ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE PETROLEUM INDUSTRY - PowerPoint PPT Presentation

1 / 111
About This Presentation
Title:

ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE PETROLEUM INDUSTRY

Description:

ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE PETROLEUM INDUSTRY: Sustainable Development and Industrial Practice PURPOSE OF MODULE STRUCTURE OF MODULE 2 Tier 1 ... – PowerPoint PPT presentation

Number of Views:472
Avg rating:3.0/5.0
Slides: 112
Provided by: polymtlCa
Category:

less

Transcript and Presenter's Notes

Title: ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE PETROLEUM INDUSTRY


1
(No Transcript)
2
ENVIRONMENTAL CHALLENGES OVERVIEW FACING THE
PETROLEUM INDUSTRY
MODULE 2
  • Sustainable Development and Industrial Practice

3
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.
4
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

5
Tier 1
  • Foundation Elements

6
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

7
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

8
Tier 1 Foundation Elements
  • ROLE OF PROCESS INTEGRATION IN FACING THE
    CHALLENGE, AVAILABLE TOOLS, TOOLS TO BE DEVELOPED

9
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.
10
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

11
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.

12
Tier 1 Foundation Elements
  • BASIC PROCESSES OF A REFINERY

13
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.

14
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

15
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.

16
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
17
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)

18
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.

19
Tier 1 Foundation Elements
  • Basic Processes of a Refinery
  • 2.2 Conversion Processes
  • Thermal Processes
  • Catalytic Processes
  • Property Improvement Processes

20
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

21
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

22
Tier 1 Foundation Elements
  • Basic Processes of a Refinery
  • 2.3 Treating Processes
  • Examples
  • Hydrotreatment/hydrogenation
  • Chemical Sweetening
  • Hydrodesulfurization
  • Acid gas removal
  • Gas Treatment

23
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.

24
Tier 1 Foundation Elements
  • Basic Processes of a Refinery
  • 2.4 Blending Processes
  • Storage
  • Blending
  • Loading
  • Unloading

25
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.

26
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

27
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

28
Tier 1 Foundation Elements
  • CLASSIFICATION
  • OF REFINERY
  • WASTES

View of the Shell/Valero Martinez oil refinery
Image taken July 20, 2004 by UserLeonard G.
29
Tier 1 Foundation Elements
  • Classification of Refinery Wastes
  • Air Emissions
  • Wastewater
  • Residuals
  • Total Environmental Discharges by Process

30
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.

31
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.

32
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.

33
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).

34
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

35
Tier 1 Foundation Elements
  • QUANTIFICATION OF WASTE
    DISCHARGES

36
Tier 1 Foundation Elements
  • Quantification of Waste Discharges
  • Air Emissions
  • Solid Wastes
  • Liquid Effluents

37
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
38
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.

39
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.
  • The maximum effluent concentration of nitrogen
    (total) may be up to 40 mg/l in processes that
    include hydrogenation
  • 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
40
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

41
Tier 1 Foundation Elements
  • BEST AVAILABLE TECHNOLOGIES FOR REFINERIES

42
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.

43
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

44
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.

45
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.

46
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
47
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
48
Tier 1 Foundation Elements
  • Best Available Technologies for Refineries
  • SOx
  • Advanced Flue Gas Desulfurization
  • Dry Flue Gas Desulfurization (Spray Dryer
    Absorption)

49
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.

50
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.

51
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.

52
Tier 1 Foundation Elements
  • Best Available Technologies for Refineries

SOx Example-Advanced Flue Gas Desulfurization
Figure 4. Advanced Flue Gas Desulfurization Source
11.
53
Tier 1 Foundation Elements
  • Best Available Technologies for Refineries
  • VOCs
  • Adsorption Systems
  • Condensation Systems
  • Thermal Oxidation Systems
  • Flares
  • Steam Stripping
  • Tank Seals

54
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.

55
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
56
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

57
Tier 1 Foundation Elements
  • REGULATORY ISSUES FOR REFINERIES IN NORTH AMERICA

58
Tier 1 Foundation Elements
  • Regulatory Issues For Refineries in North America
  • CANADA
  • CAC Emissions
  • SIC and NAICS Codes
  • Air Emissions Statistics

59
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

60
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.

61
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

62
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

63
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

64
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

65
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

66
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

67
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

68
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

69
Tier 1 Foundation Elements
  • DRIVING FORCES, HURDLES, AND POTENTIAL FOR
    ENVIRONMENTAL ISSUES

70
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.

71
Tier 2
  • Case Study Elements

72
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
  • Rossiter, Alan P. Waste Minimization through
    Process Design. MacGraw Hill. 1995.
  • Cheremisinoff, Nicholas P. Handbook of Pollution
    Prevention Practices. Marcell Dekker Inc. 2001.
  • The World Bank Group. Pollution Prevention and
    Abatement Handbook 1998.
  • http//www.ec.gc.ca/pdb/ape/cape_home_e.cfm
  • El-Halwagi, M.M. Pollution Prevention Through
    Process Integration. Academic Press. 1997.
  • Environmental Update 12, Hazardous Substance
    Research Centers/Southwest Outreach Program, June
    2003. www.hsrc.org/hsrc/html7ssw/update12.pdf
  • Energy and Environmental Profile of the U.S.
    Petroleum Industry. December 1998. U.S.
    Department of Energy, Office of Industrial
    Technologies.
  • EPA Office of Compliance Sector Notebook Project,
    Profile of the Petroleum Refining Industry,
    September 1995.

111
Resources
  • http//www.jaeger.com/brochure/steam20stripping.p
    df
  • 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.
  • http//www.naics.com/info.htm
  • http//www.netl.doe.gov/cctc/resources/database/ph
    otos/photostr3.html
  • Revista Del IMIQ. Enero Febrero 2002. Instituto
    Mexicano de Ingenieros Químicas A.C. ISSN
    0188-7319/Año XLIII, Vol 1-2.
  • PEMEX Sustainable Development Safety, Health
    and Environment, Report 2001.
  • PEMEX Sustainable Development Safety, Health
    and Environment, Report 2002. http//www.pemex.com
    /files/seguridad/Proteccionambientali.pdf
Write a Comment
User Comments (0)
About PowerShow.com