Module 2

2. ENVIRONMENTAL CHALLENGES: OVERVIEW FACING INDUSTRY Module 2

3. Purpose of Module 2 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. 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. Two major industries (pulp and paper and 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: Basic Concepts TIER 2: Case Study TIER 3: Computer-Aided Module

5. TIER 1 : BASIC CONCEPTS This tier will provide a background including a general description of the major industries in North America, and focus on current environmental challenges facing the pulp and paper as well as the petroleum refining industries.

6. TIER 1 : BASIC CONCEPTS CONTENTS This section in broken into three sections: 1. Major Industries in North America. 2. Petroleum Industry 2.1 Driving forces, hurdles and potential. 2.2 Environmental discharges. 2.3 Regulatory issues in North America. 2.4 Best available environmental technologies for specific processes 3. Pulp and Paper Industry 3.1 Driving forces, hurdles and potential. 3.2 Environmental discharges. 3.3 Regulatory issues in North America. 3.4 Best available environmental technologies for specific processes

7. 1.- MAJOR INDUSTRIES IN NORTH AMERICA

8. 1. MAYOR INDUSTRIES IN NORTH AMERICA The most important industrial sectors in North America were sought not through their production but reviewing the quantity of their releases and pollutants. Some statistics are organized by country : CANADA USA MEXICO

9. More information: Top 20 pollutants More Statistics: Canadian NPRI C A N A D A Pulp, Paper and Paperboard mills Canada is the world’s largest exporter of commodity-grade pulp and paper products, making this industry one of the most important pollutant sector.

10. Top 20 Pollutants Released On Site in the Largest Quantities, 2001 C A N A D A

11. Refineries and petroleum subproducts are included. More information: Top 20 pollutants More Statistics: TRI U S A T he U.S. petroleum industry is a strong contributor to the economic health of the United States, its production represents about the 25% of global production. T he Pulp and Paper industry is also important since the U.S. is the world’s largest consumer or these products, both in total tones per year and in terms of consumption per capita.

12. U S A

13. Gas naturalAmmonia Fertilizers More information M E X I C O Petroleum industries provide raw material for the chemical industry.e.g. Hazardous Pollutants produced by Industry I n Mexico, the petroleum industry development is strongly linked to the employment rate, inflation, economic growth and capital investment.

14. As we showed in the statistics section, there are two industries which are very important for the economy and development and also are causing serious environmental problems, making a link between the three countries. This research is attempting to show the way in which Process Integration can be used successfully. For this challenge we use the two major industries in North America: Pulp and Paper Petroleum

15. No energy industry today is more engaged than petroleum in serving the global transportation, power generation, agricultural and consumer products sectors. Oil and natural gas are essential drivers of economic growth, that implies enormous social and environmental responsibilities.. PETROLEUM INDUSTRY

16. 2. Petroleum Industry 2.1 Driving forces, hurdles and potential. 2.2 The Petroleum Refining Industry 2.2.1 Definition 2.2.2 Primary Products 2.2.3 Industrial Processes in the Petroleum Refining Industry 2.2.4 Refinery flow diagram 2.3 Environmental discharges. 2.3.1 Refinery air emission sources 2.3.2 Types of wastewater produced in refineries 2.3.3 Refinery Residuals 2.3.4 Environmental discharges by process 2.4 Regulatory issues in North America. 2.4.1 U.S. Regulations 2.4.2 Mexican Regulations 2.4.3 General Regulations 2.5 Best available environmental technologies for specific processes

17. RELIABILITY OF SUPPLY Any nation’s ability to sustain domestic development will depend on a ready resource of fuels and feedstock. No other energy supplier today is more capable of assuring such a continuity of supply than the petroleum industry. ENVIRONMENTAL PROTECTION Environment should be protected in order to achieve a sustainable development. REASONABLE PRICE These three characteristics can act as: The petroleum industry is one of the most capital-intensive, high-maintenance, heavily regulated and excessively taxed industries operating worldwide. • DRIVING FORCES • HURDLES • POTENTIALS 2.1 DRIVING FORCES, HURDLES AND POTENTIALS The characteristics of the Petroleum Industry are related. In order to understand them, the following diagram in shown. According to Abdallah S. Jum’ah, president of Saudi Aramco, energy today, must have three characteristics which are totally interdependent: In order to secure reliable supplies of oil and natural gas, there must be a price mechanism sufficiently fair and stable to maintain inflows of investment capital. In turn, the investment will help fund the industry’s considerable measures to protect environment. First beak volume 20. 10 October 2002

18. The petroleum refining industry is a strong contributor to the economic health of the United States and Mexico. • For Mexico, this industry has become the most important part in the national economy, it is the first 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. DRIVING FORCES Economic and environmental situations are involved in the development of the petroleum industry, but its final challenge must be to fulfill the society needs.

19. Volatile crude prices HURDLES The petroleum industry has been dramatically impacted over the last three decades by geopolitical disruptions and volatile world oil prices. Today refiners must deal with: Crude quality variability Low marketing and transport profit margins Increasing capital and operating costs of environmental compliance.

20. HURDLES • The environmental impact produced by the petroleum industry covers the effects of all and each step in the energetic cycle, which means: • explotation • extraction • refining • transportation • storage • consumption • releases

21. The natural source itself and the reliability of supply must be the greatest potential for the country that posses them. Technology plays an important role in developing the petroleum industry. Also, research and development have a great deal to do with keeping petroleum prices reasonable. In the past, new technologies had improved our methods of exploration and production, along with downstream efficiencies that yield cleaner-burning automotive fuels and higher-value products from every barrel of crude oil, allowing the increase and the improvement of the industry. The U.S. is the largest, most sophisticated producer of refined petroleum products in the world, representing about 25% of global production. POTENTIALS Social and environmental issues will be decisive for the framework conditions for the future oil and gas industry. Technology is a tool that could help in achieving this task.

22. 2.2 PETROLEUM REFINING INDUSTRY 2.2.1 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.

23. motor gasoline, diesel and distillate fuel oil, jet fuel, residual fuel oil, kerosene and coke naphtha, ethane, propane, butane, ethylene, propylene, butylenes, butadiene, benzene, toluene and xylene solvents, lubricating oils, greases, petroleum wax, petroleum jelly, asphalt and coke These products are used as primary input to a vast number of products: fertilizers, pesticides, paints, waxes, thinners, solvents cleaning fluids, detergents, refrigerants, anti-freeze, resins, sealants, insulations, latex, rubber compounds, hard plastics, plastic sheeting and synthetic fibers. 2.2.2 The primary products of this industry are divided into three categories: CHEMICAL INDUSTRY FEEDSTOCKS FINISHED NON FUEL PRODUCTS FUELS

24. 2.2.3 INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY In order to understand where the environmental discharges come from, we will make a review of the refining process. The process of oil refining involves five major processes which are briefly described: SEPARATION CONVERSION TREATING BLENDING AUXILIARY SEPARATION PROCESSES These processes involve separating the different fractions of hydrocarbon compounds that make up crude oil base on their boiling point differences. Additional processing of these fractions is usually needed to produce final products to be sold within the market. ASSOCIATED OPERATIONS • Atmospheric distillation • Vacuum distillation • Light ends recovery (gas processing)

25. 2.2.3 INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY SEPARATION CONVERSION TREATING BLENDING AUXILIARY ASSOCIATED OPERATIONS CONVERSION PROCESSES • Cracking (thermal and catalytic) • Reforming • Alkylation • Polymerization • Isomerization • Coking • Visbreaking Include processes used to bread down large longer chain molecules into smaller ones by heating using catalysts.

26. 2.2.3 INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY SEPARATION CONVERSION TREATING BLENDING AUXILIARY ASSOCIATED OPERATIONS TREATING PROCESSES Petroleum-treating processes are used to separate the undesirable components and impurities such as sulfur, nitrogen and heavy metals from the products. • Hydrodesulfurization • Hydrotreating • Chemical sweetening • Acid gas removal • Deasphalting

27. 2.2.3 INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY SEPARATION CONVERSION TREATING BLENDING AUXILIARY BLENDING/COMBINATION PROCESSES These are used to create mixtures with the various problem fractions to produce a desired final product, some examples of this are lubricating oils, asphalt, or gasoline with different octane ratings. ASSOCIATED OPERATIONS • Storage • Blending • Loading • Unloading

28. 2.2.3 INDUSTRIAL PROCESSES IN THE PETROLEUM REFINING INDUSTRY SEPARATION CONVERSION TREATING BLENDING AUXILIARY 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. ASSOCIATED OPERATIONS • Boilers • Waste water treatment • Hydrogen production • Sulfur recovery plant

29. LPH and Gas Refinery fuel gas Gasoline Sweet Gasoline LPG Stabilizer Naphta Gasoline Middle Distillates Middle Distillates Solvents Aviation fuels Gas Atmospheric Distillation Gasoline Diesels Gas Oil Treating and Blending Light Gas Oil Heating oils Lube oils Lube-Base Stocks Lube Oil Waxes Greases Gasoline, Naphtha and Middle distillates Asphalts Vacuum Distillation Fuel Oil Industrial fuels Asphalt Refinery fuel oil 2.2.4 REFINERY FLOW DIAGRAM Sweetening Unit Hydrotreating Washed Crude Catalytic Cracking Solvent Extraction and Dewaxing Visbreaker

30. 2.3 ENVIRONMENTAL DISCHARGES • Now, that we have seen an overview of the Refinery Process, we can make some questions: • What is this industry discharging? • How is it discharged? • Where does it come from? In order to answer these questions, this section will show: • Air emission sources • Wastewater sources • Residuals • Environmental discharges by process

31. 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. 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 TAND EMISSIONS released when product is transferred to and from storage tanks. 2.3.1 REFINERY AIR EMISSIONS SOURCES

32. 2.3.2 TYPES OF WASTEWATER PRODUCED IN REFINERIES • 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. 2.3.3 REFINERY RESIDUALS Most refinery residuals are in the form of sludge, spend caustics, spend process catalysts, filter clay, and incinerator ash. These residuals could be classified as follows: • 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. 2.3.4 DISCHARGES LIQUID EFFLUENTS AIR EMISSIONS Approximately 3.5-5 cubic meters of wastewater per ton of crude are generated when cooling water is recycled. 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 or the presence of toxic organics and heavy metals.

35. 2.3.4 ENVIRONMENTAL DISCHARGES BY PROCESS PART 1

36. 2.3.4 ENVIRONMENTAL DISCHARGES BY PROCESS PART 2

37. 2.3.4 ENVIRONMENTAL DISCHARGES BY PROCESS PART 3

38. 2.3.4 ENVIRONMENTAL DISCHARGES BY PROCESS PART 4

39. Requirements mandating specific product qualities for the purpose of reducing the environmental impacts associated with the downstream use of the product. Requirements directed at reducing the environmental impacts of the refineries themselves. 2.4 REGULATORY ISSUES IN NORTH AMERICA The Petroleum Refining Industry is unique in that the environmental requirements aimed at the industry are of two basic types: For the purpose of this module, we focus on refineries, which will be used to show some Process Integration techniques. Petroleum refineries are complex plants, and the combination and sequence of processes is usually very specific to the characteristics of the raw material and the products. For this reason the regulations for this sector become very specific and dispersed because an unit have regulations for water, air and land discharges, all of these managed by different official documents.

40. 2.4.1 U.S. REGULATIONS EPA website In the case of the United States, there are numerous federal regulations affecting the Refinery Industry. The Environmental Protection Agency (EPA) contains several regulatory documents depending on the kind of resource that they pretend to protect, (e.g. Air, water and soil). Each one of these documents presents requirements which apply for every industrial sector. Then, when the requirements for a certain industry are needed, specific parts of the document should be used. For example, The Clean Air Act Amendments of 1990 has some programs for reducing air emissions from industry in which refineries are included: New Source Review, New Source Performance Standards National Emission Standards for Hazardous Air Pollutants At the same time, the New Source Performance Standards have some sections for Refineries: Subpart J Standards of Performance for Petroleum Refineries Subpart KKK Standards of Performance for Volatile Organic Liquid Storage Vessels. Subpart GG Standard of Performances for Stationary Gas Turbines. Subpart GGG Standards of Performance for Equipment Leaks of VOC in Petroleum Refineries

41. 2.4.1 U.S. REGULATIONS All these sections contain flow diagrams, where depending on the process that is being used, it must be applied certain norm. To find more information: http://www.tnrcc.state.tx.us/permitting/airperm/opd/60/60hmpg.htm

42. FEDERAL REQUIREMENTS AFFECTING THE REFINERY INDUSTRY

43. 2.4.2 MEXICAN REGULATIONS 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 Then, if the complete document is needed, you can check here: http://cronos.cta.com.mx/cgi-bin/normas.sh/cgis/index.p

44. 2.4.3 GENERAL REGULATIONS Solid Wastes 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. Besides all these complicated regulations, an specialized agency of the United Nations, 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. Emissions from the Petroleum Industry (milligrams per normal cubic meter) Effluents from the Petroleum Industry (milligrams per liter) World Band Group, 1998. Pollution Prevention and Abatement Handbook. World Bank Group. Pages 377-381.

45. 2.5 ENVIRONMENTAL TECHNOLOGIES USED IN THE PETROLEUM INDUSTRY Primary wastewater treatment Consists on the separation of oil, water and solids in two stages. 1st stage API separator or Corrugated plate interceptor. More information about the equipment www.panamenv.com Physical methods may include the use of series of settling ponds with a long retention time, or the use of dissolved air flotation (DAF). 2nd stage Chemical and physical methods are utilized to separate emulsified oils from the wastewater. More information about the equipment www.panamenv.com Chemicals, such as ferric hydroxide or aluminum hydroxide are used to coagulate impurities.

46. 2.5 ENVIRONMENTAL TECHNOLOGIES PETROLEUM INDUSTRY Secondary wastewater treatment Dissolved oil and other organic pollutants may be consumed biologically. Biological treatment may require oxygen through different techniques: • Activated sludge units • Trickling filters • Rotating biological contactors. Polishing Some refineries employ it as an additional stage of wastewater treatment to meet discharge limits. Generates bio-mass waste which is treated anaerobically. • Activated carbon • Anthracite coal • Sand

47. 2.5 ENVIRONMENTAL TECHNOLOGIES PETROLEUM INDUSTRY Gas treatment and Sulfur Recovery In order to meet the SOx emissions limits and to recover saleable sulfur, refinery process off-gas streams should be treated. These fuel gases (methane and ethane) need to be separated before elemental sulfur can be recovered. • This is accomplished by: • Dissolving the hydrogen sulfide in a chemical solvent such as diethanolamine (DEA) in an absorption tower. • Using dry adsorbents such as molecular sieves, activated carbon, iron sponge and zinc oxide. Process off-gas streams contain high concentrations of: hydrogen sulfide + light refinery fuel gases. Is then heated and steam stripped to remove the hydrogen sulfide gas. Amine + hydrogen sulfide Two processes are typically combined to remove sulfur from the hydrogen sulfide gas streams: hydrogen sulfide Beaven Process Scot Process Wellman-Land Process Claus Process

48. 2.5 ENVIRONMENTAL TECHNOLOGIES PETROLEUM INDUSTRY Gas treatment Other emissions sources come from periodic regeneration of catalysts, these emissions may contain: high levels of carbon monoxide + particulates + VOCs. www.e2t.com/E2T/app_pc05.htm CARBON MONOXIDE BOILER To burn carbon monoxide and VOCs Before being released to the atmosphere ELECTROSTATIC PRECIPITATOR OR CYCLONE SEPARATOR To remove particulate matter More information: www.ppcesp.com Solid waste treatment Sludge treatment use bioremediation or solvent extraction, followed by combustion of the residues or by use for asphalt. The residue could require stabilization before disposal to reduce the leachability of toxic metals.

49. As we showed in the statistics section, there are two industries which are very important for the economy and development and also are causing serious environmental problems, making a link between the three countries. This research is attempting to show the way in which Process Integration can be used successfully. For this challenge we use the two major industries in North America: Pulp and Paper Petroleum

50. PULP AND PAPER INDUSTRY The uses and applications for paper and paper products are limitless. It is important because it gives us the opportunity or recording, storage and dissemination of information. Also, it is the most widely used wrapping and packaging material and it is also used for structural applications.