Residual waste generated: Spent catalyst containing phosphoric acid.

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Purpose of Catalytic Reforming in catalytic reforming, the hydrocarbon molecular structures are rearranged to form higher-octane motor gasoline.

Environmental impact of Catalytic Reforming:

Catalytic Reforming

Air Emissions: CO, SOx, NOx, HCl, and particulates. Vents and fugitive emissions (hydrocarbons).

Residual waste generated: Spent catalyst

Effluent to Water: High levels of oil, suspended solids, CODand relatively low amount of H2S. Amount of wastewater produced= 6.0 Gal/Bbl crude oil processed

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Purpose of Dewaxing is to lower cloud and pour points by removing waxes from refinery feedstocks or products using organic solvents.

Environmental impact of Dewaxing:

Dewaxing

Air Emissions: Fugitive solvents

Residual waste generated: Little or no residual wastes generated

Effluent to Water: Oil and organic solvents.

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Purpose of Propane Deasphalting is to produce asphalt from lube feedstocks and also to increase gas oil yield from crude.

Environmental impact of Propane Deasphalting:

Propane Deasphalting

Air Emissions: CO, SOx, NOx, HCl, hydrocarbons and particulates. Fugitive propane.

Effluent to Water: Oil and organic solvents.

Residual waste generated: Little or no residual wastes generated

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Purpose of Blending is to allocate the available blending components in such a way as to meet product demands and specifications at the least cost and maximum possible profit.

Environmental impact of Propane Blending:

Blending

Air Emissions: Fugitive emissions (hydrocarbons)

Effluent to Water: Little or no wastewater generated

Residual waste generated: Little or no residual wastes generated

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Purpose of Heat Exchanger Cleaning is to remove foulings from the inside surfaces of heat exchangers.

Environmental impact of Heat Exchanger Cleaning:

Heat Exchanger Cleaning

Air Emissions: Periodic fugitive emissions (hydrocarbons)

Effluent to Water: Oily wastewater generated

Residual waste generated: Heat exchanger sludge (contains oil, metals and suspended solids)

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Purpose of Storage Tanks is to store refinery feedstocks and products.

Environmental impact of Storage Tanks:

Storage Tanks

Air Emissions: Fugitive emissions (hydrocarbons)

Effluent to Water: Water drained from tanks contaminated with tank contents.

Residual waste generated: Tank bottom sludge (contains iron rust, metals, emulsified oil and wax)

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Parameter Maximum valuepH 6--9BOD 30COD 150TSS 30Oil and grease 10Chromium Hexavalent 0.1 Total 0.5Lead 0.1Phenol 0.5Benzene 0.05Benzo(a)pyrene 0.05Sulfide 1Nitrogen(total) 10Temperature increase <=3 C

The World Bank, has established emission levels for the design and operation of refineries, although country legislation should be accomplished. The guidelines given below present emissions levels normally acceptable to the World Bank Group.

Gas Emissions from the Petroleum Industry (mg/m3 crude processed)

Water Effluents from the Petroleum Industry(g/m3 crude processed)

Generation of sludges should be minimized to 0.3 kg per ton of crude processed, with a maximum of 0.5 kg per ton of crude processed.

Solid Wastes

World General Regulations on Discharges from Refineries

Parameter Maximum valuePM 50Nitrogen oxides 460Sulfur oxides 150 for sulfur recovey

units; 500 for other units

Nickel and vanadium (combined)

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Hydrogen sulfide 152

(Total Suspended Solid)

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Reduction of Air EmissionsPreserving air quality around a refinery involves controlling the

gas and hydrocarbon vapor emissions to the atmosphere.

Reduction of CO Emissions: through complete burning of CO to CO2 and then using CO2 capture and sequestration (or biological) methods to dispose CO2.

Preventing H2S Emissions: by converting it into elemental sulfur

Reduction of SOx Emissions: through sulfur recovery from tail gases in high-efficiency sulfur recovery units

Reduction of NOx Emissions: through converting it to less harmful and useful chemicals such as NH3 and N2

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Reduction of Air Emissions.. ContinuedReduction of NH3 Emissions: By converting it to useful chemicals

such as urea.

Minimization of fugitive emissions of hydrocarbons and organic solvents: Through

1. Proper design with regular maintenance of refinery equipments.2. By installing floating roofs in storage tanks to prevent

evaporation and so that there is no space for vapor to gather in the tanks.

3. Vapour recovery system - absorbed back into the product stream.

4. Prevent leakage in pumps and valvesPrevention of particulate emissions: through removal of particulates from gases (by, for example, filtration) and dispose the particulates appropriately.

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Wastewater Treatment Refinery wastewater treatment plants are integrated

systems that use both primary and secondary treatment.

Oil water separator Settling pond for sedimentation. Also known as settling pond or decant pond.

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Primary TreatmentPrimary treatment: Used to separate oil and solids from water in two stages. First stage: API oil-water separator based on differences in specific gravities.Process: allow sufficient time for free oil to float to the surface and be skimmed off, while solids settle to the bottom of the unit and are removed by mechanical scraping and depositing of the sludge into a collection hopper.

Second stage: relies on physical or chemical methods to separate emulsified oils and fine particles from the wastewater:

Physical methods are typically a series of settling ponds designed to have long retention times to allow settling.

Chemicals such as ferric hydroxide or aluminum hydroxide are used to coagulate impurities into a froth or sludge, which can be skimmed off the surface.

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Secondary Treatment Biological treatment: Dissolved oil and other organic pollutants

may be consumed biologically. Biological treatment may require oxygen. Treatment can be done through different techniques: • Activated sludge units

• Trickling filters• Rotating biological contactors.

PolishingSome refineries employ it as an additional stage of wastewater treatment to meet discharge limits.

• Activated carbon• Anthracite coal• Sand

Generates bio-mass waste which is treated anaerobically.

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Sludge treatment use bioremediation or solvent extraction, followed by combustion of the residues or using it as asphalt additive. The residue could require stabilization before disposal to reduce the leachability of toxic metals.

Solid Waste Treatment

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End of Environmental Impacts of Petroleum Refining Processes