membranes on polyolefins plants vent recovery

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IME

Membranes on Polyolefins Plants

Vent Recovery

Copyrights © 2012 by Intratec Solutions LLC. All rights reserved. Printed in the United States of America. Except as permitted under the United

States 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 or

retrieval system, without the prior written permission of the publisher.

Intratec Report #IME001A

Membranes on Polyolefins Plants Vent Recovery

ISBN: 978-0-615-67891-7

Abstract

Gas 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 recovery

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Contents

Terms and Conditions ........................................................................................................................................................8

About the Program..............................................................................................................................................................9

Program Description .........................................................................................................................................................................................................9

Related Publication Programs .....................................................................................................................................................................................9

Introductory Pricing Offer ..............................................................................................................................................................................................9

University Discount ............................................................................................................................................................................................................9

Buy Options..........................................................................................................................................................................................................................10

About 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........................................................................................................................................................................................................................14

Process & 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 ..................................................................................................................................................................................................................19

Process Analysis................................................................................................................................................................. 21

Process Description & Conceptual Flow Diagram.......................................................................................................................................21

Compression and Cooling.....................................................................................................................................................................................................21

Flashing .............................................................................................................................................................................................................................................21

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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........................................................................................................................................................................................................44

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Buy Options..........................................................................................................................................................................................................................44

Economic Data Bank: Free Economic Updates ...................................................................................................... 45

Product Overview.............................................................................................................................................................................................................45

Product Description........................................................................................................................................................................................................45

Access Economic Data Bank......................................................................................................................................................................................45

Latest & Upcoming Reports .......................................................................................................................................... 46

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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..................................................................................................................................................................................................42

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List of Figures

Figure 1 - Membrane Separation Schematic...................................................................................................................................................................11

Figure 2 - Column Overhead Membrane Recovery ....................................................................................................................................................14

Figure 3 – Reactor Purge Membrane Recovery .............................................................................................................................................................14

Figure 4 - Purge Vent Membrane Recovery .....................................................................................................................................................................14

Figure 5 – Three-Layer Composite Membrane ..............................................................................................................................................................16

Figure 6 – Membrane Modules Schematic.......................................................................................................................................................................16

Figure 7 – Process Simplified Flow Diagram....................................................................................................................................................................18

Figure 8 – Multi-Stage/Multi-Step Membrane Separation .....................................................................................................................................19

Figure 9 - Conceptual Process Flow Diagram.................................................................................................................................................................24

Figure 10 – CAPEX per Location (USD Million)...............................................................................................................................................................29

Figure 11 – OPEX and Product Sales History (USD/ton) ...........................................................................................................................................30

Figure 12 – Operating Costs Breakdown per Location (USD/ton).....................................................................................................................31

Figure 13 – Improvement Earnings Comparison (USD Million)...........................................................................................................................32

Figure 14 – Methodology Flowchart ....................................................................................................................................................................................39

Figure 15 – Location Factor Composition.........................................................................................................................................................................43

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The present publication does not constitute legal, technical,or financial consulting advice. It is offered as an informationservice to readers. For specific guidance for legal, technical,and/or financial matters, readers are referred to professionalassistance, which Intratec Solutions LLC and its subsidiariesand affiliates (collectively known as “Intratec”) can provide(more information at www.intratec.us).

Information, analyses and/or models herein presented areprepared on the basis of information that is publiclyavailable and non-confidential information disclosed bytechnology licensors and other third parties. Intratec doesnot believe that such information will contain anyconfidential technical information of third parties butcannot provide any assurance that any third party may,from time to time, claim a confidential obligation to suchinformation. The aforesaid information, analyses andmodels are developed independently by Intratec and, assuch, are the opinion of Intratec and do not represent thepoint of view of any third parties nor imply in any way thatthey have been approved or otherwise authorized by thirdparties that are mentioned in this publication. Theapplication of the technologies reviewed in this publicationwithout license from the owners infringes on theintellectual property rights of the owners, including patentrights, trademark rights, copyrights, and rights to tradesecrets and proprietary information.

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Terms and Conditions

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Program Description

Intratec, recognized for its expertise in creative and low-investment solutions in the areas of technology and processconsulting for the global chemical industry, is pleased topresent Intratec's Improvement Economics Program (IME).

IME is a multi-client program that, by way of periodicreports, provides insightful and unbiased reviews onprocess improvement opportunities, from both technicaland economic perspectives. The reports examine existingsolutions and approaches that are designed to maximizeproductivity, increase plant availability or addressenvironmental issues of existing processes. IME readers willlearn about the value-creation potential of processimprovement options available through independentappraisals encompassing:

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Introduction

Membranes can be defined as barriers capable ofseparating two phases and, simultaneously, limitingchemical components transport in a selective manner. Atypical membrane system can generate a permeateproduct, in separation processes, or a residue product, inpurification processes, as depicted in Figure 1.

Membranes can have a wide range of characteristics andproperties, which suit them for an equally wide range ofapplications, ranging from industrial to medicine, forexample. The artificial kidney (utilized in clinical therapysince the early 1960s) and the membrane blood oxygenator(which enabled open-heart surgeries) are remarkableexamples of the success of membranes.

The concept of a membrane has been known since theeighteenth century, but it remained as only a tool forphysical / chemical theories development until the end ofWorld War II, when drinking water supplies in Europe werecompromised and membrane filters were used to test forwater safety. However, due to the lack of reliability, slowoperation, reduced selectivity and elevated costs,membranes were not widely exploited.

In the early 1960s, Loeb and Sourirajan developed apreparation method of asymmetric high flux membranesfor reverse osmosis applied to water desalinization. Thisadvance, along with large investments from the USDepartment of Interior, contributed to the

commercialization of reverse osmosis and, also, thedevelopment of microfiltration and ultrafiltrationtechnologies. That was the first use of membranes on alarge scale.

Since the 1980’s, these separation processes, along withelectrodialysis, are employed in large plants and, today, anumber of experienced companies serve the market.

Certain features of membranes are responsible for theinterest in using them as substitutes to consolidatedindustrial separation processes, like distillation, absorption,adsorption or extraction. Some advantages noted include:

Less energy-intensive, since they do not require majorphase changes

Do not demand adsorbents or solvents, which may beexpensive or difficult to handle

Equipment simplicity and modularity, which facilitatesthe incorporation of more efficient membranes

Spurred by the advances in membrane materials, a widerange of processes became commercialized. Some of theseprocesses and their respective applications are summarizedin Table 1.

Membranes for Gas Separation

Although the asymmetric membranes developed forreverse osmosis enhanced separation performance,extending this concept to gas separation was not simple.

The first commercial application was only launched in 1980by Monsanto, which developed composite membranes forhydrogen separation, particularly from purge gases inammonia plants. Its success established the commercialfeasibility of gas separation with membranes and was anincentive for other companies to market their ownmembrane technologies.

Gas separation by membranes is, now, a relatively well-established unit operation in the petrochemical industry.However, it did not achieve a maturity level comparable tomicrofiltration or ultrafiltration, for example.

About Membrane Separation Processes

Figure 1 - Membrane Separation Schematic

Feed ResidueStream

Permeate Stream

MembraneLayer

Membrane Module

Source: Intratec – www.intratec.us

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Oil-and-Gas and Petrochemical Industries

Applications

Aligned with new environmental standards and aimed atreducing the costs of industrial processes, separation ofgaseous mixtures through membranes is likely to expandapplications in refineries and petrochemical industries.Table 2 summarizes some petrochemical, refineries andnatural gas applications of membranes.

Natural gas purification is a segment in which membraneshave a great potential to expand, due to several aspects.Firstly, raw gas composition can vary greatly depending onits source, but the composition of the delivered gas mustfollow tight specifications. Hence, treatment steps arerequired, in smaller or larger extension. Secondly, naturalgas processing historically ranges from 15-20 trillion cubicfeet, only in the U.S., and membranes still accounts for asmall percentage of this market, with the main applicationstanding in CO2 removal.

A smaller but growing application is the use of membranesin recovering organic vapors, motivated by both valuablecomponents’ losses and by the establishment of more strictemission regulations, notably in Germany and in the U.S.A.Monomer recovery from polyolefin plants vents andgasoline capture from tank farms or fuel terminals werealready available in the mid-1990s.

Similarly, unreacted vinyl chloride monomer (VCM) used inPVC production is not properly recovered by simplecondensation of the reactor vent stream. Grounded byregulations associated with its emission, membrane unitsfor VCM recovery were applied even before their use inmonomer separation.

The large volumes of hydrocarbons processed in refineriesand in the petrochemical industry may limit membrane usedue to the extremely large surface areas that would berequired to achieve determined separations.

Table 1 – Industrial Membrane Processes

Microfiltration Large Liquid Liquid Pressure Bacteria and suspensions

Ultrafiltration Medium Liquid Liquid Pressure Emulsions and polymers

Nanofiltration Small Liquid Liquid Pressure Low molecular weightcomponents (microsolutes)

Reverse Osmosis Very Small Liquid Liquid Pressure Desalination (NaCl)

Pervaporation Very Small Liquid Vapor Vapor PressureDehydration of organicsolvents (ethanol, iso-propanol, etc)

Gas Separation Very Small Gas Gas Vapor Pressure Gases, such as N2/O2

Vapor Permeation Very Small Vapor Vapor Vapor Pressure Monomer recovery, naturalgas drying, etc


Table 2 – Membrane Applications in the Oil-and-Gas

and Petrochemical Industries

Petrochemical

Ethylene recovery in ethylene oxideproduction

Polyolefin plants monomer recovery

PVC plants monomer recovery

Syngas ratio adjustment

Refining

Hydrogen recovery from various streams(FCC overhead gas, catalyst-cracker off-gas, etc)

Catalytic reformer hydrogen upgrading

LPG recovery

Natural Gas

CO2 and N2 removal

Natural gas liquids removal

Digester off-gas treatment


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Meanwhile, the larger market share remains in treating“clean gases” streams, i.e., those that do not presentcomponents that might cause fouling or plasticize themembrane. N2 separation from air and H2 separation fromammonia purge vent or syngas can be cited.

Membrane Materials and Modules

The most widely employed materials in gas separation arepolymeric dense membranes, although only a smallnumber (about 10 polymers) are employed commercially.

To be recognized as a suitable industrial separation material,the membrane must show characteristics such as:

Stability

Thin selective layer

Defect-free structure

Proper mechanical resistance or available physicalsupport

After selection of the more suitable material, is necessary topackage the membrane to obtain compact, high surfacearea modules. The characteristics of the material can limitthe modules manufacturing possibilities and, consequently,the type of modules.

The modules are factory-built and are replaced entirelywhen necessary. On one hand, this modular characteristicfacilitates maintenance and minimizes plants’ downtimesbut, on the other hand, little economy of scale is verified.The order of magnitude for the membrane area requiredmay range from hundreds to thousands of square meters;hence, a large number of modules are required.

The most frequently employed types of modules for gasseparation are hollow-fiber and spiral-wound. Table 3presents some examples of applications and theirrespective modules.

Polyolefin Plants Opportunities

In essence, industrial polymerization processes can bedescribed as catalytic reactions wherein monomers formmacromolecules characterized by a certain conjunct ofcommercially appealing properties. Standing as the mainvapor permeation application, polyolefin plants presentimportant stages in which membranes can be applied.

Raw Material Purification

The first (and significant) stage in polymerization process isfitting the raw materials to the sensitiveness of the catalystsystem and/or to avoid the accumulation of inertsubstances. Depending on monomer’s specific source,direct use is not always suitable and removal of light gasessuch as N2, H2 and CH4 is often necessary.

In polyethylene (PE) plants, this may be accomplished by anethylene stripper, but light gases build-up in the columnoverhead requires a purge that can carry considerableamounts of ethylene. To minimize this issue, it is possible toimplement a membrane unit to receive the lights streamand recycle enriched ethylene permeate to the column.Additionally, the column size required could be reduced.

Table 3 – Types of Modules and Applications

O2 / N2 Hollow-fiber

H2 / N2 Hollow-fiber

CO2 / CH4 Spiral-wound and hollow-fiber

VOC / N2 Spiral-wound

H2O / AIR Capillary-fiber


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Reaction System

This sort of application is mainly present in polyethyleneproduction. In both linear low density polyethylene (LLDPE)and high density polyethylene (HDPE), control of the partialpressure of ethylene in the reactor requires the addition ofnitrogen. The purge of the reactor not only removesnitrogen, but also unreacted monomers, which allows amembrane unit to be used to reduce monomer losses.

Product Finishing

The degassing/drying stage is largely responsible formonomer losses in polypropylene (PP) plants and anadditional recovery point in polyethylene production.

Typically, the newly formed polyolefin contains entrainedmonomers, water used to deactivate catalyst residues, andinert components, such as propane. In order to suit thepolymer for extrusion and pelletizing and increase thesafety, environmental, and product quality aspects of theprocess, hot nitrogen is generally used, resulting in a ventgas containing hydrocarbons, nitrogen and water.

The earning potential of recovering monomer rather thanburning it as fuel, as in older plants, encouraged companiesto consider the use of membrane separation units.Although most state-of-the-art technologies may providealternatives for such recovery, most older plants lack properseparation methods. Nowadays, near 50 of thesemembrane systems have been installed in polyolefin plants.

Figure 4 depicts this type of application in a HDPE plant.

Figure 2 – Column Overhead Membrane Recovery

MonomerFeed

OlefinProduct

Residueto Flareor Fuel

Membrane Unit

C2-EnrichedPermeate

Ethylene-Ethane Splitter

Heavies


Figure 3 – Reactor Purge Membrane Recovery

MembraneUnit

PolymerDischarge

C2-depletedresidue

PEReactor

C2-enrichedpermeate

MonomerFeed

Purge

RecycleGas


Figure 4 - Purge Vent Membrane Recovery

MembraneUnit

RecoveredIso-Butane

Condenser

Resin

N2 feed

Polymer

ToFlare

PurgeBin

Permeate


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Supplier(s) & Historical Aspects

The two main suppliers of vapor/gas membrane separationsystems are licensees of GKSS (Borsig, Dalian Eurofilm andSihi) and MTR.

The first applications of VOC removal from air were inrecovering gasoline vapors or solvents in the early 1990s.Nowadays, hundreds of larger and smaller systems withapplications such as resin degassing vent recovery, gasolinevapor recovery, and MVC recovery have been installedaround the world.

In terms of polyolefin applications, membrane technologiesfor monomer/nitrogen separation currently available arevery similar, but MTR is the leader in this application. MTR’sfirst order dates from 1996 and was installed in a PP plant inthe Netherlands.

Eurofilm has a number of installed units in China forpropylene recovery, most of them in smaller batchprocesses. Until 2011, only two membrane units forcontinuous processes had been installed, for JPP andSinopec Wuhan.

Although these membrane systems are relatively new,major polyolefins producers around the world utilize them.In addition to the aforementioned JPP and Sinopec Wuhan,Borealis, ExxonMobil, Formosa Plastics, INEOS, Lummus,SABIC, and Sasol can be cited. In fact, both the INEOSInnovene™ and Lummus Novolen® polypropyleneprocesses can be provided with membrane recovery units.

Improvement Summary

The current publication assesses in detail a technology fornitrogen and propylene recovery in a polypropylene plant,having low purity propylene (about 83 wt. %) as its mainproduct. A process similar to MTR VaporSep® is analyzedand employed in the finishing section of the plant. Thistype of system is often called a propylene recovery unit(PRU).

All the data and figures presented were prepared based onpublicly available information. This information wascarefully analyzed through a structured methodology

involving process simulations, design procedures andmathematical models developed by Intratec.

Description

The improvement consists of a vapor permeation systemcombining membrane and cryogenic separationtechniques (hybrid process). The membrane components’characteristics are described in this section, while the otherequipment in the system are only discussed in theoperation description.

The PRU consists of a skid of about 15 m2 of footprint, withthe compressor occupying a similar skid. Generally, thesupplier provides the entire solution.

Membrane Material

The membrane itself usually consists of a multilayeredcomposite structure in which the different materials exhibitdistinct functions. In polyolefin production, the vent gasrecovery membranes are often described as follows:

Selective thin layer. Rubbery polymers such aspolydimethylsiloxane (also called PDMS or siliconerubber) are chosen to selectively permeate propylenerather than nitrogen.

Micro-porous support layer. Employed formechanical support, provides a smooth surface onwhich the selective thin layer can be coated.

Non-woven fabric. Also employed to providemechanical strength, serve as substrate to themembrane. Its pores are too large to be coateddirectly with the selective thin layer.

Figure 5 shows a schematic of such a structure. Theselective layer’s chemical structure is often very simple andsimilar, regardless of the supplier. Certain gaseous mixtures,however, may demand more specific and complexmembranes.

PDMS is generally chosen for this application due to theirhigh permeability when compared to glassy polymers and,also, because the latter often do not demonstrate highenough selectivity.

Process & Economics Overview

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The use of a membrane more selective to the monomer inthe purge bin vent leads to smaller membrane arearequirements. Otherwise, the bulk of the vent would haveto permeate. Propane contained in the mixturedemonstrates similar separation characteristics whencompared to propylene.

Modules

Since rubbery polymers are not easily fabricated into the

lower cost hollow-fibers, spiral-wound modules are used.Moreover, the spiral-wound modules can operate at higherfeed flows, unlike hollow-fibers.

Spiral-wound modules standard sizes are 100-150 cm longand 10 - 30 cm diameter. Their size is ideally guided by theease of handling, with one or two persons being able tohandle a weight of up to approximately 20 kg.

In essence, spiral-wound module consists of multiplemembrane layers, feed and permeate spacers rolled arounda permeate collection tube. Spacers are also represented inFigure 5.

Modules Organization

Whereas packing the membrane in a compact andeconomical module is desirable, the same concept must beextended to the modules’ organization. Figure 6 presentsan assembling possibility for the membrane system.

From 2 to 6 cylindrical modules, arranged end-to-end, canbe placed in permanent housings made of carbon steel orstainless steel, which permit the system to operate atpressures other than atmospheric. In order to simplifymodules’ replacement, each one possesses its ownpermeate collection tube, which may protrude beyond themodule and be joined by gas-tight connectors. Hence, thepermeate gas path is formed, and may be collected by

Figure 5 – Three-Layer Composite Membrane

Permeate flow (permeate spacer)

Selectivelayer

Micro-poroussupport layer

Non-wovenfabric

Feed flow (feed spacer)


Figure 6 – Membrane Modules Schematic

Feedinlet

Permeatepipes

Residueoutlet

Membranemodules

Permeateoutlet

Membranehousing

Pressurevessel

Pressure vessel side view


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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 Assumptions

This 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 Diagram

The 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.

The 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.

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After condensation and flashing, the low temperatureliquid, containing mainly propylene and propane, is used forheat integration and, then, sent to a cracker unit forpurification.

A two-step membrane scheme is assumed for separation,with steps placed in series. The first step is responsible forconcentrating propylene, while the second one purifiesnitrogen to the purge bin.

The first membrane step generates a residue streamenriched in nitrogen, which is sent to the secondmembrane step. The permeate is recycled to the inlet ofthe compressor.

In the second membrane step, a residue stream containingnitrogen at 99 wt% purity is obtained. This stream issuitable for direct reuse without further purification. Thepermeate stream, in turn, is not sufficiently pure and isemployed as boiler fuel.

Table 4 - Implementation Assumptions

Plant UnderAnalysis

Initial Scenario

ImprovementProposed

Scenario afterImprovement

OSBLRequirements


Figure 7 – Process Simplified Flow Diagram

Wet Resin

FreshNitrogen

Dry Resin

ResinDegassing Bin

Propylene-RichPermeate

PureNitrogen

Low PurityPropylene toPurification

Off-GasCondenser

2nd MembraneStep

1st MembraneStep

To Boiler

Notes:

The blue lines represent the additional equipment and streams of the improvement, while the black lines represent processequipment and streams relative to the initial scenario.

Compressor

Flash

to CompressorInlet

Source: MTR website, Intratec analysis

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Economic Summary

The table below summarizes the main economic indicatorsof 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.

CAPEX (USD Million)

TFI

Other Initial Expenses

Net Product Sales (USD Million/yr)

OPEX (USD Million/yr)

EBITDA (USD Million/yr)

Substitute Solutions

Table 5 – Capital Cost & Economic Summary


Figure 8 – Multi-Stage/Multi-Step Membrane

Separation

Propylene-enrichedpermeate

Propylene/N2 mixture

N2

N2purification

Propyleneconcentration


Alternatives Overview

Different Implementations

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Process Description &Conceptual Flow Diagram

This 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 areconsidered: 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

Process Analysis

Flashing

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Key Consumptions

Membrane Replacement

Propylene PG

Cooling Water

Electricity

Fuel By-product

Nitrogen

Table 6 - Raw Materials & Consumptions (per ton of

Product)


Membrane Separation

Technical Assumptions

All process design and economics are based on world-classcapacity PRU units that are installed in globally competitivepolypropylene plants.

Assumptions regarding the thermodynamic model used inthe process simulation, main improvement design basis andthe raw materials composition are shown in Table 7. Alldata used to develop the process flow diagram was basedon publicly available information.

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Simulation Software

Thermodynamic Model

Feed Flow

Operating Hours per Year

Nitrogen

Propane

Propylene

Propylene Purity

Propylene Recovery from Feed

Nitrogen Purity

Nitrogen Recovery from Feed

Temperature

Residue Pressure

Permeate Pressure

Temperature

Residue Pressure

Permeate Pressure

Selective Layer Material

Expected Lifetime

The assumed operating hours per year indicated does notrepresent any technology limitation; it is rather anassumption based on usual industrial operating rates.

Table 7 – Design & Simulation Assumptions


The future is

just aheadResearch

Economics Program

Guidelines for research and

planning within the process

industry arena.

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Figure 9 - Conceptual Process Flow Diagram


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Major Equipment List

Table 9 shows the equipment list, besides a briefdescription and the main materials used.

For complete equipment list, including sizing, see theChapter titled “Premium Tools: Deepen Your Analysis”,presented in this publication.

Name

Phase

Temperature (°C)

Pressure (bara)

Mass Flow (kg/h)

Propylene (wt%)

Propane (wt%)

Nitrogen (wt%)

Table 8 – Main Streams Operating Conditions and Composition


Table 9 – Major Equipment List

E-101 Comp. Intercooler CS


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General Assumptions

This study strictly evaluates the earnings, operating andcapital expenditures associated with the improvement itself.All figures are in addition to the economics of a suitableexisting plant. Such plants’ operating and capitalexpenditures are not in the scope of the presentpublication.

The general assumptions for the base case of this analysisare outlined below.

Engineering & Construction Location

Analysis Date

IC Index

Nominal Capacity

Operating Hours per Year

Annual Production

Project Complexity

Technology Maturity

Evaluation Phase

Data Reliability

Economic Analysis

Table 10 – Base Case General Assumptions


In Table 10, the IC Index stands for Intratec chemical plantConstruction 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.

Additionally, 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

of economic estimates can be found in this publication inthe chapter “Methodology of the Analysis”.

Capital Expenditures

Fixed Investment

Table 11 discloses the breakdown of the total fixedinvestment (TFI) per item (direct & indirect costs and projectcontingencies).

Fundamentally, the direct costs are the total direct materialand labor costs associated with the equipment (includinginstallation bulks). The total direct cost represents the totalbare equipment installed cost.

After defining the total direct cost, the TFI is established byadding field indirects, engineering costs, overhead, contractfees and contingencies.

For further information about the components of the TFIplease see the chapter “Methodology of the Analysis”.

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Direct Project Expenses

Bare Equipment

Equipment Setting

Piping

Civil

Steel

Instrumentation and Control

Electrical Equipment

Insulation

Paint

Indirect Project Expenses

Engineering & Procurement

Construction Material & Indirects

G & A Overheads

Contract Fee

Project Contingency (15% of TPC)

Other - Scaling Exponent (Lang Factor)

Up

Down

Indirect costs are defined by the American Association ofCost Engineers (AACE) Standard Terminology as those"costs which do not become a final part of the installationbut which are required for the orderly completion of theinstallation".

Fixed Investment Discussion

Other Capital Expenses

Start-up Expenses

Operator training

Commercialization costs

Start-up Inefficiencies

Unscheduled System Adjustments

Plant Layout Modifications

Total Fixed Investment


Table 11 – Total Fixed Investment Breakdown (USD

Thousands)


Table 12 – Other Capital Expenses (USD Million)


Table 13 – CAPEX (USD Million)


Total Capital Expenses

Table 13 presents a summary of the total CapitalExpenditures (CAPEX) detailed in previous sections.

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Regional Comparison

Operational Expenditures

Manufacturing Costs

The manufacturing costs, also called OperationalExpenditures (OPEX), are composed of two elements: a fixedcost and a variable cost. OPEX figures presented regardexclusively the operation of the improvement underanalysis.

Table 14 shows the manufacturing fixed cost.

breakdown.

Figure 10 – CAPEX per Location (USD Million)


Table 14 – Manufacturing Fixed Cost (USD/ton)


Operating Labor Cost

Maintenance Cost

Operating Charges

Table 15 details the manufacturing variable cost

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Propylene PG

Fuel By-product

Nitrogen

Cooling Water

Electricity

Table 17 shows the project depreciation value and theassumptions used in its calculation.

Table 15 – Manufacturing Variable Cost (USD/ton)


Figure 11 – OPEX and Product Sales History (USD/ton)


Table 16 – OPEX (USD/ton)


Table 16 shows the OPEX of the presented technology.

Figure 11 depicts Sales and OPEX historic data.

Depreciation

Depreciation, while not a true manufacturing cost, isconsidered to be a manufacturing cost for tax purposes.

Manufacturing Fixed Cost

Manufacturing Variable Cost

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Depreciation Method

Economic Life of Project

Depreciation Annual Value

Regional Comparison

An OPEX breakdown structure for three different locations ispresented in Figure 12.

Economic Datasheet &Discussion

Implementation BenefitsReturn on Investment

Table 17 – Depreciation Value & Assumptions


Figure 12 – Operating Costs Breakdown per Location (USD/ton)


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To extend your analysis of the PRU presented in this report,check our available tools presented in the final chapters ofthis report:

Premium Tools: Deepen Your Analysis

Economic Data Bank: Free Economic Updates

Economic Assumptions

Fixed costs are estimated based upon the specificcharacteristics of the process. Table 18 shows the industriallabor requirements for the improvement operation. Otherfixed costs, like operating charges and plant overhead, thatare typically calculated as a percentage of the industriallabor costs are shown, if pertinent.

For further information about the fixed costs considered,please see the chapter “Methodology of the Analysis”.

Figure 13 – Improvement Earnings Comparison (USD Million)


Table 18 – Fixed Cost Assumptions

Operators Required

Supervisors Required

Operating Charges (Percent of Operating LaborCosts)


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Table 19 – Technology Economics Datasheet: Polypropylene Plant Vent Recovery

Location

Nominal Capacity

Production

Date (IC Index)

TFI

Other Capital Exp.

CAPEX


Propylene PG

Fuel By-product

Nitrogen

Cooling Water

Electricity

Operating Labor

Maintenance

Operating Charges

Depreciation

Low Purity Propylene


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AACE: American Association of Cost Engineers

C: Distillation, stripper, scrubber columns (e.g., C-101 woulddenote a column tag)

C2, C3, ... Cn: Hydrocarbons with "n" number of carbonatoms

C2=, C3=, ... Cn=: Alkenes with "n" number of carbon atoms

CAPEX: Capital Expenditures

CC: Distillation column condenser

CP: Distillation column reflux pump

CR: Distillation column reboiler

CW: Cooling water

E: Heat exchangers, heaters, coolers, condensers, reboilers(e.g., E-101 would denote a heat exchanger tag)

EBITDA: Earnings before Interests, Taxes, Depreciation andAmortization

F: Furnaces, fired heaters (e.g., F-101 would denote afurnace tag)

FCC: Fluid-catalytic cracking

GS: Gas separation

HDPE: High density polyethylene

IC Index: Intratec Chemical Plant Construction Index

IRR: Internal rate of return

ISBL: Inside battery limits

K: Compressors, blowers, fans (e.g., K-101 would denote acompressor tag)

kta: thousands metric tons per year

LLDPE: Linear low density polyethylene

LPG: Liquefied petroleum gas

NGL: Natural gas liquids

OPEX: Operational Expenditures

OSBL: Outside battery limits

P: Pumps (e.g., P-101 would denote a pump tag)

PDMS: Polydimethylsiloxane

PE: Polyethylene

PG: Polymer grade

PP: Polypropylene

PRU: Propylene recovery unit

PVC: Polyvinyl chloride

R: Reactors, treaters (e.g., R-101 would denote a reactor tag)

RF: Refrigerant (Flowsheet) or Refrigeration Unit (e.g., RF-801 would denote an equipment tag)

SB: Steam boiler (e.g., SB-801 would denote an equipmenttag)

ST: Steam

T: Tanks (e.g., T-101 would denote a tank tag)

TFI: Total Fixed Investment

TPC: Total process cost

V: Horizontal or vertical drums, vessels (e.g., V-101 woulddenote a vessel tag)

VCM: Vinyl chloride monomer

WD: Demineralized water (Flowsheet) or Demineralizer(e.g., WD-801 would denote an equipment tag)

WP: Process water

Acronyms, Legends & Observations

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X: Special equipment (e.g., X-101 would denote a specialequipment tag)

Obs.: 1 ton = 1 metric ton = 1,000 kg

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General Approach

Assumptions

General Considerations

Methodology of the Analysis

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Figure 14 – Methodology Flowchart


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Fixed Investment

Start-up Expenses


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Manufacturing Costs

Table 20 – Project Contingency


Table 21 – Accuracy of Economic Estimates


Contingencies & Accuracy ofEconomic Estimates

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Location Factor

Table 22 – Criteria Description


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Figure 15 – Location Factor Composition


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Product Overview

Premium Tools is a package of tools that enable the readerto deepen the analysis of the publication purchased. Theset includes the following tools:

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Location factors for several locations (and how theindex is composed)

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Product Overview

Economic Data Bank is a yearly subscription service, offeredfor free in IME program, which enables readers to access alleconomic tables and graphics of a specific publication, withup-to-date figures regarding:Raw materials and productspricing

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With more than 10 years providing consulting services forProcess Industries, we recognize that many times properdecision making relies on up-to-date information. Faultyassumptions and overoptimistic expectations oftenundermine profitability targets.

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The list below is intended to be an easy and quick way toidentify Intratec reports of interest. For a more completeand up-to-date list, please visit the Publications section onour website, www.intratec.us.

TECHNOLOGY ECONOMICS PROGRAM (TEC)

Propylene Production via Metathesis: Propyleneproduction via metathesis from ethylene and butenes,in a process similar to Lummus OCT.

Propylene Production via Propane

Dehydrogenation: Propane dehydrogenation (PDH)process conducted in moving bed reactors, in aprocess similar to UOP OLEFLEX™.

Polypropylene Production via Gas Phase Process: Agas phase type process similar to the Dow UNIPOL™ PPprocess to produce both polypropylene homopolymerand random copolymer.

Propylene Production from Methanol: Propyleneproduction from methanol, in a process is similar toLurgi MTP®.


Dehydrogenation, Part II (Available Soon): Propanedehydrogenation (PDH) in fixed bed reactors, in aprocess is similar to Lummus CATOFIN®.


Dehydrogenation, Part III (Available Soon): Propanedehydrogenation (PDH) by applyingoxydehydrogenation, in a process similar to the STARPROCESS® licensed by Uhde.

Polypropylene Production via Bulk Phase Process

(Available Soon): PP production of homopolymer andrandom copolymer in bulk phase. The ExxonMobil PPProcess, LyondellBasell SPHERIPOL and Mistui HYPOL IItechnologies have their main features discussed.

Polypropylene Production via Hybrid Process

(Available Soon): PP production of bothhomopolymer and random copolymer in a hybridtype, similar to the Borealis BORSTAR® PP process.

Polypropylene Production via Gas Phase Process,

Part II (Available Soon): A gas phase type processsimilar to Lummus NOVOLEN® for production of bothhomopolymer and random copolymer.

Polypropylene Production via Gas Phase Process,

Part III (Available Soon): PP gas phase type process toproduce polypropylene homopolymer and randomcopolymer. The INEOS INNOVENE™ and JPPHORIZONE technologies have their main featuresdiscussed.

IMPROVEMENT ECONOMICS PROGRAM (IME)

Membranes on Polyolefins Plants Vent Recovery:

The Report evaluates membrane units for theseparation of monomer and nitrogen in PP plants,similar to the VaporSep® system commercialized byMTR.

Impact Polypropylene Production (Available Soon):

The Report analyzes additional reactors for impact PPproduction in a process similar to the Dow UNIPOL™PP process.

RESEARCH ECONOMICS PROGRAM (REC)

Researches on Green Butadiene Production

(Available Soon): The Report evaluates theproduction of 1,3-butadiene from sucrose. In theprocess analyzed, sucrose is fermented to crotylalcohol, which is then dehydrated to 1,3-butadiene.

Researches on Green Ethylene Production (Available

Soon): The Report analyzes ethylene production viaethanol dehydration in a process similar to the routeproposed by BP Chemicals.

Latest & Upcoming Reports

Also, you can boost your experience with this publication,by:

Accessing for free up-to-date figures presented in thisreport, in our Economic Data Bank. For furtherinformation see the chapter “Economic Data Bank:Free Economic Updates”

Deepening your analysis, with a package of PremiumTools, available at our website www.intratec.us.

Hiring our Consulting Services, for a more customizedand detailed analysis.

Finally, you are very welcome to the Intratec PublicationPrograms. We truly thank you!

The Intratec Team

PS.: We are eager to hear from you!

Acknowledgments

We 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 [email protected]. 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 thisreport, in our Economic Data Bank. For furtherinformation see the chapter “Economic Data Bank:Free Economic Updates”

Deepening your analysis, with a package of PremiumTools, available at our website www.intratec.us.

Hiring our Consulting Services, for a more customizedand detailed analysis.

Finally, you are very welcome to the Intratec PublicationPrograms. We truly thank you!

The Intratec Team

PS.: We are eager to hear from you!

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IC INDEX

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Improvement Economics Program (IME)

IME provides insightful and unbiased reviews on process improvement opportunities, from both technical and economic perspectives. Amid the ever-growing pressure faced by industries to deliver profitability, IME reports scrutinize existing solutions and approaches, designed to maximize productivity, increase plant availability or address environmental issues of existing processes.

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