ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE PETROLEUM INDUSTRY:

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(No Transcript)
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ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE
PETROLEUM INDUSTRY
MODULE 2

• Sustainable Development and Industrial Practice

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PURPOSE OF MODULE
This module is part of a system of modules
developed to promote the understanding and use of
process integration in engineering
curricula. Process Integration is the synthesis
of process control, process engineering and
process modeling and simulation into tools that
can deal with the large quantities of operating
data now available from process information
systems. Once synthesized the tools can then be
applied to various challenges facing industry and
even challenges beyond the realm of
industry. This module presents an overview of
the major environmental problems facing various
industries in North America.
It also presents Process Integration as a
systematic approach to solving environmental
problems.
Petroleum refineries are used as proof of the
concept.
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STRUCTURE OF MODULE 2
The module is divided into three tiers as follows

• Tier 1 Foundation Elements
• Tier 2 Case Study Elements
• Tier 3 Open-Ended Problem

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Tier 1

• Foundation Elements

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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery ion of Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• ROLE OF PROCESS INTEGRATION IN FACING THE
  CHALLENGE, AVAILABLE TOOLS, TOOLS TO BE DEVELOPED

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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed

During the past years, the perceptions of
pollutions have changed, industry has to find
ways to make products without creating pollution
or to recover and reuse the materials that we
have considered wastes, this philosophy is called
pollution prevention. Process Integration is
highly compatible with this philosophy and
complementary to it. This discipline encompasses
a number of methodologies for designing and
changing industrial processes, based on the unity
of the whole process.
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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• This tier will introduce the basic concepts of
  industrial refining including refinery processes,
  identifying refinery wastes, and exploring
  technologies that deal with refinery wastes.

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Tier 1 Foundation Elements

• BASIC PROCESSES OF A REFINERY

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

DEFINITION

• Petroleum refining is the physical, thermal and
  chemical separation of crude oil into its major
  distillation fractions which are then further
  processed through a series of separation and
  conversion steps into finished petroleum
  products.
• Petroleum refineries are a complex system of
  multiple operations and the operations used at a
  given refinery depend upon the properties of the
  crude oil to be refined and the desired products.

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.1 Separation Processes
• 2.2 Conversion Processes
• 2.3 Treatment Processes
• 2.4 Blending Processes
• 2.5 Auxiliary Processes

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.1 Separation Processes
• These processes involve separating the different
  fractions of hydrocarbon compounds that make up
  crude oil based on their boiling point
  differences. Additional processing of these
  fractions is usually needed to produce final
  products to be sold within the market.

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.1 Separation Processes
• Absorption
• Adsorption
• Crystallization
• Distillation
• Extraction
• Other Separation Processes

Figure 1. Separation of Crude oil into fractions
by fractional distillation Diagram drawn by
Theresa Knott
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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.1 Separation Processes
• Examples
• Distillation
• Atmospheric distillation (Primary Distillation)
• Vacuum distillation (Secondary Distillation)
• Absorption
• Light ends recovery (Gas processing)
• Extraction
• Solvent extraction (Deasphalting)

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.2 Conversion Processes
• Include processes used to break down long chain
  molecules into smaller ones by heating using
  catalysts.

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.2 Conversion Processes
• Thermal Processes
• Catalytic Processes
• Property Improvement Processes

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.2 Conversion Processes
• Examples
• Cracking (thermal and catalytic)
• Catalytic Reforming
• Alkylation
• Polymerization
• Isomerization
• Coking
• Visbreaking

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.3 Treating Processes
• Petroleum-treating processes are used to separate
  the undesirable components and impurities such as
  sulfur, nitrogen and heavy metals from the
  products.
• Finishing Processes
• Treatment Processes

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.3 Treating Processes
• Examples
• Hydrotreatment/hydrogenation
• Chemical Sweetening
• Hydrodesulfurization
• Acid gas removal
• Gas Treatment

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.4 Blending Processes
• These are used to create mixtures with the
  various fractions to produce a desired final
  product, some examples of this are lubricating
  oils, asphalt, or gasoline with different octane
  ratings.

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.4 Blending Processes
• Storage
• Blending
• Loading
• Unloading

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.5 Auxiliary Processes
• Processes that are vital to operations by
  providing power, waste treatment and other
  utility services. Products from these facilities
  are usually recycled and used in other processes
  within the refinery and are also important in
  regards to minimizing water and air pollution.

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Tier 1 Foundation Elements

• Basic Processes of a Refinery

• 2.5 Auxiliary Processes
• Boilers
• Waste water treatment
• Stack gas processing
• Hydrogen production
• Sulfur recovery plant

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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• CLASSIFICATION
• OF REFINERY
• WASTES

View of the Shell/Valero Martinez oil refinery
Image taken July 20, 2004 by UserLeonard G.
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Tier 1 Foundation Elements

• Classification of Refinery Wastes

• Air Emissions
• Wastewater
• Residuals
• Total Environmental Discharges by Process

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Tier 1 Foundation Elements

• Classification of Refinery Wastes

• Air Emissions
• Sources
• 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.
• WASTEWATER SYSTEM EMISSIONS from tanks, ponds and
  sewer system drains.

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Tier 1 Foundation Elements

• Classification of Refinery Wastes

• Air Emissions
• Sources (Continued)
• 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.
• STORAGE TANK EMISSIONS released when product is
  transferred to and from storage tanks.

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Tier 1 Foundation Elements

• Classification of Refinery Wastes

• Wastewater
• Types
• 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
  scaling and biological growth in heat exchanger
  pipes.
• SURFACE WATER RUNOFF is generated intermittently
  and may contain constituents from spills to the
  surface, leaks in equipment and materials in
  drains.
• PROCESS WASTEWATER that has been contaminated by
  direct contact with oil accounts for a
  significant portion of total refinery wastewater.
  Many of these are sour water streams and are
  also subjected to treatment to remove hydrogen
  sulfide and ammonia.

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Tier 1 Foundation Elements

• Classification of Refinery Wastes

• Residuals
• Types
• 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 are regulated under the Resource
  Conservation and Recovery Act (RCRA). Listed
  hazardous wastes include oily sludge, slop oil
  emulsion solids, dissolved air flotation floats,
  leads tank bottom corrosion solids and waster
  from the cleaning of heat exchanger bundles.
• TOXIC CHEMICALS are also use in large quantities
  by refineries. These are monitored through the
  Toxic Release Inventory (TRI).

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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• QUANTIFICATION OF WASTE
  DISCHARGES

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Tier 1 Foundation Elements

• Quantification of Waste Discharges

• Air Emissions
• Solid Wastes
• Liquid Effluents

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Tier 1 Foundation Elements

• Quantification of Waste Discharges

Air Emissions
Table 1. Average rate of air pollutants in
crude Source 3. Pollution Prevention and
Abatement Handbook
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Tier 1 Foundation Elements

• Quantification of Waste Discharges

• Solid Wastes
• Refineries generate solid wastes and sludges
  ranging from 3 to 5 kg per ton of crude
  processed, 80 of this sludge may be considered
  hazardous because or the presence of toxic
  organics and heavy metals.

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Tier 1 Foundation Elements

• Quantification of Waste Discharges

• Liquid Effluent
• Approximately 3.5-5 cubic meters of wastewater
  per ton of crude are generated when cooling water
  is recycled.

1. The maximum effluent concentration of nitrogen
   (total) may be up to 40 mg/l in processes that
   include hydrogenation
2. The effluent should result in a temperature
   increase of no more than 3oC at the edge of the
   zone where initial mixing and dilution take
   place. Where the zone is not defined, use 100
   meters from the point of discharge, provided
   there are no sensitive ecosystems within this
   range.

Table 2. Average rate of liquid pollutants in
crude Source 3. Pollution Prevention and
Abatement Handbook
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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• BEST AVAILABLE TECHNOLOGIES FOR REFINERIES

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• While it is important to reduce the various
  types of refinery emissions and discharges (air,
  liquid, and solid), air emissions are generally
  of particular interest and concern
• There are various Best Available Technologies
  (BATs) that are available for the reduction of
  air emissions such as NOx, SOx, and VOCs.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• NOx
• Flue Gas Recirculation
• Low NOx Burners
• Ultra-Low NOx Burners
• Selective Catalytic Reduction
• Selective Non-Catalytic Reduction
• Combination System

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Tier 1 Foundation Elements
Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• NOx
• Example-Low NOx Burners
• Low-NOx burner (LNB) technology utilizes
  advanced burner design to reduce NOx formation
  through the restriction of oxygen, flame
  temperature, and/or residence time. The two
  general types of low NOx burners are staged fuel
  and staged air burners. Staged fuel LNBs separate
  the combustion zone into two regions.
• The first region is a lean primary combustion
  region where the total quantity of combustion air
  is supplied with a fraction of the fuel.
  Combustion in the primary region (first stage)
  takes place in the presence of a large excess of
  oxygen at substantially lower temperatures than a
  standard burner.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• NOx
• Example-Low NOx Burners
• In the second region (second stage), the
  remaining fuel is injected and combusted with any
  oxygen left over from the primary region. In the
  secondary combustion region, fuel/oxygen are
  mixed diffusively (rather than turbulently) which
  maximizes the reducing conditions. This technique
  inhibits the formation of thermal NOx, but has
  little effect on fuel NOx.
• Thus staged fuel LNBs are particularly well
  suited for boilers and process heaters burning
  process and natural gas which generate higher
  thermal NOx. For fuel oil fired boilers and
  process heaters the staged air LNBs are generally
  preferred, given the higher nitrogen content
  usually present in fuel oils. By increasing
  residence times staged air LNBs provide reducing
  conditions which has a greater impact on fuel NOx
  than staged fuel burners. The estimated NOx
  control efficiency for LNBs where applied to
  petroleum refining fuel burning equipment is
  generally around 40 percent.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

NOx Example-Low NOx Burner
Figure 2. Low NOx Burner Equipment Source
http//www.netl.doe.gov/cctc/resources/database/ph
otos/photostr3.html
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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

NOx Example-Low NOx Burner
Figure 3. Low NOx Burner Equipment Source
http//www.netl.doe.gov/cctc/resources/database/ph
otos/photostr3.html
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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• SOx
• Advanced Flue Gas Desulfurization
• Dry Flue Gas Desulfurization (Spray Dryer
  Absorption)

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• SOx
• Example-Advanced Flue Gas Desulfurization
• The Advanced Flue Gas Desulfurization process
  accomplishes SO2 removal in a single absorber
  which performs three functions prequenching the
  flue gas, absorption of SO2, and oxidation of the
  resulting calcium sulfite to wallboard-grade
  gypsum.
• Incoming flue gas is cooled and humidified with
  process water sprays before passing to the
  absorber. In the absorber, two tiers of
  fountain-like sprays distribute reagent slurry
  over polymer grid packing that provides a large
  surface area for gas/liquid contact. The gas then
  enters a large gas/liquid disengagement zone
  above the slurry reservoir in the bottom of the
  absorber and exits through a horizontal mist
  eliminator.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• SOx
• Ejemplo-Desulfuración Avanzada de Gas de Chimenea
• As the flue gas contacts the slurry, the sulfur
  dioxide is absorbed, neutralized, and partially
  oxidized to calcium sulfite and calcium sulfate.
  The overall reactions are shown in the following
  equations CaCO3 SO2 ? CaSO3 1/2 H2O CO2
• CaSO3 1/2 H2O 3H2O O2 ? 2 CaSO4
  2 H2O
• After contacting the flue gas, slurry falls into
  the slurry reservoir where any unreacted acids
  are neutralized by limestone injected in dry
  powder form into the reservoir. The primary
  reaction product, calcium sulfite, is oxidized to
  gypsum by the air rotary spargers, which both mix
  the slurry in the reservoir and inject air into
  it. Fixed air spargers assist in completing the
  oxidation. Slurry from the reservoir is
  circulated to the absorber grid.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• SOx
• Example-Advanced Flue Gas Desulfurization
• A slurry stream is drawn from the tank,
  dewatered, and washed to remove chlorides and
  produce wallboard quality gypsum. The resultant
  gypsum cake contains less than 10 percent water
  and 20 ppm chlorides. The clarified liquid is
  returned to the reservoir, with a slipstream
  being withdrawn and sent to the wastewater
  evaporation system for injection into the hot
  flue gas ahead of the electrostatic precipitator.
  Water evaporates and dissolved solids are
  collected along with the flash for disposal or
  sale.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

SOx Example-Advanced Flue Gas Desulfurization
Figure 4. Advanced Flue Gas Desulfurization Source
11.
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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• VOCs
• Adsorption Systems
• Condensation Systems
• Thermal Oxidation Systems
• Flares
• Steam Stripping
• Tank Seals

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

• VOCs
• Example-Steam Stripping
• Refinery wastewater streams containing VOCs can
  emit these compounds to the atmosphere unless
  they are removed from the wastewater. Steam
  stripping has been employed for separation of
  these compounds from refinery wastewater. It is
  essentially distillation to volatize the VOCs in
  order to separate them from the wastewater. The
  volatized compounds are then condensed and may be
  recycled within the refinery complex.

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Tier 1 Foundation Elements

• Best Available Technologies for Refineries

VOCs Example-Steam Stripping
Figure 5. Steam Stripping Source 9.
http//www.jaeger.com/Brochure/steam20stripping
.pdfsearch'steam20stripping20equipment
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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• REGULATORY ISSUES FOR REFINERIES IN NORTH AMERICA

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• CANADA
• CAC Emissions
• SIC and NAICS Codes
• Air Emissions Statistics

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• CANADA
• CAC Emissions
• The emissions of various air pollutants that
  affect public health and contribute to air
  pollution problems such as smog are tracked by
  Environment Canada.
• These emissions originate from a number of
  sources located across the country which include
  industrial production, fuel combustion,
  transportation vehicles, incineration, paved and
  unpaved roads, forest fires, etc.
• Emission summaries for selected air pollutants
  such as Total Particulate Matter (TPM),
  Particulate Matter less than or equal to 10
  Microns (PM10), Particulate Matter less than or
  equal to 2.5 Microns (PM2.5), Sulphur Oxides
  (SOx), Nitrogen Oxides (NOx), Volatile Organic
  Compounds (VOCs), Carbon Monoxide (CO) and
  Ammonia (NH3) are available on the Environment
  Canada website. These pollutants are also
  referred to as Criteria Air Contaminants (CAC).
• http//www.ec.gc.ca/pdb/ape/cape_home_e.cfm

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• CANADA
• SIC and NAICS Codes
• The Standard Industrial Classification (SIC) was
  originally developed in the 1930's to classify
  establishments by the type of activity in which
  they are primarily engaged and to promote the
  comparability of establishment data describing
  various facets of the U.S. economy.
• NAICS industries are identified by a 6-digit
  code, in contrast to the 4-digit SIC code. The
  longer code accommodates the larger number of
  sectors and allows more flexibility in
  designating subsectors. It also provides for
  additional detail not necessarily appropriate for
  all three NAICS countries. The international
  NAICS agreement fixes only the first five digits
  of the code. The sixth digit, where used,
  identifies subdivisions of NAICS industries that
  accommodate user needs in individual countries.
  Thus, 6-digit U.S. codes may differ from
  counterparts in Canada or Mexico, but at the
  5-digit level they are standardized.

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• CANADA
• SIC and NAICS Codes
• Three-country comparability of the North American
  Industry Classification System (NAICS) 2002
  NAICS 2002 has a five-digit classification
  structure, with a six-digit structure for
  national industries. With some important
  exceptions, it provides a set of standard 5-digit
  industries that describe the industrial structure
  and composition of the Canadian, United States
  and Mexican economies at selected levels of
  aggregation where agreement occurred among the
  three countries on a compatible classification.
  Below the agreed-upon level of compatibility each
  country has added additional detailed six-digit
  industries, as necessary to meet national needs,
  provided that this additional detail aggregates
  to the NAICS level.
• Some useful links for more about these codes
• http//www.census.gov/epcd/www/naicstab.htm
• http//www.naics.com/info.htm

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• USA
• Environmental Laws Affecting the Petroleum
  Industry
• Clean Air Act
• Clean Water Act
• Resource Conservation and Recovery Act
• Safe Drinking Water Act
• Comprehensive Environmental Response,
  Compensation, and Liability Act (CERCLA)
• Emergency Planning and Community Right to Know
  Act
• Oil Pollution Act
• OSHA
• Toxic Substances Control Act
• Energy Policy Act

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• USA
• Environmental Laws Affecting the Petroleum
  Industry
• Clean Air Act (1970)-National Ambient Air Quality
  Standards (NAAQS) for six constituents new more
  stringent standards for ozone under NAAQS (more
  than doubles non-attainment areas) new standards
  under NAAQS that require control of particulate
  matter of 2.5 microns or smaller lead-free
  gasoline low-sulfur fuel reformulated gasoline
  hazardous air pollutants visibility
  requirements New Source Performance Standards
• Clean Air Act (1990 Amendments)-Oxygenated Fuels
  Program for nonattainment areas low-sulfur
  highway diesel fuel Reformulated Fuels Program
  Leaded Gasoline Removal Program Reid Vapor
  Pressure regulations to reduce VOCs and other
  ozone precursors New Source Review for new or
  expanded facilities or process modifications
  National Emission Standards for Hazardous Air
  Pollutants Risk Management Plans National
  Ambient Air Quality Standards

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• USA
• Environmental Laws Affecting the Petroleum
  Industry
• Clean Water Act-Regulates discharges and spills
  to surface waters wetlands
• Resource Conservation and Recovery Act-Standards
  and regulations for handling and disposing of
  solid and hazardous wastes
• Safe Drinking Water Act-Regulates disposal of
  wastewater in underground injection wells
• Comprehensive Environmental Response,
  Compensation, and Liability Act
  (CERCLA)-Superfund liability for CERCLA
  hazardous substances could apply to wastes
  generated during refining includes past
  releases exempts petroleum and crude oil
  provides for natural resource damages

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• USA
• Environmental Laws Affecting the Petroleum
  Industry
• Emergency Planning and Community Right to Know
  Act (EPCRA)-Requires annual reporting on the
  releases and transfers of listed toxic chemicals
  (313) reporting presence of extremely
  hazardous substances in excess of threshold
  planning quantities (302) reporting certain
  releases of CERCLA hazardous substances and EPCRA
  extremely hazardous substances (304) presence
  of hazardous chemicals over specified thresholds,
  to state and local governments and local fire
  departments, to help local government to respond
  in case of spills or accidental releases
  (311-312)
• Oil Pollution Act (1990) and Spill Prevention
  Control and Countermeasure Plans-Liability
  against facilities that discharge oil to
  navigable waters or pose a threat of doing so

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• USA
• Environmental Laws Affecting the Petroleum
  Industry
• Occupational Safety and Health Act (OSHA)-Health
  Standards and Process Safety Management Rules
  Limits benzene and other chemical exposures in
  the workplace safety plans required in all
  refineries
• Toxic Substances Control Act (TSCA)-Collection of
  data on chemicals for risk evaluation, mitigation
  and control can ban chemicals that pose
  unreasonable risks
• Energy Policy Act-Use of alternative fuels for
  transportation efficiency standards for new
  federal buildings, buildings with federally
  backed mortgages, and commercial and industrial
  equipment RD programs for technologies will
  reduce demand for petroleum products

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Tier 1 Foundation Elements

• Regulatory Issues For Refineries in North America

• MEXICO
• In Mexico, SEMARNAT (Secretaria de Medio Ambiente
  y Recursos Naturales) is in charge or the
  environmental regulations, but it does not cover
  all aspects of a refinery because some of them
  are very specific.
• For example
• Proyecto NOM-088-ECOL-1994 Establish the maximum
  permissible levels of pollutants in the water
  discharges that become from storage and
  distribution of petroleum and its derivates.
• A classification of these norms is found in this
  website
• http//www.semarnat.gob.mx
• If the complete document is needed it can be
  obtained at the following site
• http//cronos.cta.com.mx/cgi-bin/normas.sh/cgis/i
  ndex.p

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Tier 1 Foundation Elements

• Role of Process Integration in Facing the
  Challenge, Available Tools, Tools to be Developed
• Basic Processes of a Refinery
• Classification of Refinery Wastes
• Quantification of Waste Discharges
• Best Available Technologies for Refineries
• Regulatory Issues for Refineries in North America
• Driving Forces, Hurdles, Potential for
  Environmental Issues

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Tier 1 Foundation Elements

• DRIVING FORCES, HURDLES, AND POTENTIAL FOR
  ENVIRONMENTAL ISSUES

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Tier 1 Foundation Elements

• Driving Forces Hurdles and Potential for
  Environmental Issues

• The petroleum refining industry is a strong
  contributor to the economic health of the United
  States and Mexico.

Oil well near Sarnia, Ontario

• For Mexico, this industry has become a vital part
  of the national economy, it is a primary source
  of currency for the country.

• Hydrocarbons will long remain the resource of
  choice to fuel future economic progress
  worldwide. This is a reason not only to protect
  air, water and land resources, but also to keep
  serving society through these products.

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Tier 2

• Case Study Elements

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Tier 2 Case Study

• Earlier it was stated that process integration is
  a systematic approach to solving environmental
  problems. The following case study utilizes a
  typical petroleum refinery to establish
  preliminary material and energy balances and
  ultimately develop preliminary targets for
  environmental discharges using process
  integration. We will then identify priority
  pollutants, quantify energy-related issues and
  their relation to pollution.

73
Tier 2 Case Study

• Preliminary Material and Energy Balances for a
  typical refinery
• Priority Pollutants
• Quantification of Energy-Related Issues in
  Regards to Pollution
• Preliminary Targets for Environmental Discharges
  Using Process Integration

74
Tier 2 Case Study
Typical Refinery
Figure 6. Schematic of Mexican Petroleum
Refining Process Source E Aguuilar R. Revista
del IMIQ. Año XLIII, Vol. 1-2, Enero Febrero 2002
75
Tier 2 Case Study

• Preliminary Material and Energy Balances for a
  typical refinery
• Priority Pollutants
• Quantification of Energy-Related Issues in
  Regards to Pollution
• Preliminary Targets for Environmental Discharges
  Using Process Integration

76
Tier 2 Case Study

• Preliminary Material and Energy Balances for a
  typical refinery

Overall Material Balance
LPG (11,161)
NC4 (5,844)
Crude Oil (223,992)
Naphtha (11,276)
223,992 BPCD Refinery
Gasoline (103,000)
Refinery C5-(899)
Xylenes (11,267)
Benzene (3,165)
Kerosine/Jet (21,200)
Diesel (41,200)
Residual Fuel Oil (13,500)
Coke (3,278)

• The above overall material balance is for a U.S.
  Gulf Coast Refinery and 223,992 BPCD (barrels per
  calendar day) of Maya Crude Oil
• For more specific material balances and process
  descriptions, see SRI Report No. 215 Petroleum
  Refining Profitability

Figure 7. Material Balance for a U.S. Gulf Coast
Refinery, 223,992 BPCD of Maya Crude Source
SRI Report No. 215 Petroleum Refining
Profitability
77
Tier 2 Case Study

• Preliminary Material and Energy Balances for a
  typical refinery
• Priority Pollutants
• Quantification of Energy-Related Issues in
  Regards to Pollution
• Preliminary Targets for Environmental Discharges
  Using Process Integration

78
Tier 2 Case Study

• Priority Pollutants

Pemex Refinancíon (PR)
Table 3. Pemex Refinery Emissions and Discharges

• Air emissions are the major contributors to
  environmental pollution contributing 90.4 in
  2001 and 76.0 in 2002.

79
Tier 2 Case Study

• Priority Pollutants

Pemex Refinancíon (PR)
Table 4. Pemex Refinery Air Emissions

• Of the air emissions, the priority pollutants are
  SOX contributing 81.8 in 2001 and 78.9 in 2002.
• Volatile Organic Compounds are the second major
  contributors to air emissions accounting for
  approximately 8 (7.98 in 2001 and 8.15 in
  2002).
• 1Excluding VOCs (already accounted for in total
  organic compounds (TOCs).

80
Tier 2 Case Study

• Priority Pollutants

Pemex Refinancíon (PR)
Table 5. Pemex Refinery Discharges to Water

• Of the discharges to water, the priority
  pollutants are the total suspended solids
  contributing 47.9 in 2001 and 57.2 in 2002.
• Note that there is an overall decrease in total
  discharges to water in 2002 including a decrease
  in total suspended solids the increase in
  percentage in 2002 is reflective of the overall
  decrease in discharges.

81
Tier 2 Case Study

• Priority Pollutants

Pemex Refinancíon (PR)
Table 6. Pemex Refinery Hazardous Waste

• Greenhouse gases, namely CO2 emissions, are the
  major source of hazardous wastes.
• Carbon Dioxide emissions steadily declined from
  1999 to 2001 (1999 -15.09 millions of tons,
  2000-14.18 millions of tons).
• Total generation of non-greenhouse wastes
  accounted for a significant portion of total
  emissions and discharges (7.90 in 2001 and
  20.53 in 2002).

82
Tier 2 Case Study

• Priority Pollutants

Pemex Refinancíon (PR)
Table 7. Pemex Refinery Hydrocarbon Spills

• Hydrocarbon spills on land account for the
  majority of hydrocarbon spills and leaks.

83
Tier 2 Case Study

• Preliminary Material and Energy Balances for a
  typical refinery
• Priority Pollutants
• Quantification of Energy-Related Issues in
  Regards to Pollution
• Preliminary Targets for Environmental Discharges
  Using Process Integration

84
Tier 2 Case Study

• Quantification of Energy-Related Issues in
  Regards to Pollution

Energy Use
Table 8. Estimated Energy Use by Refining Process
85
Tier 2 Case Study

• Quantification of Energy-Related Issues in
  Regards to Pollution

Table 9. Air Emission Factors by Process
86
Tier 2 Case Study

• Preliminary Material and Energy Balances for a
  typical refinery
• Priority Pollutants
• Quantification of Energy-Related Issues in
  Regards to Pollution
• Preliminary Targets for Environmental Discharges
  Using Process Integration

87
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

• A major concern in refineries is the release of
  phenols, although described as this, the category
  may include a variety of similar chemical
  compounds among which are polyphenols,
  chlorophenols, and phenoxyacids. The concern is
  because of their toxicity to aquatic life and the
  high oxygen demand they sponsor in the streams
  that receive it. Phenols are toxic to fish and
  also they can cause taste and odor problems when
  present in potable water.

88
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Problem Statement

• The next study case applies some of the skills of
  Process Integration to show the methodology once
  again and make it more understandable. This case
  was taken from El-Halwagi, M. Pollution
  Prevention through Process Integration, 1997.
• The process generates two major sources of
  phenolic wastewater one from the catalytic
  cracking unit and the other from the visbreaking
  system. Two technologies can be used to remove
  phenol from R1 and R2 solvent extraction using
  light gas oil S1 (a process MSA) and adsorption
  using activated carbon S2(an external MSA). A
  minimum allowable composition difference, ej, of
  0.01 can be used for the two MSAs.
• By constructing a pinch diagram for the problem,
  find the minimum cost of MSAs needed to remove
  phenol from R1 and R2. How do you characterize
  the point at which both composite streams touch?
  Is it a true pinch point?

89
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Data
Tables 10 11. Data for Phenolic Wastewater
Problem
90
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

The Process
Sweetening Unit
Hydrotreating
Catalytic Cracking
Solvent Extraction and Dewaxing
Visbreaker
Figure 8. Petroluem Refining Process
91
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Process Description

• The first step in a petroleum refinery is to
  preheat the crude, then it is washed with water
  to remove various salts.
• Gas oil and heavy stocks are fed to a
  catalytic-cracking unit to be converted to lower
  molecular weight fractions. The main waste
  stream from this process is the condensate from
  stripping in the fractionating column. This
  condensate commonly contains ammonia, phenols and
  sulfides as contaminants, this has to be stripped
  to remove ammonia and sulfides. The bottom
  product of the stripper must be treated to
  eliminate phenols.

92
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Process Description

• The light gas oil leaving the fractionator can
  serve as a lean-oil solvent in a phenol
  extraction process. This can be a beneficiary
  mass transfer because in addition to purifying
  water, phenols can act as oxidation inhibitors
  and as color stabilizers.
• The main objectives of visbreaking are to reduce
  the viscosity and the pour points of vacuum-tower
  bottoms and to increase the feed stocks to
  catalytic cracking. The source of wastewater is
  the overhead accumulator on the fractionator,
  where water is separated from the hydrocarbon
  vapor. This water contains phenols, ammonia an
  sulfides.

93
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Rich Stream Plot
Figure 10. Plot of Rich Stream
94
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Rich Stream Plot
Figure 11. Plot of Rich Stream
95
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

One-To-One Correspondence

• To generate the one-to-one correspondence, we use
  the following equationyf(xjej)
• Where ej is the minimum allowable composition
  difference. ej0.01
• In this case the equilibrium equation is linear
  y m(xe) b
• y1s 2(0.010.01) 0.04 y2s 0.02(0.000.01)
  0.0002
• y1t 2(0.020.01) 0.06 y2t 0.02(0.110.01)
  0.0024

96
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Lean Stream Plot
Figure 12. Plot of Lean Stream
97
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Obtain A Pinch-Point
Figure 13. Plot of Lean Stream with Pinch Point
Indicated
98
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Obtain A Pinch-Point

• Stream 1 would not be useful, since external MSAs
  should be used before and after using this
  stream. That means that this is not a true pinch
  point (see Figure 13).

99
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Interpret Results
Figure 14. Shifting the Lean Stream
100
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Interpret Results

• The lean stream can be moved to remove the
  pollutant in another range of composition, but
  still three units would be needed (see Figure 14).

101
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Interpret Results
Figure 15. Shifting the Lean Stream
102
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Interpret Results

• If the lean stream is moved to a still higher
  composition, it can remove the pollutant and just
  2 units are needed (see Figure 15).

103
Tier 2 Case Study

• Preliminary Targets for Environmental Discharges
  Using Process Integration

Interpret Results
Mass removed by Process MSA
Mass removed by External MSA
y
Figure 16. Mass Removed by Process MSA and
External MSA
104
Tier 3

• Open-Ended Problem

105
Tier 3 Open-Ended Problem
Utilizing Case Study

• There are 6 refineries in Mexico
• A typical refinery (See Figure 6.)produces
  roughly 250,000 BPD.
• The major products as shown in Figure 8 are heavy
  fuel oil, gasoline, diesel, kerosine, and LPG.

106
Tier 3 Open-Ended Problem
Utilizing Case Study
Heavy Fuel Oil (33.3)
Gasoline (33.0)
250,000 BPD Refinery
Oil
Diesel (22.0)
Kerosine (6.6)
LPG (5.1)
Figure 17. Overall mass balance for a typical
Mexican refinery.

• Note Keep in mind that in a detailed overall
  refinery balance, there are other outputs besides
  the desired products.

107
Tier 3 Open-Ended Problem
Utilizing Case Study

• Below is an example of an open ended problem that
  might be faced in industry
• Consider the example of a typical Mexican
  petroleum refinery (figure 6). Based on the
  assumption that no low NOx burners are used and
  that boilers with no combustion cleaning process
  (i.e. for SO2 and NOx) are also used and using
  Tables 4-8, determine the amount of NO2
  discharged from a typical refinery. Compare this
  amount to the standards presented in Table 1.
• Utilize the mass integration techniques presented
  in Tier 2 to meet the NO2 emissions
  specifications.

108
Acronyms

• TSP-Total Suspended Particles
• TOC-Total Organic Compound
• VOC-Volatile Organic Compound
• OG-Oils and Greases
• TSS-Total Suspended Solids
• MMBCOE-Million Barrells of Crude Oil Equivalent

109
End of Module

• CONGRATULATIONS!!!

• This is the end of Module 2.
• Please submit your report to your professor for
  grading.

110
Resources

1. Rossiter, Alan P. Waste Minimization through
   Process Design. MacGraw Hill. 1995.
2. Cheremisinoff, Nicholas P. Handbook of Pollution
   Prevention Practices. Marcell Dekker Inc. 2001.
3. The World Bank Group. Pollution Prevention and
   Abatement Handbook 1998.
4. http//www.ec.gc.ca/pdb/ape/cape_home_e.cfm
5. El-Halwagi, M.M. Pollution Prevention Through
   Process Integration. Academic Press. 1997.
6. Environmental Update 12, Hazardous Substance
   Research Centers/Southwest Outreach Program, June
   2003. www.hsrc.org/hsrc/html7ssw/update12.pdf
7. Energy and Environmental Profile of the U.S.
   Petroleum Industry. December 1998. U.S.
   Department of Energy, Office of Industrial
   Technologies.
8. EPA Office of Compliance Sector Notebook Project,
   Profile of the Petroleum Refining Industry,
   September 1995.

111
Resources

1. http//www.jaeger.com/brochure/steam20stripping.p
   df
2. Midwest Regional Planning Organization (RPO),
   Petroleum Refinery Best Available Retrofit
   Technology (BART) Engineering Analysis, Prepared
   for The Lake Michigan Air Directors Consortium
   (LADCO), Prepared by MACTEC Federal Programs /
   MACTEC Engineering and Consulting, Inc.(MACTEC),
   March 30, 2005.
3. http//www.naics.com/info.htm
4. http//www.netl.doe.gov/cctc/resources/database/ph
   otos/photostr3.html
5. Revista Del IMIQ. Enero Febrero 2002. Instituto
   Mexicano de Ingenieros Químicas A.C. ISSN
   0188-7319/Año XLIII, Vol 1-2.
6. PEMEX Sustainable Development Safety, Health
   and Environment, Report 2001.
7. PEMEX Sustainable Development Safety, Health
   and Environment, Report 2002. http//www.pemex.com
   /files/seguridad/Proteccionambientali.pdf