Membranes on Polyolefins Plants Vent Recovery

COVERIME Membranes on Polyolefins Plants Vent Recovery 1

Intratec Report #IME001A Membranes on Polyolefins Plants Vent Recovery ISBN: 978-0-615-67891-7 AbstractGas separation by membranes has acquired increasing importance in the petrochemical industry and is now a relatively well-established unit operation, especially in the production of polymers. The process of polymer degassing is necessary to suitpolymer for extrusion and pelletizing, increasing safety, environmental, and product quality aspects. Nitrogen is generally used forthis purpose, resulting in a vent gas primarily composed of monomers and nitrogen.In early polyolefin plants, these streams were often used as boiler fuel. However, considering the current tight monomers market,particularly in propylene, and the benefits of membrane-based recovery processes, major polyolefin producers around the worldalready employ them in new state-of-the-art plants. In order to enhance the competitiveness of older plants, the use of a recoverysolution is becoming mandatory.In this report, the recovery of propylene and nitrogen from a polypropylene degassing vent stream is reviewed and comparedwith its use as boiler fuel. Included in the analysis is an overview of the technology and economics of a process similar to MTRVaporSep®. Both the capital investment and the operating costs are presented for a propylene recovery unit (PRU) operating inthe US Gulf Coast, Germany, and Brazil.The economic analysis presented in this report is based upon a recovery unit installed in a 450 kta polypropylene plant. Theestimated CAPEX for such unit is USD 5.8 million on the US Gulf Coast, the lowest figure among the regions under analysis. Due topropylene scarcity, which raised its market value, and the low fuel prices due to natural gas growing offerings, installation of amembrane unit for this type of recovery is advantageous. This fact is proven by the calculated internal rate of return of more than40% per year in the region.Furthermore, local propylene and fuel market dynamics are the key drivers in evaluating a membrane separation unit’sattractiveness. If fuel can be obtained from inexpensive sources and propylene is priced high, the unit’s installation could beconsidered. This improvement is already part of state-of-the-art polypropylene technologies such as INEOS Innovene™ andLummus Novolen®, and is a remarkable solution for this type of recoveryCopyrights © 2012 by Intratec Solutions LLC. All rights reserved. Printed in the United States of America. Except as permitted under the UnitedStates Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a database orretrieval system, without the prior written permission of the publisher.

ContentsTerms and Conditions ........................................................................................................................................................8About the Program..............................................................................................................................................................9 Program Description .........................................................................................................................................................................................................9 Related Publication Programs .....................................................................................................................................................................................9 Introductory Pricing Offer ..............................................................................................................................................................................................9 University Discount ............................................................................................................................................................................................................9 Buy Options..........................................................................................................................................................................................................................10About Membrane Separation Processes.................................................................................................................. 11 Introduction.........................................................................................................................................................................................................................11 Membranes for Gas Separation ...............................................................................................................................................................................11 Oil-and-Gas and Petrochemical Industries Applications....................................................................................................................................12 Membrane Materials and Modules..................................................................................................................................................................................13 Polyolefin Plants Opportunities...............................................................................................................................................................................13 Raw Material Purification........................................................................................................................................................................................................13 Reaction System ..........................................................................................................................................................................................................................14 Product Finishing........................................................................................................................................................................................................................14Process & Economics Overview ................................................................................................................................... 15 Supplier(s) & Historical Aspects ...............................................................................................................................................................................15 Improvement Summary...............................................................................................................................................................................................15 Description......................................................................................................................................................................................................................................15 Implementation Assumptions............................................................................................................................................................................................17 Operation & Block Flow Diagram......................................................................................................................................................................................17 Economic Summary .......................................................................................................................................................................................................19 Alternatives Overview....................................................................................................................................................................................................19 Different Implementations....................................................................................................................................................................................................19 Substitute Solutions ..................................................................................................................................................................................................................19Process Analysis................................................................................................................................................................. 21 Process Description & Conceptual Flow Diagram.......................................................................................................................................21 Compression and Cooling.....................................................................................................................................................................................................21 Flashing .............................................................................................................................................................................................................................................21 3

Membrane Separation.............................................................................................................................................................................................................22 Key Consumptions ..........................................................................................................................................................................................................22 Technical Assumptions.................................................................................................................................................................................................22 Major Equipment List.....................................................................................................................................................................................................25 Economic Analysis ............................................................................................................................................................ 27 General Assumptions.....................................................................................................................................................................................................27 Capital Expenditures.......................................................................................................................................................................................................27 Fixed Investment.........................................................................................................................................................................................................................27 Other Capital Expenses ...........................................................................................................................................................................................................28 Total Capital Expenses .............................................................................................................................................................................................................28 Regional Comparison...............................................................................................................................................................................................................29 Operational Expenditures ...........................................................................................................................................................................................29 Manufacturing Costs.................................................................................................................................................................................................................29 Depreciation...................................................................................................................................................................................................................................30 Regional Comparison...............................................................................................................................................................................................................31 Economic Datasheet & Discussion ........................................................................................................................................................................31 Implementation Benefits........................................................................................................................................................................................................31 Return on Investment ..............................................................................................................................................................................................................31 Economic Assumptions................................................................................................................................................................................................32 References............................................................................................................................................................................ 35 Acronyms, Legends & Observations .......................................................................................................................... 36 Methodology of the Analysis........................................................................................................................................ 38 General Approach............................................................................................................................................................................................................38 Assumptions........................................................................................................................................................................................................................38 General Considerations...........................................................................................................................................................................................................38 Fixed Investment.........................................................................................................................................................................................................................40 Start-up Expenses .......................................................................................................................................................................................................................40 Other Capital Expenses ...........................................................................................................................................................................................................40 Manufacturing Costs.................................................................................................................................................................................................................41 Contingencies & Accuracy of Economic Estimates.....................................................................................................................................41 Location Factor ..................................................................................................................................................................................................................42 Premium Tools: Deepen Your Analysis .................................................................................................................... 44 Product Overview.............................................................................................................................................................................................................44 Product Description........................................................................................................................................................................................................444

Buy Options..........................................................................................................................................................................................................................44Economic Data Bank: Free Economic Updates ...................................................................................................... 45 Product Overview.............................................................................................................................................................................................................45 Product Description........................................................................................................................................................................................................45 Access Economic Data Bank......................................................................................................................................................................................45Latest & Upcoming Reports .......................................................................................................................................... 46 5

List of Tables Table 1 – Industrial Membrane Processes .........................................................................................................................................................................12 Table 2 – Membrane Applications in the Oil-and-Gas and Petrochemical Industries...........................................................................12 Table 3 – Types of Modules and Applications ................................................................................................................................................................13 Table 4 - Implementation Assumptions .............................................................................................................................................................................18 Table 5 – Capital Cost & Economic Summary.................................................................................................................................................................19 Table 6 - Raw Materials & Consumptions (per ton of Product) ............................................................................................................................22 Table 7 – Design & Simulation Assumptions...................................................................................................................................................................23 Table 8 – Main Streams Operating Conditions and Composition .....................................................................................................................25 Table 9 – Major Equipment List ...............................................................................................................................................................................................25 Table 10 – Base Case General Assumptions.....................................................................................................................................................................27 Table 11 – Total Fixed Investment Breakdown (USD Thousands)......................................................................................................................28 Table 12 – Other Capital Expenses (USD Million)..........................................................................................................................................................28 Table 13 – CAPEX (USD Million) ...............................................................................................................................................................................................28 Table 14 – Manufacturing Fixed Cost (USD/ton) ..........................................................................................................................................................29 Table 15 – Manufacturing Variable Cost (USD/ton) ....................................................................................................................................................30 Table 16 – OPEX (USD/ton).........................................................................................................................................................................................................30 Table 17 – Depreciation Value & Assumptions ..............................................................................................................................................................31 Table 18 – Fixed Cost Assumptions.......................................................................................................................................................................................32 Table 19 – Technology Economics Datasheet: Polypropylene Plant Vent Recovery............................................................................33 Table 20 – Project Contingency...............................................................................................................................................................................................41 Table 21 – Accuracy of Economic Estimates ...................................................................................................................................................................41 Table 22 – Criteria Description..................................................................................................................................................................................................426

List of FiguresFigure 1 - Membrane Separation Schematic...................................................................................................................................................................11Figure 2 - Column Overhead Membrane Recovery ....................................................................................................................................................14Figure 3 – Reactor Purge Membrane Recovery .............................................................................................................................................................14Figure 4 - Purge Vent Membrane Recovery .....................................................................................................................................................................14Figure 5 – Three-Layer Composite Membrane ..............................................................................................................................................................16Figure 6 – Membrane Modules Schematic.......................................................................................................................................................................16Figure 7 – Process Simplified Flow Diagram....................................................................................................................................................................18Figure 8 – Multi-Stage/Multi-Step Membrane Separation .....................................................................................................................................19Figure 9 - Conceptual Process Flow Diagram.................................................................................................................................................................24Figure 10 – CAPEX per Location (USD Million)...............................................................................................................................................................29Figure 11 – OPEX and Product Sales History (USD/ton) ...........................................................................................................................................30Figure 12 – Operating Costs Breakdown per Location (USD/ton).....................................................................................................................31Figure 13 – Improvement Earnings Comparison (USD Million)...........................................................................................................................32Figure 14 – Methodology Flowchart....................................................................................................................................................................................39Figure 15 – Location Factor Composition.........................................................................................................................................................................43 7

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About Membrane Separation Processes commercialization of reverse osmosis and, also, theIntroduction development of microfiltration and ultrafiltration technologies. That was the first use of membranes on aMembranes can be defined as barriers capable of large scale.separating two phases and, simultaneously, limitingchemical components transport in a selective manner. A Since the 1980’s, these separation processes, along withtypical membrane system can generate a permeate electrodialysis, are employed in large plants and, today, aproduct, in separation processes, or a residue product, in number of experienced companies serve the market.purification processes, as depicted in Figure 1. Certain features of membranes are responsible for the interest in using them as substitutes to consolidatedFigure 1 - Membrane Separation Schematic industrial separation processes, like distillation, absorption, adsorption or extraction. Some advantages noted include:  Less energy-intensive, since they do not require major Membrane Module phase changes Residue Feed Stream  Do not demand adsorbents or solvents, which may be Membrane expensive or difficult to handle Layer Permeate Stream  Equipment simplicity and modularity, which facilitates the incorporation of more efficient membranesSource: Intratec – www.intratec.us Spurred by the advances in membrane materials, a wide range of processes became commercialized. Some of these processes and their respective applications are summarizedMembranes can have a wide range of characteristics and in Table 1.properties, which suit them for an equally wide range ofapplications, ranging from industrial to medicine, forexample. The artificial kidney (utilized in clinical therapy Membranes for Gas Separationsince the early 1960s) and the membrane blood oxygenator(which enabled open-heart surgeries) are remarkable Although the asymmetric membranes developed forexamples of the success of membranes. reverse osmosis enhanced separation performance, extending this concept to gas separation was not simple.The concept of a membrane has been known since the The first commercial application was only launched in 1980 Intratec | About Membrane Separation Processeseighteenth century, but it remained as only a tool forphysical / chemical theories development until the end of by Monsanto, which developed composite membranes forWorld War II, when drinking water supplies in Europe were hydrogen separation, particularly from purge gases incompromised and membrane filters were used to test for ammonia plants. Its success established the commercialwater safety. However, due to the lack of reliability, slow feasibility of gas separation with membranes and was anoperation, reduced selectivity and elevated costs, incentive for other companies to market their ownmembranes were not widely exploited. membrane technologies.In the early 1960s, Loeb and Sourirajan developed a Gas separation by membranes is, now, a relatively well-preparation method of asymmetric high flux membranes established unit operation in the petrochemical industry.for reverse osmosis applied to water desalinization. This However, it did not achieve a maturity level comparable toadvance, along with large investments from the US microfiltration or ultrafiltration, for example.Department of Interior, contributed to the 11

Table 1 – Industrial Membrane Processes Microfiltration Large Liquid Liquid Pressure Bacteria and suspensions Ultrafiltration Medium Liquid Liquid Pressure Emulsions and polymers Low molecular weight Nanofiltration Small Liquid Liquid Pressure components (microsolutes) Reverse Osmosis Very Small Liquid Liquid Pressure Desalination (NaCl) Dehydration of organic Pervaporation Very Small Liquid Vapor Vapor Pressure solvents (ethanol, iso- propanol, etc) Gas Separation Very Small Gas Gas Vapor Pressure Gases, such as N2/O2 Monomer recovery, natural Vapor Permeation Very Small Vapor Vapor Vapor Pressure gas drying, etc Source: Intratec – www.intratec.us Oil-and-Gas and Petrochemical Industries Natural gas purification is a segment in which membranes have a great potential to expand, due to several aspects. Applications Firstly, raw gas composition can vary greatly depending on Aligned with new environmental standards and aimed at its source, but the composition of the delivered gas must reducing the costs of industrial processes, separation of follow tight specifications. Hence, treatment steps are gaseous mixtures through membranes is likely to expand required, in smaller or larger extension. Secondly, natural applications in refineries and petrochemical industries. gas processing historically ranges from 15-20 trillion cubic Table 2 summarizes some petrochemical, refineries and feet, only in the U.S., and membranes still accounts for a natural gas applications of membranes. small percentage of this market, with the main application standing in CO2 removal. A smaller but growing application is the use of membranes Table 2 – Membrane Applications in the Oil-and-Gas in recovering organic vapors, motivated by both valuable and Petrochemical Industries components’ losses and by the establishment of more strict emission regulations, notably in Germany and in the U.S.A. Ethylene recovery in ethylene oxide Monomer recovery from polyolefin plants vents and production gasoline capture from tank farms or fuel terminals were Petrochemical Polyolefin plants monomer recovery already available in the mid-1990s. PVC plants monomer recoveryIntratec | About Membrane Separation Processes Similarly, unreacted vinyl chloride monomer (VCM) used in Syngas ratio adjustment PVC production is not properly recovered by simple Hydrogen recovery from various streams condensation of the reactor vent stream. Grounded by (FCC overhead gas, catalyst-cracker off- regulations associated with its emission, membrane units Refining gas, etc) for VCM recovery were applied even before their use in Catalytic reformer hydrogen upgrading monomer separation. LPG recovery The large volumes of hydrocarbons processed in refineries CO2 and N2 removal and in the petrochemical industry may limit membrane use Natural Gas Natural gas liquids removal due to the extremely large surface areas that would be Digester off-gas treatment required to achieve determined separations. Source: Intratec – www.intratec.us 12

Meanwhile, the larger market share remains in treating“clean gases” streams, i.e., those that do not present Table 3 – Types of Modules and Applicationscomponents that might cause fouling or plasticize themembrane. N2 separation from air and H2 separation fromammonia purge vent or syngas can be cited. O2 / N2 Hollow-fiberMembrane Materials and Modules H2 / N2 Hollow-fiber CO2 / CH4 Spiral-wound and hollow-fiberThe most widely employed materials in gas separation are VOC / N2 Spiral-woundpolymeric dense membranes, although only a smallnumber (about 10 polymers) are employed commercially. H2O / AIR Capillary-fiber Source: Intratec – www.intratec.usTo be recognized as a suitable industrial separation material,the membrane must show characteristics such as:  Stability Polyolefin Plants Opportunities In essence, industrial polymerization processes can be  Thin selective layer described as catalytic reactions wherein monomers form  Defect-free structure macromolecules characterized by a certain conjunct of commercially appealing properties. Standing as the main  Proper mechanical resistance or available physical vapor permeation application, polyolefin plants present support important stages in which membranes can be applied.After selection of the more suitable material, is necessary to Raw Material Purificationpackage the membrane to obtain compact, high surfacearea modules. The characteristics of the material can limit The first (and significant) stage in polymerization process isthe modules manufacturing possibilities and, consequently, fitting the raw materials to the sensitiveness of the catalystthe type of modules. system and/or to avoid the accumulation of inert substances. Depending on monomer’s specific source,The modules are factory-built and are replaced entirely direct use is not always suitable and removal of light gaseswhen necessary. On one hand, this modular characteristic such as N2, H2 and CH4 is often necessary.facilitates maintenance and minimizes plants’ downtimesbut, on the other hand, little economy of scale is verified. In polyethylene (PE) plants, this may be accomplished by anThe order of magnitude for the membrane area required ethylene stripper, but light gases build-up in the columnmay range from hundreds to thousands of square meters; overhead requires a purge that can carry considerablehence, a large number of modules are required. amounts of ethylene. To minimize this issue, it is possible to implement a membrane unit to receive the lights streamThe most frequently employed types of modules for gas and recycle enriched ethylene permeate to the column.separation are hollow-fiber and spiral-wound. Table 3 Additionally, the column size required could be reduced. Intratec | About Membrane Separation Processespresents some examples of applications and theirrespective modules. 13

Typically, the newly formed polyolefin contains entrained monomers, water used to deactivate catalyst residues, and Figure 2 – Column Overhead Membrane Recovery inert components, such as propane. In order to suit the polymer for extrusion and pelletizing and increase the Membrane Unit safety, environmental, and product quality aspects of the Residue to Flare process, hot nitrogen is generally used, resulting in a vent or Fuel gas containing hydrocarbons, nitrogen and water. Olefin Product The earning potential of recovering monomer rather than Monomer burning it as fuel, as in older plants, encouraged companies Feed to consider the use of membrane separation units. C2-Enriched Permeate Although most state-of-the-art technologies may provide Heavies alternatives for such recovery, most older plants lack proper Ethylene-Ethane Splitter separation methods. Nowadays, near 50 of these membrane systems have been installed in polyolefin plants. Source: Intratec – www.intratec.us Figure 4 depicts this type of application in a HDPE plant. Reaction System Figure 4 - Purge Vent Membrane Recovery This sort of application is mainly present in polyethylene production. In both linear low density polyethylene (LLDPE) Permeate and high density polyethylene (HDPE), control of the partial To Condenser pressure of ethylene in the reactor requires the addition of Flare nitrogen. The purge of the reactor not only removes Membrane nitrogen, but also unreacted monomers, which allows a Unit Resin membrane unit to be used to reduce monomer losses. Purge N2 feed Bin Recovered Iso-Butane Figure 3 – Reactor Purge Membrane Recovery Polymer C2-depleted Purge residue Source: Intratec – www.intratec.us Recycle Gas Membrane Unit PE Reactor Polymer Discharge C2-enriched permeateIntratec | About Membrane Separation Processes Monomer Feed Source: Intratec – www.intratec.us Product Finishing The degassing/drying stage is largely responsible for monomer losses in polypropylene (PP) plants and an additional recovery point in polyethylene production. 14

Process & Economics Overview involving process simulations, design procedures andSupplier(s) & Historical Aspects mathematical models developed by Intratec.The two main suppliers of vapor/gas membrane separationsystems are licensees of GKSS (Borsig, Dalian Eurofilm and DescriptionSihi) and MTR. The improvement consists of a vapor permeation systemThe first applications of VOC removal from air were in combining membrane and cryogenic separationrecovering gasoline vapors or solvents in the early 1990s. techniques (hybrid process). The membrane components’Nowadays, hundreds of larger and smaller systems with characteristics are described in this section, while the otherapplications such as resin degassing vent recovery, gasoline equipment in the system are only discussed in thevapor recovery, and MVC recovery have been installed operation description.around the world. The PRU consists of a skid of about 15 m2 of footprint, withIn terms of polyolefin applications, membrane technologies the compressor occupying a similar skid. Generally, thefor monomer/nitrogen separation currently available are supplier provides the entire solution.very similar, but MTR is the leader in this application. MTR’sfirst order dates from 1996 and was installed in a PP plant in Membrane Materialthe Netherlands. The membrane itself usually consists of a multilayeredEurofilm has a number of installed units in China for composite structure in which the different materials exhibitpropylene recovery, most of them in smaller batch distinct functions. In polyolefin production, the vent gasprocesses. Until 2011, only two membrane units for recovery membranes are often described as follows:continuous processes had been installed, for JPP andSinopec Wuhan.  Selective thin layer. Rubbery polymers such as polydimethylsiloxane (also called PDMS or siliconeAlthough these membrane systems are relatively new, rubber) are chosen to selectively permeate propylenemajor polyolefins producers around the world utilize them. rather than nitrogen.In addition to the aforementioned JPP and Sinopec Wuhan,Borealis, ExxonMobil, Formosa Plastics, INEOS, Lummus,  Micro-porous support layer. Employed for mechanical support, provides a smooth surface onSABIC, and Sasol can be cited. In fact, both the INEOS which the selective thin layer can be coated.Innovene™ and Lummus Novolen® polypropyleneprocesses can be provided with membrane recovery units.  Non-woven fabric. Also employed to provide mechanical strength, serve as substrate to theImprovement Summary membrane. Its pores are too large to be coated directly with the selective thin layer.The current publication assesses in detail a technology for Intratec | Process & Economics Overviewnitrogen and propylene recovery in a polypropylene plant, Figure 5 shows a schematic of such a structure. Thehaving low purity propylene (about 83 wt. %) as its main selective layer’s chemical structure is often very simple andproduct. A process similar to MTR VaporSep® is analyzed similar, regardless of the supplier. Certain gaseous mixtures,and employed in the finishing section of the plant. This however, may demand more specific and complextype of system is often called a propylene recovery unit membranes.(PRU). PDMS is generally chosen for this application due to theirAll the data and figures presented were prepared based on high permeability when compared to glassy polymers and,publicly available information. This information was also, because the latter often do not demonstrate highcarefully analyzed through a structured methodology enough selectivity. 15

lower cost hollow-fibers, spiral-wound modules are used. Moreover, the spiral-wound modules can operate at higher Figure 5 – Three-Layer Composite Membrane feed flows, unlike hollow-fibers. Feed flow (feed spacer) Spiral-wound modules standard sizes are 100-150 cm long and 10 - 30 cm diameter. Their size is ideally guided by the Selective layer ease of handling, with one or two persons being able to handle a weight of up to approximately 20 kg. Micro-porous support layer In essence, spiral-wound module consists of multiple Non-woven membrane layers, feed and permeate spacers rolled around fabric a permeate collection tube. Spacers are also represented in Figure 5. Permeate flow (permeate spacer) Modules Organization Source: Intratec – www.intratec.us Whereas packing the membrane in a compact and economical module is desirable, the same concept must be extended to the modules’ organization. Figure 6 presents The use of a membrane more selective to the monomer in an assembling possibility for the membrane system. the purge bin vent leads to smaller membrane area requirements. Otherwise, the bulk of the vent would have From 2 to 6 cylindrical modules, arranged end-to-end, can to permeate. Propane contained in the mixture be placed in permanent housings made of carbon steel or demonstrates similar separation characteristics when stainless steel, which permit the system to operate at compared to propylene. pressures other than atmospheric. In order to simplify modules’ replacement, each one possesses its own Modules permeate collection tube, which may protrude beyond the Since rubbery polymers are not easily fabricated into the module and be joined by gas-tight connectors. Hence, the permeate gas path is formed, and may be collected by Figure 6 – Membrane Modules Schematic Membrane housing Pressure Membrane Residue vessel modules outletIntratec | Process & Economics Overview Feed Permeate inlet outlet Permeate pipes Pressure vessel side view Source: Intratec – www.intratec.us 16

manifolds, for example.These tubes are then placed in a cylindrical pressure vessel,which contain a number of parallel tubes. Sucharrangements, besides reducing the unit’s footprint, reducethe costs of vessels and associated components (pipes,valves, etc.), which may greatly surpass that of themembrane.The pressure vessel is composed of two removable headsand a cylindrical shell; their number will depend on thespecific area requirement. Size and weight must also betaken in consideration at this point.The feed gas is admitted and enters one of the housings’ends. Annular seals in each housing force the feed to axiallypenetrate the membranes and the permeate can bewithdrawn by the collection tube. The residue stream ofeach module usually suffers little pressure drop whencompared to the feed and, due to the annular seals, isforced to enter the next module, gradually reducing thepropylene/propane content. On the last section of eachtube, an opening is provided for the final residue stream,which then exits the system.Implementation AssumptionsThis section describes in which scenario the improvementwould be implemented, i.e., both previous characteristics ofthe plant and expected benefits/performance.Table 4 summarizes the assumptions supporting theanalysis presented in the following sections.Operation & Block Flow DiagramThe process can be separated in three different sections:compression and cooling; flashing; and membraneseparation. Figure 7 shows a simplified flow diagram for theprocess. The blue lines represent the additional streamsand equipment associated with the improvement. Intratec | Process & Economics OverviewThe mixture of propylene, propane, and nitrogen from thepurge (off-gas) is mixed with recycled streams beforecompressing. The compressor outlet is sent to a condenser,where streams generated during the process are used forheat integration.Compression and cooling are employed so as tocondensate at least a part of the monomer and minimizemembrane requirements. 17

After condensation and flashing, the low temperature liquid, containing mainly propylene and propane, is used for Table 4 - Implementation Assumptions heat integration and, then, sent to a cracker unit for purification. Plant Under Analysis A two-step membrane scheme is assumed for separation, with steps placed in series. The first step is responsible for Initial Scenario concentrating propylene, while the second one purifies Improvement nitrogen to the purge bin. Proposed The first membrane step generates a residue stream enriched in nitrogen, which is sent to the second Scenario after membrane step. The permeate is recycled to the inlet of Improvement the compressor. In the second membrane step, a residue stream containing OSBL nitrogen at 99 wt% purity is obtained. This stream is Requirements suitable for direct reuse without further purification. The permeate stream, in turn, is not sufficiently pure and is employed as boiler fuel. Source: Intratec – www.intratec.us Figure 7 – Process Simplified Flow Diagram Off-Gas Wet Resin Condenser To Boiler 1st Membrane Step Compressor Resin Degassing Bin to Compressor 2nd Membrane Inlet Step Fresh Nitrogen Flash Low Purity Propylene to Purification Propylene-RichIntratec | Process & Economics Overview Permeate Dry Resin Pure Nitrogen Notes: The blue lines represent the additional equipment and streams of the improvement, while the black lines represent process equipment and streams relative to the initial scenario. Source: MTR website, Intratec analysis 18

Economic Summary Figure 8 – Multi-Stage/Multi-Step MembraneThe table below summarizes the main economic indicators Separationof the improvement proposed, including the CAPEX, OPEX,Sales, and EBITDA. All figures are additions to theeconomics of a suitable existing plant, following a typicalimprovement design. N2 Propylene/ N2 mixture N2 purificationTable 5 – Capital Cost & Economic Summary Propylene concentration Propylene-enriched permeateCAPEX (USD Million) Source: Intratec – www.intratec.us TFI Other Initial Expenses Substitute SolutionsNet Product Sales (USD Million/yr)OPEX (USD Million/yr)EBITDA (USD Million/yr)Source: Intratec – www.intratec.usAlternatives OverviewDifferent Implementations Intratec | Process & Economics Overview 19

Process AnalysisProcess Description &Conceptual Flow DiagramThis section describes the PRU for separation of amonomer/nitrogen mixture arising from a typical polyolefinplant purge bin in detail. This description refers to a processsimilar to MTR VaporSep® system, but some differences maybe found, since all the information herein presented isbased on publicly available information. For purposes ofillustration, a polypropylene plant is investigated, but theanalysis could be easily extended to polyethylenemanufacturing processes. It is worth mentioning thatresults presented (equipment required, processconsumptions, etc.) are strictly limited to the PRU.The process consists of a gas separation system combiningcryogenic separation techniques and membranes. Fordescriptive purposes, three different sections are Flashingconsidered: compression and cooling; flashing; andmembrane separation.For a better understanding of the process, please refer tothe Conceptual Process Flow Diagram; the Main StreamsOperating Conditions and Composition; and the MajorEquipment List, presented in the next pages.Compression and Cooling Intratec | Process Analysis 21

Key Consumptions Table 6 - Raw Materials & Consumptions (per ton of Product) Membrane Replacement Propylene PG Membrane Separation Cooling Water Electricity Fuel By-product Nitrogen Source: Intratec – www.intratec.us Technical Assumptions All process design and economics are based on world-class capacity PRU units that are installed in globally competitive polypropylene plants. Assumptions regarding the thermodynamic model used in the process simulation, main improvement design basis and the raw materials composition are shown in Table 7. All data used to develop the process flow diagram was based on publicly available information.Intratec | Process Analysis 22

Table 7 – Design & Simulation Assumptions Simulation Software The Thermodynamic Model future is just Feed Flow Operating Hours per Year Nitrogen Propane ahead Propylene Propylene Purity Research Propylene Recovery from Feed Economics Nitrogen Purity Program Nitrogen Recovery from Feed Guidelines for Temperature research and Residue Pressure planning within Permeate Pressure the process industry arena. Temperature Residue Pressure Permeate Pressure Selective Layer Material Expected LifetimeSource: Intratec – www.intratec.usThe assumed operating hours per year indicated does not Intratec | Process Analysisrepresent any technology limitation; it is rather anassumption based on usual industrial operating rates. 23

Figure 9 - Conceptual Process Flow DiagramIntratec | Process Analysis Source: Intratec – www.intratec.us 24

Table 8 – Main Streams Operating Conditions and CompositionNamePhaseTemperature (°C)Pressure (bara)Mass Flow (kg/h)Propylene (wt%)Propane (wt%)Nitrogen (wt%)Source: Intratec – www.intratec.us For complete equipment list, including sizing, see theMajor Equipment List Chapter titled “Premium Tools: Deepen Your Analysis”, presented in this publication.Table 9 shows the equipment list, besides a briefdescription and the main materials used.Table 9 – Major Equipment ListE-101 Comp. Intercooler CSSource: Intratec – www.intratec.us Intratec | Process Analysis 25

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Economic Analysis of economic estimates can be found in this publication inGeneral Assumptions the chapter “Methodology of the Analysis”.This study strictly evaluates the earnings, operating andcapital expenditures associated with the improvement itself. Capital ExpendituresAll figures are in addition to the economics of a suitableexisting plant. Such plants’ operating and capital Fixed Investmentexpenditures are not in the scope of the presentpublication. Table 11 discloses the breakdown of the total fixed investment (TFI) per item (direct & indirect costs and projectThe general assumptions for the base case of this analysis contingencies).are outlined below. Fundamentally, the direct costs are the total direct material and labor costs associated with the equipment (includingTable 10 – Base Case General Assumptions installation bulks). The total direct cost represents the total bare equipment installed cost.Engineering & Construction Location After defining the total direct cost, the TFI is established byAnalysis Date adding field indirects, engineering costs, overhead, contractIC Index fees and contingencies.Nominal CapacityOperating Hours per YearAnnual ProductionProject ComplexityTechnology MaturityEvaluation PhaseData ReliabilitySource: Intratec – www.intratec.us For further information about the components of the TFIIn Table 10, the IC Index stands for Intratec chemical plant please see the chapter “Methodology of the Analysis”.Construction Index, an indicator, published monthly byIntratec Solutions to scale capital costs from one timeperiod to another. This index reconciles prices trends offundamental components of a chemical plant constructionsuch as labor, material and energy, providing meaningfulhistorical and forecast data for our readers and clients. Intratec | Economic AnalysisAdditionally, Table 10 discloses assumptions regarding theproject complexity, technology maturity, data reliability andthe evaluation phase, which are of major importance forattributing reasonable contingencies for the investmentand for evaluating the overall accuracy of estimates.Definitions and figures for both contingencies and accuracy 27

Table 11 – Total Fixed Investment Breakdown (USD Thousands) Direct Project Expenses Bare Equipment Other Capital Expenses Equipment Setting Piping Civil Steel Instrumentation and Control Electrical Equipment Insulation Paint Indirect Project Expenses Engineering & Procurement Construction Material & Indirects G & A Overheads Table 12 – Other Capital Expenses (USD Million) Contract Fee Start-up Expenses Operator training Project Contingency (15% of TPC) Commercialization costs Start-up Inefficiencies Other - Scaling Exponent (Lang Factor) Unscheduled System Adjustments Up Plant Layout Modifications Down Source: Intratec – www.intratec.us Source: Intratec – www.intratec.us Indirect costs are defined by the American Association of Total Capital Expenses Cost Engineers (AACE) Standard Terminology as those Table 13 presents a summary of the total Capital "costs which do not become a final part of the installation Expenditures (CAPEX) detailed in previous sections. but which are required for the orderly completion of the installation". Fixed Investment Discussion Table 13 – CAPEX (USD Million)Intratec | Economic Analysis Total Fixed Investment Other Capital Expenses Source: Intratec – www.intratec.us 28

Regional ComparisonFigure 10 – CAPEX per Location (USD Million)Source: Intratec – www.intratec.usOperational Expenditures Table 14 – Manufacturing Fixed Cost (USD/ton)Manufacturing Costs Operating Labor CostThe manufacturing costs, also called Operational Maintenance CostExpenditures (OPEX), are composed of two elements: a fixed Operating Chargescost and a variable cost. OPEX figures presented regardexclusively the operation of the improvement underanalysis. Source: Intratec – www.intratec.us Intratec | Economic AnalysisTable 14 shows the manufacturing fixed cost. Table 15 details the manufacturing variable cost breakdown. 29

Table 15 – Manufacturing Variable Cost (USD/ton) Table 16 – OPEX (USD/ton) Membrane Replacement Manufacturing Fixed Cost Propylene PG Manufacturing Variable Cost Fuel By-product Source: Intratec – www.intratec.us Nitrogen Figure 11 depicts Sales and OPEX historic data. Cooling Water Electricity Depreciation Depreciation, while not a true manufacturing cost, is considered to be a manufacturing cost for tax purposes. Source: Intratec – www.intratec.us Table 16 shows the OPEX of the presented technology. Table 17 shows the project depreciation value and the assumptions used in its calculation. Figure 11 – OPEX and Product Sales History (USD/ton)Intratec | Economic Analysis Source: Intratec – www.intratec.us 30

Table 17 – Depreciation Value & Assumptions Depreciation Method Economic Life of Project Depreciation Annual ValueSource: Intratec – www.intratec.usRegional ComparisonAn OPEX breakdown structure for three different locations ispresented in Figure 12.Economic Datasheet &Discussion Return on InvestmentImplementation BenefitsFigure 12 – Operating Costs Breakdown per Location (USD/ton) Intratec | Economic AnalysisSource: Intratec – www.intratec.us 31

Economic Assumptions Fixed costs are estimated based upon the specific characteristics of the process. Table 18 shows the industrial labor requirements for the improvement operation. Other fixed costs, like operating charges and plant overhead, that are typically calculated as a percentage of the industrial labor costs are shown, if pertinent. For further information about the fixed costs considered, please see the chapter “Methodology of the Analysis”. Table 18 – Fixed Cost Assumptions Operators Required To extend your analysis of the PRU presented in this report, Supervisors Required check our available tools presented in the final chapters of this report: Operating Charges (Percent of Operating Labor Costs)  Premium Tools: Deepen Your Analysis Source: Intratec – www.intratec.us  Economic Data Bank: Free Economic Updates Figure 13 – Improvement Earnings Comparison (USD Million)Intratec | Economic Analysis Source: Intratec – www.intratec.us 32

Table 19 – Technology Economics Datasheet: Polypropylene Plant Vent RecoveryLocation TFINominal Capacity Other Capital Exp.Production CAPEXDate (IC Index)Membrane ReplacementPropylene PGFuel By-productNitrogenCooling WaterElectricityOperating LaborMaintenanceOperating ChargesDepreciationLow Purity PropyleneSource: Intratec – www.intratec.us Intratec | Economic Analysis 33

References Intratec | References35

Acronyms, Legends & Observations AACE: American Association of Cost Engineers LPG: Liquefied petroleum gas C: Distillation, stripper, scrubber columns (e.g., C-101 would NGL: Natural gas liquids denote a column tag) OPEX: Operational Expenditures C2, C3, ... Cn: Hydrocarbons with "n" number of carbon atoms OSBL: Outside battery limits C2=, C3=, ... Cn=: Alkenes with "n" number of carbon atoms P: Pumps (e.g., P-101 would denote a pump tag) CAPEX: Capital Expenditures PDMS: Polydimethylsiloxane CC: Distillation column condenser PE: Polyethylene CP: Distillation column reflux pump PG: Polymer grade CR: Distillation column reboiler PP: Polypropylene CW: Cooling water PRU: Propylene recovery unit E: Heat exchangers, heaters, coolers, condensers, reboilers PVC: Polyvinyl chloride (e.g., E-101 would denote a heat exchanger tag) R: Reactors, treaters (e.g., R-101 would denote a reactor tag) EBITDA: Earnings before Interests, Taxes, Depreciation and Amortization RF: Refrigerant (Flowsheet) or Refrigeration Unit (e.g., RF- 801 would denote an equipment tag) F: Furnaces, fired heaters (e.g., F-101 would denote a furnace tag) SB: Steam boiler (e.g., SB-801 would denote an equipment tag) FCC: Fluid-catalytic cracking ST: Steam GS: Gas separation T: Tanks (e.g., T-101 would denote a tank tag) HDPE: High density polyethylene TFI: Total Fixed Investment IC Index: Intratec Chemical Plant Construction Index TPC: Total process costIntratec | Acronyms, Legends & Observations IRR: Internal rate of return V: Horizontal or vertical drums, vessels (e.g., V-101 would ISBL: Inside battery limits denote a vessel tag) K: Compressors, blowers, fans (e.g., K-101 would denote a VCM: Vinyl chloride monomer compressor tag) WD: Demineralized water (Flowsheet) or Demineralizer kta: thousands metric tons per year (e.g., WD-801 would denote an equipment tag) LLDPE: Linear low density polyethylene WP: Process water 36

X: Special equipment (e.g., X-101 would denote a specialequipment tag)Obs.: 1 ton = 1 metric ton = 1,000 kg Intratec | Acronyms, Legends & Observations 37

Methodology of the Analysis General Approach Assumptions General ConsiderationsIntratec | Methodology of the Analysis 38

Figure 14 – Methodology Flowchart Intratec | Methodology of the AnalysisSource: Intratec – www.intratec.us 39

Start-up Expenses Fixed InvestmentIntratec | Methodology of the Analysis Other Capital Expenses 40

Manufacturing Costs Table 20 – Project ContingencyContingencies & Accuracy of Source: Intratec – www.intratec.usEconomic Estimates Table 21 – Accuracy of Economic Estimates Intratec | Methodology of the Analysis Source: Intratec – www.intratec.us 41

Table 22 – Criteria Description Source: Intratec – www.intratec.us Location FactorIntratec | Methodology of the Analysis 42

Figure 15 – Location Factor CompositionSource: Intratec – www.intratec.us Intratec | Methodology of the Analysis 43

Premium Tools: Deepen Your Analysis  IRR (Internal Return Rate) & NPV (Net Present Value) Product Overview  EBITDA (Earnings Before Interest, Taxes, Depreciation Premium Tools is a package of tools that enable the reader and Amortization) to deepen the analysis of the publication purchased. The set includes the following tools:  Sensitivity analyses 1) Several valuable supporting information, not Clients willing to develop analyses for particular contained in the acquired publication. circumstances are able to customize their inputs: 2) Economic Analyzer tool that provides key investment  Plant capacity, operating rate profile (on-stream factor), indicators based on cash flows compiled from construction duration and start-up year; customizable inputs.  Factors impacting capital investment: capital 3) Broad support through an email inquiry service. disbursement profile, percentage of materials imported, working capital strategy, among others Product Description  Price series for products, by-products, feedstock, Valuable Supporting Information: Allows a deeper utilities and labor costs; analysis of the condensed information provided in the publication. The supporting information, according to the Email Support: Premium Tools buyers are encouraged to theme examined, may include: contact our experts via email in order to have specific questions answered about the publication acquired or  Detailed process data, heat & material balances and Premium Tools. key process indicators A total of two man-days (16 hours) is granted.  Streams data, including physical properties and operating conditions Buy Options  Major equipment sizing and specifications For further information about the acquisition of Premium Tools, please visit our website, www.intratec.us.  Estimation of carbon equivalents generated in the process and/or by consumption of process utilities  Detailed operating costs for all locations consideredIntratec | Premium Tools: Deepen Your Analysis  All economic data and assumptions adopted  Location factors for several locations (and how the index is composed) Technology Economic Analyzer: An interactive spreadsheet-like tool able to yield, from a series of user- defined inputs, industrially accepted economic performance indicators for the associated technology. Results are provided in a format ready to be used in your presentation or can be easily tailored. They may consist of: 44

Economic Data Bank: Free Economic Updates  Detailed manufacturing costs (fixed and variable costs)Product Overview  Detailed capital costs breakdownEconomic Data Bank is a yearly subscription service, offeredfor free in IME program, which enables readers to access all  Economic indicators (EBITDA, EBITDA margin, EBITeconomic tables and graphics of a specific publication, with margin)up-to-date figures regarding:Raw materials and productspricing  Total fixed investment  Detailed manufacturing costs  Working capital and other capital expenses  Total fixed investment and working capital Also, subscribers will have the option to download data in editable Microsoft Excel format. Indeed, Economic Data  Economic indicators Bank will give subscribers the information they need to help them to conduct timely assessments on specificProduct Description technologies and solutions within the process industries arena.With more than 10 years providing consulting services forProcess Industries, we recognize that many times proper Access Economic Data Bankdecision making relies on up-to-date information. Faultyassumptions and overoptimistic expectations oftenundermine profitability targets.In this context, wouldn’t it be great having this publicationconstantly updated?Sure it would, and that is why we offer our publicationreaders the Economic Data Bank: a yearly subscriptionservice that enables readers to access all economic tablesand graphics of a publication, with up-to-date figures.More specifically, the Economic Data Bank subscriptionprovides full online access to quarterly updated economicdata of a specific publication, such as:. Intratec | Economic Data Bank: Free Economic Updates  Pricing of products, by-products, feedstock, utilities and labor costs 45

Latest & Upcoming Reports The list below is intended to be an easy and quick way to  Polypropylene Production via Gas Phase Process, identify Intratec reports of interest. For a more complete Part II (Available Soon): A gas phase type process and up-to-date list, please visit the Publications section on similar to Lummus NOVOLEN® for production of both our website, www.intratec.us. homopolymer and random copolymer. TECHNOLOGY ECONOMICS PROGRAM (TEC)  Polypropylene Production via Gas Phase Process, Part III (Available Soon): PP gas phase type process to  Propylene Production via Metathesis: Propylene produce polypropylene homopolymer and random production via metathesis from ethylene and butenes, copolymer. The INEOS INNOVENE™ and JPP in a process similar to Lummus OCT. HORIZONE technologies have their main features discussed.  Propylene Production via Propane Dehydrogenation: Propane dehydrogenation (PDH) IMPROVEMENT ECONOMICS PROGRAM (IME) process conducted in moving bed reactors, in a process similar to UOP OLEFLEX™.  Membranes on Polyolefins Plants Vent Recovery: The Report evaluates membrane units for the  Polypropylene Production via Gas Phase Process: A separation of monomer and nitrogen in PP plants, gas phase type process similar to the Dow UNIPOL™ PP similar to the VaporSep® system commercialized by process to produce both polypropylene homopolymer MTR. and random copolymer.  Impact Polypropylene Production (Available Soon):  Propylene Production from Methanol: Propylene The Report analyzes additional reactors for impact PP production from methanol, in a process is similar to production in a process similar to the Dow UNIPOL™ Lurgi MTP®. PP process.  Propylene Production via Propane RESEARCH ECONOMICS PROGRAM (REC) Dehydrogenation, Part II (Available Soon): Propane dehydrogenation (PDH) in fixed bed reactors, in a  Researches on Green Butadiene Production process is similar to Lummus CATOFIN®. (Available Soon): The Report evaluates the production of 1,3-butadiene from sucrose. In the  Propylene Production via Propane process analyzed, sucrose is fermented to crotyl Dehydrogenation, Part III (Available Soon): Propane alcohol, which is then dehydrated to 1,3-butadiene. dehydrogenation (PDH) by applying oxydehydrogenation, in a process similar to the STAR  Researches on Green Ethylene Production (Available PROCESS® licensed by Uhde. Soon): The Report analyzes ethylene production via ethanol dehydration in a process similar to the route  Polypropylene Production via Bulk Phase Process proposed by BP Chemicals. (Available Soon): PP production of homopolymer andIntratec | Latest & Upcoming Reports random copolymer in bulk phase. The ExxonMobil PP Process, LyondellBasell SPHERIPOL and Mistui HYPOL II technologies have their main features discussed.  Polypropylene Production via Hybrid Process (Available Soon): PP production of both homopolymer and random copolymer in a hybrid type, similar to the Borealis BORSTAR® PP process. 46

AcknowledgmentsWe would like to thank all our readers and clients for sharingtheir views and expertise with us during the entiredevelopment of this issue. It is important that our effortsmeet your requirements, so we highly value your feedbackto improve future editions. Moreover, if you would like tosuggest a new technology, process or product as thesubject of a future Publication, please do not hesitate tocontact us at support@intratec.us. Your comments andsuggestions are more than welcome.Also, you can boost your experience with this publication,by:  Accessing for free up-to-date figures presented in this report, in our Economic Data Bank. For further information see the chapter “Economic Data Bank: Free Economic Updates”  Deepening your analysis, with a package of Premium Tools, available at our website www.intratec.us.  Hiring our Consulting Services, for a more customized and detailed analysis.Finally, you are very welcome to the Intratec PublicationPrograms. We truly thank you!The Intratec TeamPS.: We are eager to hear from you!

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Membranes on Polyolefins Plants Vent Recovery

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Membranes on Polyolefins Plants Vent Recovery Document Transcript