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Program for North American Mobility in Higher Education Introducing Process Integration for Environmental Control in Engineering Curricula Module 4: Environmental.

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1 Program for North American Mobility in Higher Education Introducing Process Integration for Environmental Control in Engineering Curricula Module 4: Environmental Challenges – Pulp & Paper Industry Caroline Gaudreault Created at: École Polytechnique de Montréal & Texas A&M University, 2003

2 2 Purpose of Module X What is the purpose of this module? This module is intended to overview the environmental challenges of the pulp & paper industry and, more specifically, the reduction of environmental impacts related with the kraft pulping process.

3 3 Structure of the Module X What is the structure of this module? Module X is divided into 3 “tiers”, each with a specific goal: Tier 1: Basic introduction Tier 2: Case study applications Tier 3: Open-ended problem These tiers are intended to be completed in order. Students are quizzed at various points, to measure their degree of understanding, before proceeding. Each tier contains a statement of intent at the beginning, and a quiz at the end.

4 4 LEGEND Go to the web site Go to next subject More information on the same subject Look for the answer to the question

5 Tier I: Background Information

6 6 Tier I: Statement of Intent The purpose of this module is to provides a general overview of the concepts related to minimum impact manufacturing in the Kraft process, and an introduction to pertinent PI tools. Tier 1 also includes some selected readings, to help the student acquire a deeper understanding of this subject.

7 7 Tier I: Content Tier I is broken into three sections: 1.1 Introduction to the kraft pulping process, its related environmental impacts and related regulations 1.2 Introduction to minimum impact manufacturing 1.3 Related PI tools At the end of Tier I, there is a short multiple- answer quiz

8 1.1 Introduction to the kraft pulping process and its related environmental impacts and related regulations

9 9 General Description of the Kraft Pulping Process  The kraft process is a form of chemical pulping. This means that, in order to degrade and dissolve away the lignin and keep most of the cellulose and hemicellulose, the wood chips are cooked with appropriate chemicals in an aqueous solution at elevated temperature and pressure. The main challenge is to form fibers that are practically intact.  More specifically, the kraft process involves cooking of the chips using a solution of sodium hydroxide (NaOH) and sodium sulfide (Na 2 S)  One major characteristic of the kraft process is that the cooking chemicals are regenerated in a recovery process that will be discussed later.

10 10 Advantages and Disadvantages of Kraft Process Advantages:  High strength pulp  Utilizes proven technology for chemical recovery  Handles with a wide variety of wood species  Tolerates bark in the pulping process Disadvantages:  Unbleached pulp is characterized by a dark brown color  It is associated malodorous gases (organic sulfides)

11 11 Definitions and Nomenclature (1) White liquor: Liquor containing the active cooking chemicals (NaOH and Na 2 S) and used to cook chips. Black liquor: Residual liquor from cooking containing the reaction products of lignin solubilization. This liquor is concentrated and burnt into a recovery furnace and yields an inorganic smelt of Na 2 CO 3. Green liquor: Liquor obtained by dissolving the latter smelt. The green liquor is reacted with CaO in order to convert the Na 2 CO 3 in NaOH and regenerate the white liquor. Cooking & Washing Chips Pulp Evaporation & Burning Causticizing BLACK LIQUOR Alkali lignin Hydrolysis salts Sulphonation products WHITE LIQUOR NAOH NA 2 S GREEN LIQUOR Na 2 CO 3 Na 2 S The kraft sodium cycle (Source:Smook, 1994)

12 12 Definitions and Nomenclature (2) TERMDEFINITIONUNITS Total Alkali Total of all viable sodium alkali compounds i.e. NaOH + Na 2 S + Na 2 CO 3 + Na 2 SO 4 + Na 2 S 2 O 3 + Na 2 SO 3 (does not include NaCl) g/L as Na 2 O Total Titrable Alkali (TTA)Total NaOH + Na 2 S + Na 2 CO 3 g/L as Na 2 O Active Alkali (AA)Total NaOH + Na 2 Sg/L as Na 2 O Effective Alkali (EA)Total NaOH + ½ Na 2 Sg/L as Na 2 O ActivityAA / TTA ratio% CausticityNaOH / [NaOH + Na 2 CO 3 ] ratio% (on a Na 2 O basis) SulfidityNa 2 S / AA (or TTA) ratio% (on a Na 2 O basis) Causticizing Efficiency (White liquor) Same as causticity. (However, the concentration of NaOH in the green liquor should be subtracted so that the value of NaOH represents only the portion produced by the causticizing reaction.) % (on a Na 2 O basis) Residual Alkali (Black liquor)Alkali concentration determined by titrationg/L as Na 2 O Reduction Efficiency (Green liquor) Na 2 S / (soda sulfur coumpounds) ratio (often simplified as Na 2 S / [Na 2 S + Na 2 SO 4 ] ratio) % (on a Na 2 O basis) (Source:Smook, 1994)

13 13 Sodium vs. Calcium Cycle (Adapted from European Comission IPPC, 2001)

14 14 Wood Fibers Pulp fibers are manufactured by chemically dissolving those wood components (mainly lignin) that keep wood cells together to form the original wood structure by minimizing the damages to these components. Wood Lignin Extractive Carbohydrates Terpenes Resin acids (softwood) Fatty acids Phenols Unsaponifiables 2-8% 21% Hardwoods 25% Softwoods Hemicellulose Cellulose 45% 35% Hardwoods 25% Softwoods Glucose Mannose Galactose Xylose Arabinnose Glucose Chemical Components of Wood Structure of cellulose Source: Smook, 1994

15 15 Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Pulp to bleaching Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994

16 16 Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Pulp to bleaching Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994  The wood is mechanically debarked and cut into chips that are screened prior the chemical treatment.  Lignin and some carbohydrate material are dissolved from wood chips during cooking in aqueous solution of alkaline, neutral or acidic components at elevated temperature and pressure.  Chips maintain their wood structure during chemical pulping but this latter is so weak that it will break down to individual fiber by modest mechanical action.

17 17 Overview of the Kraft Process Digester Chips Blow tank Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994  Washing: Spent inorganic and dissolved organic materials are separated from the pulp by multistage counter-current washing system. Spent liquor is sent to the regeneration system.  Screening: Solid impurities contained in the washed pulp (mainly incompletely delignified wood and knots) are separated by screening. The rejects are reprocessed.  Bleaching: Depending in the intended application, pulp can be bleached. Pulp made by the kraft process is darker than the original wood. Bleaching is the purification process that modify colored substance so they either loose their light absorption ability or they dissolve. Pulp Washers Bleaching

18 18 Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994 In order to be used as a fuel, kraft liquor must be evaporated in a multistage evaporation system. Pulp Bleaching

19 19 Bleaching Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994  The strong black liquor is then burned in a recovery furnace where inorganic substances are converted into regenerable substances.  Sodium and sulfur salts are converted to a smelt of Na 2 S and Na 2 CO 3 and brought to a dissolved tank Pulp

20 20 Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994 The smelt is dissolved in weak wash liquor from the recausticizing plant. Pulp Bleaching

21 21 Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Source: Smook, 1994 Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994 The green liquor is clarified. Pulp Bleaching

22 22 Overview of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994 The green liquor is causticized with reburned lime to form white liquor:  CaO and water are reacted in a slaker to form CaOH, which in turn reacts with Na 2 CO 3 in the green liquor to form NaOH and CaCO 3.  The CaCO 3, which is insoluble, is separated by filtering and is washed free from sodium salts.  It is then calcinated in a lime kiln to CaO and reused.  The regenared white liquor is reused in cooking. Pulp Bleaching

23 23 Pollutants in the P&P Industry What is a pollutant? A pollutant is “a substance that can alter the natural environment” (Springer and al., 2000). US EPA classification of pollutants Oxygen-demanding substances Disease-causing agents Synthetic organic compounds Plant nutrients Inorganic chemical and mineral substances Sediments Radioactive substances Thermal discharges

24 24 Environmental Impacts of the Kraft Process Digester Chips Blow tank Washers Weak black liquor storage Evaporators Strong black liquor storage White liquor clarifier Causticizers Slaker Green liquor storage Green liquor clarifier Dissolving tank Recovering furnace Lime mud washer Lime mud thickener Lime kiln Dregs washer Weak liquor storage White liquor storage Water Contaminated condensates Pulp Grits Lime Weak Liquor storage Lime mud Water Dregs Smelt Source: Smook, 1994 Wood preparation To learn about major environmental impacts of the kraft process: Click on the yellow then pink boxes! Bleaching

25 25 Wood Preparation Air Pollution: Transportation of logs, production, screening, transportation and storage of chips as well as debarking activities can result in the emission of particulate matters. That are extremely difficult to measure. Another type of fugitive emission associated with wood preparation activities is gaseous such as volatile organic compounds (VOC). Water Pollution: Water is used for 3 purposes: log conveyance?, log washing and wet debarking. Return to the flowsheet For more information

26 26 Pulp Production Air Pollution: The cooking process results in formation and releases of VOC’s and reduced components (TRS) that are odorous. These compounds can exit the digester either in gaseous or liquid form. The gas are sent to condensers to remove water and other condensable compounds. The non-condensable gas are incinerated in order to eliminate the odorous ones. The remainder are condensed and used to pre-heat the chips. Water Pollution: Wood chips are cooked in aqueous solution. Return to the flowsheet For more information

27 27 Pulp Washing, Screening and Deknotting Air Pollution: The pulp washing, screening and deknotting do not result in new pollutant but volatile compounds contained in the pulp can escape during those operations. Water Pollution: Pulp is washed to remove pulping chemicals and soluble wood components and diluted with water. Return to the flowsheet For more information

28 28 Bleaching: Oxygen Delignification (OD) – Air Pollution In OD, steam, caustic (as oxidized white liquor), and oxygen are added to the pulp in order to reduce the lignin content before further bleaching. VOC’s are present in the incoming pulp, white liquor and washer shower water and can be released. CO 2 and CO are formed in the reactor during the delignification.

29 29 Bleaching – Air Pollution Bleaching occurs in a multistep process involving the use of chemicals that will oxidize and dissolve the lignin. Following this process, the cellulose and the hemicellulose will be separated from the undesirable material. This process also involves chemical utilization. Traditionally, chlorine was used in the first stage of bleaching but it was replaced by ClO 2 because of the possible formation of unwanted chlorine compounds. Use of sodium hypochlorite in the third stage has also mostly been discontinued because of concerns related with chloroform and AOX formation. Exhausts gases from bleaching will contain VOC’s, unreacted bleaching chemical, and inadvertently formed compounds. Most VOC’s are returned to the unbleached pulp slurry. It is also possible that ClO 2 and Cl are present in small amounts in the bleach plant gases. CO is mostly formed in the first stage of bleaching.

30 30 Bleaching – Water Pollution Different chemicals are used in a multi-stage process to bleach the pulp. Aqueous washing is performed between stages to remove bleaching chemicals and any dissolved wood components extracted during bleaching. Water is also used to prepare bleaching chemical solutions and in air emission control scrubbers. Because waste water from bleaching usually has a high content in content in chlorine, it is incompatible with chemical recovery process and it is sent directly to the wastewater treatment. Return to the flowsheet For more information

31 31 Chemical Recovery: Evaporation Air Pollution: Following the cooking, the spent cooking liquor referred to as weak black liquor. This liquor is composed of around 85% water and 15% solids that are a complex mixture of sulfur and sodium containing organic and inorganic compounds. During the evaporation of water, gaseous volatile compounds can be formed. Also, because of the presence of sodium sulfide in Kraft cooking liquor, TRS compounds can be released during the evaporation. To avoid bad odors, these gas are sent to combustion in order to oxidize the TRS. Water Pollution: Water from weak black liquor is evaporated and the condensates from the evaporators comprise the excess water from liquor concentration. These condensates can be reused in other processes but excess condensates are discharged to the wastewater treatment. The condensates can contain high level of TRS, methanol and acetone. Return to the flowsheet For more information

32 32 Chemical Recovery: Recovery Furnace – Air Pollution When the liquor has a minimum of 60% solids, it is sent in the recovery furnace where the organic compounds are burnt and the inorganic compounds transformed in a molten smelt. The recovery furnace is the recovery furnace is the predominant source of TRS emissions. Particulates such as sodium sulfate and sodium carbonate are also emitted by the recovery furnace. Potassium compounds and other metals can be present in smaller quantities. Recovery furnaces also emit SO 2, NO x, CO, volatile organic compounds and other products from incomplete combustion. There is also a potential for SO 3, H 2 SO 4, HCL and NH 3 emissions. There are possibilities for other chlorinated compounds emissions but in very small quantities. Return to the flowsheet

33 33 Chemical Recovery: Dissolving and Clarification – Air Pollution Molten smelt drains from the furnace to a tank and the smelt is broken up with steam. The smelt particles fall into an agitated solution of weak wash. The mixture is called green liquor that is pumped to the clarifier where suspended solids are removed. Most of the emissions from the dissolving tank are TRS and particulate matter that are similar to the ones from the recovery furnace. VOC and NH 3 can also be released. Return to the flowsheet

34 34 Chemical Recovery: Lime Kiln Return to the flowsheet Air Pollution: Lime mud is calcinated to form CaO and CO 2 in the lime kiln. Most of the emissions from the lime kiln are TRS and particulate matter. SO 2 emissions are low because of the alkaline atmosphere in the lime kiln. Lime kiln can also emit NO x, CO and VOC from incomplete combustion. Water Pollution Water is used to wash the solid precipitates formed in the recovery cycle. Washing recovers sodium and sulfur containing from green liquor dregs and lime mud. This weak wash is reused to dissolve recovery furnace and the excess is sent to the wastewater treatment. For more information

35 35 Chemical Recovery: Slaker – Air Pollution CaO from the kiln and green liquor from the dissolving tank are mixed together to give NaOH, CaCO 3. A large amount of steam that must be ventiled is formed. The steam contains a lot a particulate matter that are mostly calcium and sodium carbonates and sulfates. NH 3 can also be formed. Return to the flowsheet

36 36 Chemical Recovery Other Causticizing Area Equipment Air Pollution: Other equipment associated with the processing of green liquor (clarifiers, storage, surge tanks and dregs washers), white liquor (causticizers tanks, clarifiers, pressure filters and storage tanks), and lime mud (mix tanks, dilution tanks, storage tanks, pressure filters and pumps) can vent to the atmosphere. However, gas flow rates such as VOC and NH 3 from this equipment are usually very small and concentrations low. Return to the flowsheet

37 37 Representative Bleached Kraft Mill Water Loads  The highest volume of discharges comes from the paper mill.  The largest BOD loads occur at the bleach plant.  The paper mill process the highest amount of TSS. (Source: Springer and al., 1997) Return to Lime KillnReturn to EvaporationReturn to BleachingReturn to Pulp Washing Return to Pulp ProductionReturn to Wood Preparation

38 38 Most Impacting Environmental Regulations  Legislation is one of the drivers for implementing environmental changes and it is also recognized as a important factor to conserve an advantage over competitors.  Also, there is a consensus that legislations will be more and more stringent over the next 25 years.  For this reason, the regulations that have the most significant impact on the pulp and paper industry will be described in the following slides.  The importance of legislation as well as of other drivers for environmental change will be described in tier II.

39 39 US EPA Clean Water Act  The Clean Water Act launched in 1977 established the basic structure for regulating discharges of pollutants into the waters of the United States. By this, the USEPA has the authority to implement pollution control programs (e.g. setting wastewater standards for industry).  It aims at reducing direct pollutant discharges into waterways, finance municipal wastewater treatment facilities, and manage polluted runoff using regulatory and non-regulatory tools.

40 40 US EPA Cluster Rule  The US EPA Cluster Rule integrates air and water regulations.  It was first published in 1998 and was applying to bleached paper grade kraft, soda and paper grade sulfite mills.  Key features of the Cluster Rule are: Implementation within 3 years; Bleach plant eflluent limitations for dioxin, chlorinated phenolics, and chloroform; AOX limitations; Establishment of best management practices (BMP) for control of spills of spent pulping liquor, turpentine and soap; Encouragement of project XL; No Change on BOD and TSS limits; No limits on color, methylene chloride, or methy ethyl ketone; No current COD limitations, but it changes in the future.

41 41 US EPA Project XL Project XL stands for "eXcellence and Leadership” and is a US pilot program that allows state and local governments, businesses and federal facilities to develop with EPA innovative strategies to test better or more cost-effective ways of achieving environmental and public health protection. Project XL has 8 selection criteria: 1.Produce superior environmental results beyond those that would have been achieved under current and reasonably anticipated future regulations or policies; 2.Produce benefits such as cost savings, paperwork reduction, regulatory flexibility or other types of flexibility that serve as an incentive to both project sponsors and regulators; 3.Supported by stakeholders; 4.Achieve innovation/pollution prevention; 5.Produce lessons or data that are transferable to other facilities; 6.Demonstrate feasibility; 7.Establish accountability through agreed upon methods of monitoring, reporting, and evaluations; and 8.Avoid shifting the risk burden, i.e., do not create worker safety or environmental justice problems as a result of the experiment. In addition, projects must present economic opportunities and incorporate community planning.

42 42 Industrial Depollution Attestations (Quebec) Program for Industrial Waste Reduction: The Program for waste reduction was launched in Quebec Ministry of Environment has developed an intervention strategy integrating all receiving medias. The target industrials sectors were those whom contaminant rejects, more specifically releases of toxic substances had the largest impacts on local environments. Industrial Depollution Attestations: The Industrial Depollution Attestation is the legal tool that allows the ministry to operationalyze the Program for Waste Reduction.

43 43 Industrial Depollution Attestations (Quebec)  The Industrial Depollution Attestation is a permit, renewable every 5 years, that establishes the environmental conditions under which the industry must operate.  The Industrial Depollution Attestation main components are: Reject standards to respect; Requirements related to rejects follow-up; Other operation conditions as determined by the ministry; Studies to perform; Due dates and additional requirements.  Targeted Sectors: Pulp and Paper (is the only one to have completely implemented the program to date); Mines and Metallurgy; Organic and Inorganic Chemistry; Agri-food industry, wood transformation and textiles.

44 44 Integrated Pollution Prevention and Control (IPPC) - Europe What is the IPPC: The IPPC is a European set of common rules on permitting for industrial installations. The aims of the IPPC Directive is to minimize pollution from various point sources throughout the European Union. Permits, based on the concept of Best Available Techniques (or BAT), are necessary to certain industry to be able to operate.

45 45 Kyoto Protocol and GHG Mitigations Climate change is a problem which affects all countries. Many human activities emit greenhouse gases (GHGs) to the atmosphere ( heating and cooling buildings, using energy,transportation, industrial processes, etc.). When in contact with the sun radiations, the GHGs act like a greenhouse's glass to block this heat from escaping back to space increasing the earth temperature. In1997, more than 160 countries met in Kyoto (Japan), and agreed to targets to reduce GHG emissions. This agreement is called the Kyoto Protocol. Canada's target is to reduce its GHG emissions to 6 percent below 1990 levels by the period between 2008 and The Protocol will only become legally binding when it is ratified by at least 55 countries, covering at least 55 per cent of the emissions addressed by the Protocol. Neither USA or Mexico have ratified the protocol. At this time (May 2004) the implementation is pending ratification by either USA or Russia.

46 46 GHG Mitigations & Pulp and Paper In 2003, the Forest Products Association of Canada has sign an agreement with the Canadian government concerning the GHG emissions which includes a commitment by the industry to reduce its greenhouse gas (GHG) emissions intensity by an average of 15 percent by 2008 to 2012, the first Kyoto commitment period.

47 47 References  ENVIRONNEMENT QUÉBEC Le Programme de réduction des rejets industriels et l’attestation d’assainissement. (page consulted in 2004)  EUROPEAN COMISSION. Integrated Pollution Prevention and Control (IPPC) – Reference Document on Best Available Techniques in the Pulp and Paper Industry. 2001, 475 p.  Gullichsen, J. Fogelholm, C-J. (eds). Papermaking Science and Technology, Chemical Pulping, Book 6A. Tappi Press, Helsinki, Finland, 2000, 693 p.  SMOOK, G.A. Handbook for pulp & paper technologists. 2 nd ed. Angus Wilde Publications, Vancouver, Canada, 1992, 419 p.  SPRINGER, Allan M. (ed.) Industrial Environmental Control – Pulp and Paper Industry. 3 rd ed. Tappi Press, Atlanta, USA, 2000, 711 p.  USEPA Project XL. (page consulted in 2004)http://www.epa.gov/ProjectXL/  USEPA Industrial Water Pollution Controls. (page consulted in 2004).

48 1.2 Introduction to minimum impact manufacturing (MIM)

49 49 Content A.MIM concepts B.Progressive water system closure and build-up of NPE’s C.Zero discharge concepts D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

50 50 Content A.MIM concepts B.Zero discharge concepts C.Progressive water system closure and build-up of NPE’s D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

51 51 Weyerhaeuser’s Vision of MIM Minimum impact manufacturing (MIM) concept has first been introduced by Weyerhaeuser: “Using a Minimum Impact Manufacturing strategy, Weyerhaeuser directs its efforts to manufacturing quality products with minimal environmental impact and maximum return to shareholders. The strategy works to prevent pollution by continuously reducing process byproducts and finding ways to capture, reuse or recycle them.” (Weyerhaeuser website, 2004)

52 52 Weyerhaeuser’s Vision of MIM For a production facility MIM includes Weyerhaeuser's commitment to strive to close the loop by further:  Optimizing raw materials used at the mill level  Reducing water usage  Minimizing fossil fuel for energy in manufacturing  Reducing/eliminating hazardous waste  Generating less solid waste  Reducing emissions to all media  Eliminating spills  Reusing and recycling from our mills the materials and residuals that previously went to landfills  Collecting and recycling used waste paper for use as a raw material (Weyerhaeuser website, 2004)

53 53 Goals of MIM Minimum Impact Manufacturing aims to:  Eliminate process issues before they become environmental problems.  Address multiple environmental areas, including air and water quality, solid and hazardous waste minimization and more.  Use science and economics to focus on pollution prevention at the source rather than end-of-pipe remedies. (Weyerhaeuser website, 2004)

54 54 Environmental Hiearchy of Needs Acute Impacts on the environment Chronic and/or Long-Term Effects Subtle, Complex, Aesthetic Minimum Impact Resource depletion acute toxicity, raw effluent, etc. Energy, odor, color, biodiversity, etc. Completion of the Forest products cycle Chronic toxicity, bioaccumulation, etc. Source: Erickson, Zacher and Decrease, 1996

55 55 Key Environmental Parameter Related to MIM WaterAirSolid WasteOther  Water Usage  Bleach Plant Effluent Volume  Final Effluent Volume  BOD  COD  TSS  Effluent AOX  Dioxin  Color  Chronic Toxicity  Nutrients  Particulate  TRS  Methanol  Chloroform  Chlorine  Chlorine Dioxide  CO/CO2  NOx  SO2  VOCs  Opacity  HAPS  Solid Waste Generated  Solid Waste Disposition: - Landfill - Recycled - Energy  Reduction Plans/Achievements  Hazardous Waste Elimination  Accidental Releases  Non-Compliant Events  SARA 313 Releases  Energy Use/Energy Exports  Aesthetics: - Site Appearance - Odor - Noise  Improvement Projects Chemical Management  Key Environmental Accomplishments

56 56 Content A.MIM concepts B.Zero discharge concepts C.Progressive water system closure and build-up of NPE’s D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

57 57 Goal of Process Closure The goal of process closure with respect to effluent discharges is to minimize the amount of waste generated. This can be accomplished by: Using more efficient processes; Using processes that do not require water; Recovering the waste materials. (Source, NCASI, 2003)

58 58 Rapson-Reeve Process  In 1967 Rapson proposed a bleached kraft pulp manufacturing process that had the potential to greatly reduce, if not eliminate, effluent discharges.  The idea was based on a collection of technologies, including incresed use of chlorine dioxide for bleaching and a process for generating this chemical that could be fully integrated with the chemical requirements of the kraft pulping and bleaching processes.  The driver for this process was a cost effective alternative to the biological effluent treatment.  The process was implemented by the Great Lakes Paper mill in Thunder Bay, but abandoned.

59 59 Rapson-Reeve Process The original effluent-free mill concept was based on the following ideas: Replace 70-80% of the chlorine in the chlorination stage with an equivalent amount of chlorine dioxide. Use a new chlorine dioxide generating process. Use countercurrent washing in bleach plant, using wastewater from the wet end of the pulp dryer or paper machine to minimize de volume of filtrate to be recovered. Use a portion of the bleaching filtrate to wash the unbleached filtrate, allowing the dissolved from bleaching to be recovered via evaporation and burning. Use the remainder of the bleaching filtrate to wash the lime mud and green liquor dregs and to dissolve the smelt from the recovery furnace.

60 60 Rapson Reeve Process Effluent-free concept (Cont’d): Treat the evaporator condensates with a small amount of chlorine dioxide to oxidize the foul-smelling compounds and use the oxidized condensates in place of fresh water on the wet end of the pulp dryer or paper machine. Remove the sodium chloride from the liquor cycle by extracting it from the recovery furnace flue gas in the electrostatic precipitator. A portion of the extract would be used to generate chlorine dioxide for the bleach plant and the remainder would be discarded. Establish closed water systems for wood debarking, pulp screening, and cleaning.

61 61 Main Problems in Making a Mill Effluent- Free  Non-process elements can accumulate.  Pulp quality can be affected.  About one quarter of the water pollution in bleached pulp mills comes from spills and wash-up and are not well controlled.  Calcium trap: when there is any acid stage in the bleaching sequence (ozone), calcium carbonate will travel with the pulp in neutral or alkaline stages, but dissolve in acid stages. If countercurrent washing is used, the calcium will be precipitated into the pulp in any previous alkaline stage and carried forward to be re- dissolved in acid stage.  In order to obtain the appropriated displacement ratio and purge for each stage, the flow of filtrate in and out must be precisely balanced.  In order to minimize the consumption of oxidizing agent in subsequent stages throught incomplete washing, the concentration of organic matter in each filtrate must be carefully controlled.

62 62 Process Closure Technologies Definition: Process closure technologies can be defined as those which effect or enable the reduction of waterborne wastes from pulp manufacturing facilities. They serve to divert wood components and other raw materials from liquid waste streams by prevention, reuse, or recovery. These technologies were largely driven by the desire to limit the discharge of chlorinated organic compounds.

63 63 Zero Discharge Concept  For a majority of pulp mills zero-effluent discharge is impracticable.  Currently, zero effluent operation appears to be restricted to plants producing bleached chemical thermal mechanical pulp and non-chlorine bleaching agents.  Since the bleach plant is the major source of contaminated effluent in a kraft pulp mill, the closure of these circuits is an essential prerequisite for producing a zero-effluent kraft mill.  This requires the simultaneous resolution of a number of problems: water balance, chemicals balance, corrosion, precipitation of salts and removal of non-product substances.

64 64 Low Effluent Kraft Mill Examples Newest Mills of America The 3 newest mills of America were designed to be highly economical and environmentally performing using high capacity, single line facilities, and employing modern technology for pulp production and effluent treatment. None of these mills practices recovery of bleaching wastewaters but their effluent quality is among the best in the world. These mills are: Bahia Sul, Brazil; Alabama Pine Pulp, USA; Alberta-Pacific, Canada.

65 65 Low Effluent Kraft Mill Examples Mill Practicing Recovery of Bleaching Filtrates Linerboard mills: AssiDomän Frövi, Swenden; Kappa Kraftliner (formerly AssiDomän) Piteå, Sweden; SCA Munksund, Sweden.

66 66 Low Effluent Kraft Mill Examples Mill Practicing Recovery of Bleaching Filtrates Bleached papergrade kraft mills: Blue Ridge Paper Products – Canton, North Carolina, U.S.A. International Paper Company – Franklin, Virginia, U.S.A. Aspa Bruk – Smurfit Munksjö, Sweden M-Real Sverige AB – Husum, Sweden SCA Pulp AB – Östrand, Sweden Södra Cell – Mörrum, Sweden Södra Cell – Värö Bruk, Sweden Stora Enso – Skoghall, Sweden Metsä-Botnia – Rauma, Finland UPM-Kymmene Wisaforest – Pietarsaari, Finland

67 67 Content A.MIM concepts B.Zero discharge concepts C.Progressive water system closure and build-up of NPE’s D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

68 68 Progressive Water System Closure Conventional methods to achieve water closure are simple and include: Using counter-current washing in pulping and bleaching operations; Closing brownstock screen room; Using dry debarking; Using evaporator condensate for brownstock washing; Recycling excess whitewater from paper machine to bleach plant; Reusing stripped condensates from steam stripping of foul condensates; Using equipment and process that require less water; Using cooling towers for vacuum pump seal water an non-contact cooling water; Using first bleach stage washer/filtrate to dilute brown high-density stock; Recycle/reuse secondary and/or tertiary treated effluent; Applicating changes to pulping and bleaching practices will further strive to the closure.

69 69 Non Process Elements (NPEs)  NPEs are materials such as potassium (K), phosphorus (P), manganese (Mn), magnesium (Mg), iron (Fe), aluminium (Al), silicon (Si), calcium (Ca), barium (Ba), and chlorine (Cl) that enter the chemical pulping process with the wood, water and chemicals.  When we decrease fresh water consumption, there is a potential for increasing the concentration of some troublesome substances and more specifically NPEs.

70 70 NPEs Consequences  NPEs accumulate in the sodium and calcium cycle in kraft process potentially causing the following consequences: Corrosion of the recovery boiler and other equipment; Deposits on the boiler tubes that reduce heat transfer; Scale in the digester, evaporators, and heat exchangers; Blinding of white liquor and lime mud filters; Reduced reburned lime reactivity; Ring formation in the lime kiln; Increased dust formation in the lime kiln; Increased chemical consumption in bleaching; Reduced effectiveness of ozone and peroxide bleaching.

71 71 NPEs Classification There are to catogories of NPEs: 1.NPEs that form insoluble metal hydroxides or carbonates and are removed from the sodium cycle with the dregs and grits: mostly Ca, Mg, Mn and Si. 2.NPEs that form soluble compounds in alkaline solution: mostly Al, Cl, and K.

72 72 Build-up of NPEs  In an « open » mill the presence of NPEs is not importance since they are purged outside the system.  When progressively closing mill, many outlets are not available anymore. The consequence of this is the build-up of NPEs.  NPEs have a tendency to accumulate in eighter the sodium or calcium cycle in the following way: Sodium Cycle: K > Cl > Al > Fe > Si > Mn > Mg > Ca Calcium Cycle: Mg > Al > Fe > Mn > Si > Na > K > S > Cl  The most troublesome NPEs are K, Cl and Na. Na is the most tricky because it is a process and non- process element at the same time.

73 73 Content A.MIM concepts B.Progressive water system closure and build-up of NPE’s C.Zero discharge concepts D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

74 74 Tracking Models for Water, NPE’s, and Targeted Species Path diagram equation: It is a mass integration tool whose objective is to track targeted species (e.g., NPEs and water) as they propagate throughout the process and provides the right level of details to be incorporated into a mass integration analysis. A typical form of the path equations is to describe outlet flows and compositions from each critical unit as a function of inlet flow, inlet compositions, and appropriate design and operating parameters. Steps for analysis will be described in the following slides.

75 75 Main Characteristic of the Path Diagram Equation In order to optimize water allocation in a pulping process, two important activities can be used together: mass integration and process simulation. Mass integration techniques handle process objectives, data, requirements and constraints. It will allow to fix performance targets, solution strategies, and proposed changes to the process. Learn more about simulation Learn more about Mass integration Because of these changes, the performance must be reassessed using process analysis or simulation. The use of process simulation enables the update of flowrates and compositions throughout the process (Source: Lovelady, 2001)

76 76 1.Degrees of Freedom N V = N S x N C F= N V - N E = N C (N S - 1) F: degrees of freedom N V : number of variables N E : number of equations N C : number of targeted species N S : number of outlet streams Assumptions: All inlets to a unit are known and it is desired to determine the outputs of the unit. F must provided as additional modeling equations, assumptions, measurements, or data in order to have an appropriately specified (determined) set of equations that is solvable. Unit U Inlet stream (Fresh inputs or outlets from other units) Outlet streams N streams out

77 77 2.Mixer-Splitter Model  The mixer-splitter model is a modeling technique which relies on nominal data.  The nominal data are those for the plant prior to any changes and can be obtained via simulation, fundamental modeling, direct measurements, or literature data.  There are various of the mixer splitter model: Fixed split model; Flow ratio model ; Species ratio model.  Based on the knowledge of the process, choices can be made for the selected model and streams/species.  Path equations can be developed for water and targeted NPEs throughout the process.

78 78 Fixed Split Models  The fixed split model adopts a certain split for the flows of the various streams leaving the unit.  This model is useful in predicting flows out of many units, particularly separators. Fixed Split Model F αFαF (1-α)F

79 79 Flow Ratio Model  The ratio model, relates certain streams or components via fixed ratios.  The flow ratio model assumes that inlet and outlet flows of certain streams maintain a certain ratio. Flow Ratio Model F G G 2 = G 1 x F 2 F 1

80 80 Species Ratio Model  The species ratio model is another form of the ratio model.  It assumes relationship between certain species within the same stream via fixed ratios.  This is particularly useful when one component can be accurately tracked while another one cannot. Flow Ratio Model F Specy A = α Specy B = β B 2 = A 2 x (β/α )

81 81 Content A.MIM concepts B.Progressive water system closure and build-up of NPE’s C.Zero discharge concepts D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

82 82 Energy in Kraft Mill  Kraft mills are usually partly energy sufficient: They generate power using sources such as wood wastes and spent pulping liquor. This is very important since CO 2 emissions from renewable sources are not included in the greenhouse gases inventory considered under the Kyoto protocol. The emergence of new technologies will allow the kraft mill to be essentially energy- sufficient in the future.

83 83 Kraft Mill Energy Efficiency To maximize operating profit a mill requires the following technologies: Since black liquor is the largest source of energy in a kraft mill, it is important to use it in an efficient way. A higher solids content will result in more steam produced and less heat going to recovery stack as water vapor. Pulping yield must be increased using new cooking technologies with reduced energy consumption. Washing and screening must be runned at higher consistencies and their performance must be increased in order to reduce the water necessary to wash the pulp. For improved steam economies and evaporation to high solids levels with scaling, modern evaporators with heat treatment can be used.

84 84 Kraft Mill Energy Efficiency To maximize operating profit a mill requires the following technologies: New kiln technology with large precoat filters, flash dryers, product coolers and better insulating brick will reduce lost of heat. Screening and conditioning of chips will reduce fines generation and improve digester yield. Others: Economies of scale are important in terms of energy consumption; Using less water will generally reduce heating requirements; Efficient mill layout will reduce friction loss associated with long piping; Etc.

85 85 Content A.MIM concepts B.Progressive water system closure and build-up of NPE’s C.Zero discharge concepts D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

86 86 Effect of Water Closure on Energy  Effect of reducing water usage on energy flows are strong and complex.  This leads to complex process designs and an increasing need for systematic and system-oriented analysis of energy and water use in the mills.  On of the challenge is to deal with excess heat that increases the temperature of process streams and effluent.  Process integration can be an useful tool to understand this can of problems.

87 87 Content A.MIM concepts B.Progressive water system closure and build-up of NPE’s C.Zero discharge concepts D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

88 88 BAT Concept (Source: European IPPC) BAT: Best Available Technology economically achievable Key characteristics of BATs:  There is no single reference of best available techniques in pulp and paper industry. In contrast, the list of techniques to consider in the determination of BAT provides a lot of different options of an overall BAT for given mills, which may be combined in different ways.  The BAT-concept is process-related because the environmental impact is caused on this level i.e. by different manufacturing processes as for instance cooking, bleaching, de-inking, coating etc. The single processes, the raw materials used and the product properties to be achieved determine the emission of a mill. That means when approaching the pulp and paper industry different types of raw materials used and processes involved have to be distinguished.

89 89 BAT Concept (Source: European IPPC) Key characteristics of BATs (Cont’d):  As pulp and paper products are highly diverse and utilized processes even for one and the same product may vary greatly, many factors of production technology must be taken into account to guarantee a high level of environmental protection. For the pulp and paper industry the best available techniques cannot be defined solely by describing unit processes. Instead, the whole installations must be examined and dealt with as entities. BAT in pulp and paper industry is linked to the environmental performance of mills.  There are different options for suitable combinations of processes depending - besides other things - on the product properties to be achieved. As a consequence, the process-oriented approach has to be extended by a product-oriented concept i.e. the BAT approach must be linked to the environmental performance of specific types of mills where specific products are manufactured. Thus, in this document best available techniques are presented for major mill classes separately.

90 90 BAT - Remark The following programs are based on BAT:  USEPA Cluster Rules;  European IPPC.

91 91 Content A.MIM concepts B.Progressive water system closure and build-up of NPE’s C.Zero discharge concepts D.Tracking models for water, NPE’s, and targeted species E.Kraft mill energy efficiency F.Relation between minimum energy and minimum effluent G.BAT concepts H.Example of application of MIM concept

92 92 Application of MIM Concepts: The Flint River Case Study Description of the mill  Flint River is a Kraft pulp mill located in Georgia, USA.  It is producing tons per year of fluff pulp.  Flint River Operations' environmental performance has been recognized as superior within the bleached Kraft pulping industry.  Flint River was the first bleached Kraft pulp mill to employ commercially viable advanced technologies that minimize adverse impacts to the environment such as oxygen delignification, 100% chlorine dioxide substitution and bleaching and extensive water conservation practices.

93 93 Application of MIM Concepts: The Flint River Case Study Weyerhaeuser Project XL: Weyerhaeuser Company's pulp manufacturing facility in Oglethorpe, Georgia, is striving to minimize the environmental impact of its manufacturing processes on the Flint River and surrounding environment by pursuing a long-term vision of a Minimum (environmental) Impact Mill. Weyerhaeuser Company is taking immediate steps by decreasing water use and meeting or exceeding all regulatory targets. EPA and the State of Georgia have agreed to propose changes in the rules to support minimum impact manufacturing. The Final Project Agreement was signed on January 17, 1997.

94 94 Application of MIM Concepts: The Flint River Case Study MIM phases at Flint River  MIM Phase I ( ) Original Facility Design Oxygen Delignification Extensive Water Recycle / Reuse Chlorine/Chlorine Dioxide Bleaching Air Emissions / Low Odor / BACT/ NSPS Extensive Wastewater Treatment  MIM Phase II ( ) River & Lake Environmental Studies Holding Pond Addition / Delta Color Management Process Reliability I (Rate/Surge) Spill Containment & Liquor Best Management Practices

95 95 Application of MIM Concepts: The Flint River Case Study MIM phases at Flint River  MIM Phase III ( ) Process Reliability II (Statistical Process Control) Elimination Of Molecular Chlorine Bleach Plant & Chemical Generator Collection Emergency Response Team (Fire/Hazmat/EMT/Confined Space) ISO 9000 Certification  MIM Phase IV ( ) Isothermal Cooking Odor Control System Upgrade Energy Steam Reductions ISO Environmental Management System (EMS)

96 96 Application of MIM Concepts: The Flint River Case Study MIM phases at Flint River  MIM Phase V Bleach Plant Effluent Reductions Solid Waste Reductions Timberland Resource Strategies Water Use Reduction Energy Conservation Hazardous Air Pollutant (HAP) Emission Reductions MIM Phase VI: Life Cycle Inventory

97 97 References  EUROPEAN COMISSION. Integrated Pollution Prevention and Control (IPPC) – Reference Document on Best Available Techniques in the Pulp and Paper Industry. 2001, 475 p.  LOVELADY, EVA M. An Integrated Approach to the Optimization of Water Usage and Discharge in Pulp and Paper Plants. Auburn University, USA, 2002, 185 p.  Minimum Impact Manufacturing International Environmental Conference & Exhibits. 1996, p  NCASI. Pulp Mill Process Closure: A Review of Global Technology Developments and Mill Experiences in the 1990s. Technical Bulletin No. 860, May 2003, 108 p.  PAPRICAN. Energy cost reduction in the pulp and paper industry. Pointe Claire, QC, Canada : Pulp and Paper Research Institute of Canada,  USEPA. Project XL – Weyerhaeuser Company. (page consulted in 2004).  WEYERHAEUSER Minimum Impact Manufacturing. mfg.asp (page consulted in 2004) mfg.asp

98 1.3 Related PI Tools

99 99 Content  Process Simulation  Process Integration  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

100 100 Content  Process Simulation  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

101 101 What is a Model? A Simulation?  A model is an abstraction of a process operation used to build, change, improve or control that process.  Models are useful for: Equipment design, sizing, selection Comparison of possible configurations Evaluation of process performance against limits (e.g. concentrations, effluent discharge rates, …) Debottlenecking and optimization Control strategy development and evaluation  Simulation involves performing a series of experiments with a process model. Return to Path Diagram Equation

102 102 Benefits of Simulation  Better understanding of the process  Consistent set of typical mill data  Objective comparative evaluation of options for ROI etc.  Identification of bottlenecks, instabilities etc.  Perform many experiments cheaply once model built  Avoid implementing ineffective solutions Return to Path Diagram Equation

103 103 Models Are Only an Approximation of the Reality There is many type of models: Physical (e.g. mimic panel) vs. mathematical Quantitative vs. qualitative First principles vs. empirical Steady state vs. dynamic Type and level of precision of a model will depend on many factors such as: Phenomena represented Level of detail and granularity Assumptions Kind of input required Functions performed (constraint satisfaction? optimization? …) Nature of output generated Return to Path Diagram Equation

104 104 Content  Process Simulation  Process Integration  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

105 105 Process Integration Definitions:  “Process integration is a holistic approach to process design, retrofitting, and operation which emphasizes the unity of the process.” (El-Halwagi, 1997)  “The holistic analysis of processes involving the following elements: Process data; Systems and tools; Process engineering principles and in dept process sector knowledge.”(Stuart, 2002)

106 106 Content  Process Simulation  Process Integration  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

107 107 Mass Integration Definition: “Systematic methodology that provides a fundamental understanding of global flows of mass within the process and employs this holistic understanding in identifying performance targets and optimizing the generation and routing of species throughout the process” (El-Halwagi, 1997) Pollution prevention is one of the most important objectives of mass integration! Return to Path Diagram Equation

108 108 Principles of Mass Integration  Mass integration is based on chemical engineering principles combined with system analysis.  Mass flow must be represented from a species viewpoint: For each targeted species, there are sources (streams that carry the substances) and sinks (reactors, heaters/coolers, etc.). Streams living the sinks become sources. The sinks can be generator of targeted species. Each sink/generator can be manipulated through design or their operations can be changed in order to affect the flow rate and composition of what each sink/generator accepts as discharges.  Sources are generally prepared for sinks through segregation and separation via waste interception network.  Effective pollution prevention can be reached by combination of stream segragation, mixing, interception, recycle from sources to sinks and sink/generator manipulations. Return to Path Diagram Equation

109 109 Sources (back to process) Sinks/ Generators Segregated Sources Segregation, Recycle, Interception and Sink/Generator Manipulation  Segregation: Avoiding the mixing of the streams.  Recycle: Utilization of pollutant- laden stream (a source) in a process unit (a sink).  Interception: Utilization of separation unit operation to adjust the composition of the pollution-laden streams to make them acceptable for sinks.  Sink/Generator manipulation: Design or operation of changes that alter the flowrate or composition of pollutant-laden streams entering or leaving the process units. Waste Interception Network 2 1 N sink Mass and Energy-Separating Agents In Mass and Energy-Separating Agents Out (To Regeneration and Recycle) Source: El-Halwagi, 1997 Return to Path Diagram Equation

110 110 Content  Process Simulation  Process Integration  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

111 111 Energy Integration Definition: “Systematic methodology that provides a fundamental understanding of energy utilization within the process and employs this understanding in identifying energy targets and optimizing heat-recovery and energy-utility systems” (El-Halwagi, 1997) Energy integration tool: Thermal-pinch techniques are based on thermodynamic principles and are used, among others, to identify minimum heating and cooling utility requirements.

112 112 Principles of Thermal Pinch PROCESS Reduction of Utilities Internal Exchanges Utility costs decrease Costs related to exchange area increase From 100% utilies… … toward 100% internal exchanges $ Trade-off Cold Utility Hot Utility

113 113 Composite Curves Definition: Composite Curves consist of temperature-enthalpy (T-H) profiles of heat availability in the process (the “hot composite curve”) and heat demands in the process (the “cold composite curve”) together in a graphical representation.

114 114 Grand Composite Curve The grand composite curve is the tool that is used for setting multiple utility targets.

115 115 Grand Composite Curve Example of Application

116 116 Heat Exchanger Network Design Key Steps Heat and Mass Balances 1.Data Extraction 2.Analysis  Targeting  Process Modifications  Utility Selection 3.Design 4.Selection of Alternatives 5.Project Detailling PINCH ANALYSIS Process Simulation Total Site Analysis Source: Linnhoff March,1998

117 117 Content  Process Simulation  Process Integration  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

118 118 What is LCA Definitions:  A systematic set of procedures for compiling and examining the inputs and outputs of materials and energy and the associated environmental impacts directly attributable to the functioning of a product or service system throughout its life cycle.” (Source: ISO 14040: Life cycle assessment – principles and framework, 1998)  "Life Cycle Assessment is a process to evaluate the environmental burdens associated with a product, process, or activity by identifying and quantifying energy and materials used and wastes released to the environment; to assess the impact of those energy and materials used and releases to the environment; and to identify and evaluate opportunities to affect environmental improvements. The assessment includes the entire life cycle of the product, process or activity, encompassing, extracting and processing raw materials; manufacturing, transportation and distribution; use, re- use, maintenance; recycling, and final disposal". (Source: Guidelines for Life-Cycle Assessment: A 'Code of Practice', SETAC, Brussels, 1993 )

119 119 Example Life Cycle of Newspaper

120 120 LCA Methodology Applications:  Development and improvement of products Development and improvement of products  Strategic planning Strategic planning  Public policy development Public policy development  Marketing Marketing  Others Others Other tools:  Technical  Economic  Market  Social  etc Goal and Scope Definition Invetory Analysis Impact Assessment Interpretation For more information on each LCA methodology steps, click on the corresponding box. Limitations

121 121 Goal and Scope Definition The goal of an LCA study shall unambiguously state the intended application, the reasons for carrying out the study and the intended audience, i.e. to whom the results of the study are intended to be communicated.

122 122 Goal and Scope Definition  the functions of the product system, or, in the case of comparative studies, the systems ;  the functional unit ;  the product system to be studied ;  the product system boundaries ;  allocation procedures ;  data requirements ;  assumptions ;  types of impact and methodology of impact assessment, and subsequent interpretation to be used ;  limitations ;  initial data quality requirements ;  type of critical review, if any ;  type and format of the report required for the study. The scope of the LCA consists in:

123 123 Function Definition: Service supplied by a system of product or a process unit. Examples: SystemPaper RecyclingCogeneration Possible functions  Waste paper valorisation  Deinked pulp production  Etc.  Electricity generation  Steam production  Etc. Return to the scope

124 124 Functional Unit Definition: « Quantified performance of a product system for use as a reference unit in a life cycle assessment study » Examples: SystemPaper RecyclingCogeneration Possible functions  Waste paper valorisation  Deinked pulp production  Etc.  Electricity generation  Steam production  Etc. Related functional unit  Recuperation of 1000 kg of waste paper  Production of 1 ton of deinked pulp  Etc.  Generation of 1MW of electricity  Production of of steam by hour at 125 o C and 0.3 MPa  Etc. Return to the scope

125 125 Product System Definition: « Collection of materially and energetically connected unit processes which performs one or more defined functions » Unit process A Unit process B Unit process C Product flow Environment Elementary flow Intermediate flow Return to the scope

126 126 System Boundaries Definition: « Interface between a product system and the environment or other product systems » Unit process A Unit process B Unit process C Product flow Environment Elementary flow Intermediate flow System boundaries Return to the scope

127 127 Allocation  Most industrial processes comprise more that one output product, and raw material inputs include intermediate products. These processes are multifunctional.  In LCA terms, this means that the product system under system provides more functions than the one related to the functional unit. A decision will have to be taken in order to decide how to split flows and environmental intervention between these functions. This is allocation: “ partitioning the input or output flows of a unit process to the product system under study”  The allocation procedures must respect the mass conservation rules.  The production of by-products as well as the open loop recycling are two common situations implicating allocation.

128 128 By-Products Definition: A by-product can be defined as an output which is neither the primary product neither a waste. Example: Suppose you have a system with primary function to produce paper. In this system, you have a unit process which is wood sawing and which results in two products, chips and lumber. Only chips will be used in the wood manufacturing, lumber will be sent out of the system and use in another one. So, in the system which has as main funtion to produce paper, lumber is a by-product.

129 129 Open vs. Close-Loop Recycling Close-loop recycling: The product is reused in the same product system to produce the same product. No allocation required! Close-loop recycling: Recycling of one product from on system to another. Allocation of environmental impacts and credits of recycling will have to be allocated between both system. Return to the scope

130 130 Inventory Analysis Definition: “Phase of life cycle assessment involving the compilation and quantification of inputs and outputs, for a given product system throughout its life cycle” (Source: ISO 14041)

131 131 Life Cycle Impact Assessment Definition: “Phase of life cycle assessment aimed at understanding and evaluating the magnitude and significance of the potential environmental impacts of a product system” (Source: ISO 14042)

132 132 From Inventory to Impact Assessment Inventory Impact Production Processes Energy Production Waste Disposal & Management Transport Resource Depletion Emissions: CFC Pb Cd HAP COV DDT CO 2 SO2 NOX P Dust Etc. Solid wastes Resource Depletion Global Warming Ozone Depletion Ecotoxicology Human Health Smog Acidification Eutrophication Etc… Solid Wastes Resource Depletion Mortality and Diceases Ecosystem Depletion Aesthical Value Solid Wastes Agregated Indicator Problem Approach “Midpoint” Damage Approach “Endpoint” PRECISION

133 133 Interpretation Definition: “Phase of life cycle assessment in which the findings of either the inventory analysis or the impact assessment, or both, are combined consistent with the defined goal and scope in order to reach conclusions and recommendations” (Source: ISO 14043)

134 134 LCA Main Limitations  Site-specific impact are not well considered  Steady-state approach  Linear modeling  Based on a number of technical assumptions and value choices for instance: Impact categories Characterization models System boundaries Weighting of impacts  Availability and reliability of data and models

135 135 Content  Process Simulation  Process Integration  Mass Integration  Energy Integration  LCA  Integrating these tools to address MIM

136 136 In Summary  Minimum Impact Manufacturing aims at minimizing: Resource consumption Energy consumption Environmental impact (soil, air and water emissions)  Simulation are useful to better understand the process  Mass integration is a tool to reduce resource consumption and reject in the environment  Energy integration is a tool that allows for a better utilization of the energy  LCA allows for a holistic evaluation of environmental impacts over the product chain

137 137 Integration of Tools to Address MIM  MIM is a multi-objective problem involving the best trade-offs between: Minimum resource consumption; Minimum energy consumption; Minimum air emissions; Minimum water emissions; Minimum solid wastes.  This is also submitted to a lot of complicated constraints: Process constraints ; Technology constraints; Life cycle interactions; Costs.  For these reasons, integration of PI tools to address MIM is not obvious.

138 138 References  El-Halwagi, Mahmoud M. Pollution Prevention through Process Integration, Academic Press, San Diego, USA, 1997, 318 p.  ISO Management environnemental – Analyse du cycle de vie Principes et cadres. CAN/CSA-ISO 14040:1997  ISO Management environnemental – Analyse du cycle de vie – Définition de l’objectif et du champ de l’étude et analyse de l’inventaire. CAN/CSA-ISO 14041:1998  ISO Management environnemental – Analyse du cycle de vie – Analyse de l’impact du cycle de vie. CAN/CSA-ISO 14042:2000  ISO Management environnemental – Analyse du cycle de vie – Interprétation du cycle de vie. CAN/CSA-ISO 14043:2000  Linnhoff March Introduction to Pinch Technology. (page consulted in 2004)

139 QUIZ

140 140 Question 1 What is one of the main characteristics of kraft processes? a)The mechanical pulp b)The necessity to bleach the pulp c)The chemical recovery system d)Its low water consumption

141 141 Question 2 Which of the following unit processes generates the most sulfur compound emissions? a)Oxygen delignification b)Bleaching c)Pulping (digester) d)Recovery furnace

142 142 Question 3 Toward which of the following elements is MIM oriented? a)Reducing air emissions b)Reducing solid wastes c)Maximising shareholder value d)a and b e)a, b and c

143 143 Question 4 Which of these technical problem can be associated to process closure? a)Accumulation of undesirable elements in the recovery system b)Higher cost of utility c)Higher energy consumption d)Need of more pulping chemicals

144 144 Question 5 Which of these tracking model will you use if one component can be accurately tracked while another one cannot a)Fixed split model b)Flow ratio model c)Species ratio model d)Degree of freedom equation

145 145 Question 6 Which of these is not a characteristic of BAT? a)They must be economically achievable b)They must be process unit oriented c)They must be process oriented d)They must be product oriented

146 146 Question 7 Which of the following will not decrease Kraft mill energy consumption a)Water consumption reduction b)Chips screening c)Less piping d)Changing ECF bleaching for TCF bleaching

147 147 Question 8 Which of the following trade-offs is the most communly associated with energy integration? a)Reducing energy while increasing water consumption b)Capital vs. operating costs c)Energy vs. chemical costs d)Time horizon vs. energy savings

148 148 Question 9 Which of the following correspond to segregation in mass integration? a)Avoiding the mixing of the streams. b)Utilization of pollutant-laden stream (a source) in a process unit (a sink). c)Utilization of separation unit operation to adjust the composition of the pollution-laden streams to make them acceptable for sinks. d)Design or operation of changes that alter the flowrate or composition of pollutant-laden streams entering or leaving the process units.

149 149 Question 10 Which of the following can be described as a functional unit? a)The production of kraft pulp b)The production of kraft pulp during 10 hours c)The production of 1 admt kraft pulp d)b and c


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