Membranes on Polyolefins Plants Vent Recovery

COVER IME

Membranes on Polyolefins Plants Vent Recovery

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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 wellestablished unit operation, especially in the production of polymers. The process of polymer degassing is necessary to suit polymer for extrusion and pelletizing, increasing safety, environmental, and product quality aspects. Nitrogen is generally used for this 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 world already employ them in new state-of-the-art plants. In order to enhance the competitiveness of older plants, the use of a recovery solution is becoming mandatory.

In this report, the recovery of propylene and nitrogen from a polypropylene degassing vent stream is reviewed and compared with its use as boiler fuel. Included in the analysis is an overview of the technology and economics of a process similar to MTR VaporSep®. Both the capital investment and the operating costs are presented for a propylene recovery unit (PRU) operating in the 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. The estimated CAPEX for such unit is USD 5.8 million on the US Gulf Coast, the lowest figure among the regions under analysis. Due to propylene scarcity, which raised its market value, and the low fuel prices due to natural gas growing offerings, installation of a membrane unit for this type of recovery is advantageous. This fact is proven by the calculated internal rate of return of more than 40% per year in the region.

Furthermore, local propylene and fuel market dynamics are the key drivers in evaluating a membrane separation unit’s attractiveness. If fuel can be obtained from inexpensive sources and propylene is priced high, the unit’s installation could be considered. This improvement is already part of state-of-the-art polypropylene technologies such as INEOS Innovene™ and Lummus 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 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........................................................................................................................................................................................................44 4

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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Information, analyses and/or models herein presented are prepared on the basis of information that is publicly available and non-confidential information disclosed by technology licensors and other third parties. Intratec does not believe that such information will contain any confidential technical information of third parties but cannot provide any assurance that any third party may, from time to time, claim a confidential obligation to such information. The aforesaid information, analyses and models are developed independently by Intratec and, as such, are the opinion of Intratec and do not represent the point of view of any third parties nor imply in any way that they have been approved or otherwise authorized by third parties that are mentioned in this publication. The application of the technologies reviewed in this publication without license from the owners infringes on the intellectual property rights of the owners, including patent rights, trademark rights, copyrights, and rights to trade secrets and proprietary information.

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About Membrane Separation Processes Introduction Membranes can be defined as barriers capable of separating two phases and, simultaneously, limiting chemical components transport in a selective manner. A typical membrane system can generate a permeate product, in separation processes, or a residue product, in purification processes, as depicted in Figure 1.

Since the 1980’s, these separation processes, along with electrodialysis, are employed in large plants and, today, a number of experienced companies serve the market.

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

Figure 1 - Membrane Separation Schematic

 Less energy-intensive, since they do not require major

Membrane Module Residue Stream

Feed

commercialization of reverse osmosis and, also, the development of microfiltration and ultrafiltration technologies. That was the first use of membranes on a large scale.

Membrane Layer Permeate Stream

phase changes

 Do not demand adsorbents or solvents, which may be expensive or difficult to handle

 Equipment simplicity and modularity, which facilitates the incorporation of more efficient membranes

Membranes can have a wide range of characteristics and properties, which suit them for an equally wide range of applications, ranging from industrial to medicine, for example. The artificial kidney (utilized in clinical therapy since the early 1960s) and the membrane blood oxygenator (which enabled open-heart surgeries) are remarkable examples of the success of membranes.

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

In the early 1960s, Loeb and Sourirajan developed a preparation method of asymmetric high flux membranes for reverse osmosis applied to water desalinization. This advance, along with large investments from the US Department of Interior, contributed to the

Spurred by the advances in membrane materials, a wide range of processes became commercialized. Some of these processes and their respective applications are summarized in Table 1.

Membranes for Gas Separation Although the asymmetric membranes developed for reverse osmosis enhanced separation performance, extending this concept to gas separation was not simple.

The first commercial application was only launched in 1980

by Monsanto, which developed composite membranes for hydrogen separation, particularly from purge gases in ammonia plants. Its success established the commercial feasibility of gas separation with membranes and was an incentive for other companies to market their own membrane technologies.

Gas separation by membranes is, now, a relatively wellestablished unit operation in the petrochemical industry.

However, it did not achieve a maturity level comparable to microfiltration or ultrafiltration, for example.

Intratec | About Membrane Separation Processes

Source: Intratec – www.intratec.us

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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 weight components (microsolutes)

Reverse Osmosis

Very Small

Liquid

Liquid

Pressure

Desalination (NaCl)

Pervaporation

Very Small

Liquid

Vapor

Vapor Pressure

Dehydration of organic solvents (ethanol, isopropanol, etc)

Gas Separation

Very Small

Gas

Gas

Vapor Pressure

Gases, such as N2/O2

Vapor Permeation

Very Small

Vapor

Vapor

Vapor Pressure

Monomer recovery, natural gas drying, etc

Source: Intratec – www.intratec.us

Oil-and-Gas and Petrochemical Industries Applications Aligned with new environmental standards and aimed at reducing the costs of industrial processes, separation of gaseous mixtures through membranes is likely to expand applications in refineries and petrochemical industries.

Table 2 summarizes some petrochemical, refineries and natural gas applications of membranes.

Table 2 – Membrane Applications in the Oil-and-Gas and Petrochemical Industries Ethylene recovery in ethylene oxide production

Intratec | About Membrane Separation Processes

Petrochemical

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Polyolefin plants monomer recovery

Natural gas purification is a segment in which membranes have a great potential to expand, due to several aspects.

Firstly, raw gas composition can vary greatly depending on its source, but the composition of the delivered gas must follow tight specifications. Hence, treatment steps are required, in smaller or larger extension. Secondly, natural gas processing historically ranges from 15-20 trillion cubic feet, only in the U.S., and membranes still accounts for a small percentage of this market, with the main application standing in CO2 removal.

A smaller but growing application is the use of membranes in recovering organic vapors, motivated by both valuable components’ losses and by the establishment of more strict emission regulations, notably in Germany and in the U.S.A. Monomer recovery from polyolefin plants vents and gasoline capture from tank farms or fuel terminals were already available in the mid-1990s.

PVC plants monomer recovery Syngas ratio adjustment

Refining

Hydrogen recovery from various streams (FCC overhead gas, catalyst-cracker offgas, etc) Catalytic reformer hydrogen upgrading

Similarly, unreacted vinyl chloride monomer (VCM) used in PVC production is not properly recovered by simple condensation of the reactor vent stream. Grounded by regulations associated with its emission, membrane units for VCM recovery were applied even before their use in monomer separation.

LPG recovery CO2 and N2 removal Natural Gas

Natural gas liquids removal Digester off-gas treatment

Source: Intratec – www.intratec.us

The large volumes of hydrocarbons processed in refineries and in the petrochemical industry may limit membrane use due to the extremely large surface areas that would be required to achieve determined separations.

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

Membrane Materials and Modules The most widely employed materials in gas separation are polymeric dense membranes, although only a small number (about 10 polymers) are employed commercially.

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

Source: Intratec – www.intratec.us

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

 Thin selective layer  Defect-free structure  Proper mechanical resistance or available physical support After selection of the more suitable material, is necessary to package the membrane to obtain compact, high surface area modules. The characteristics of the material can limit the modules manufacturing possibilities and, consequently, the type of modules.

The modules are factory-built and are replaced entirely when necessary. On one hand, this modular characteristic facilitates maintenance and minimizes plants’ downtimes but, on the other hand, little economy of scale is verified.

The order of magnitude for the membrane area required may range from hundreds to thousands of square meters; hence, a large number of modules are required.

The most frequently employed types of modules for gas separation are hollow-fiber and spiral-wound. Table 3 presents some examples of applications and their respective modules.

Polyolefin Plants Opportunities In essence, industrial polymerization processes can be described as catalytic reactions wherein monomers form macromolecules characterized by a certain conjunct of commercially appealing properties. Standing as the main vapor permeation application, polyolefin plants present important stages in which membranes can be applied.

Raw Material Purification The first (and significant) stage in polymerization process is fitting the raw materials to the sensitiveness of the catalyst system and/or to avoid the accumulation of inert substances. Depending on monomer’s specific source, direct use is not always suitable and removal of light gases such as N2, H2 and CH4 is often necessary.

In polyethylene (PE) plants, this may be accomplished by an ethylene stripper, but light gases build-up in the column overhead requires a purge that can carry considerable amounts of ethylene. To minimize this issue, it is possible to implement a membrane unit to receive the lights stream and recycle enriched ethylene permeate to the column.

Additionally, the column size required could be reduced.

Intratec | About Membrane Separation Processes

 Stability

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Figure 2 – Column Overhead Membrane Recovery

Membrane Unit

Residue to Flare or Fuel

Olefin Product

Typically, the newly formed polyolefin contains entrained monomers, water used to deactivate catalyst residues, and inert components, such as propane. In order to suit the polymer for extrusion and pelletizing and increase the safety, environmental, and product quality aspects of the process, hot nitrogen is generally used, resulting in a vent gas containing hydrocarbons, nitrogen and water.

The earning potential of recovering monomer rather than burning it as fuel, as in older plants, encouraged companies to consider the use of membrane separation units.

Although most state-of-the-art technologies may provide alternatives for such recovery, most older plants lack proper separation methods. Nowadays, near 50 of these membrane systems have been installed in polyolefin plants.

Monomer Feed C2-Enriched Permeate Heavies Ethylene-Ethane Splitter

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) and high density polyethylene (HDPE), control of the partial pressure of ethylene in the reactor requires the addition of nitrogen. The purge of the reactor not only removes nitrogen, but also unreacted monomers, which allows a membrane unit to be used to reduce monomer losses.

Permeate

Membrane Unit Resin N2 feed

Purge Bin

Figure 3 – Reactor Purge Membrane Recovery Polymer Purge Recycle Gas

C2-depleted residue

Membrane Unit

PE Reactor

Intratec | About Membrane Separation Processes

Polymer Discharge

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C2-enriched permeate

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.

To Flare

Condenser

Source: Intratec – www.intratec.us

Recovered Iso-Butane

Process & Economics Overview Supplier(s) & Historical Aspects

involving process simulations, design procedures and mathematical models developed by Intratec.

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

Description

In terms of polyolefin applications, membrane technologies for monomer/nitrogen separation currently available are very similar, but MTR is the leader in this application. MTR’s first order dates from 1996 and was installed in a PP plant in the Netherlands.

Eurofilm has a number of installed units in China for propylene recovery, most of them in smaller batch processes. Until 2011, only two membrane units for continuous processes had been installed, for JPP and Sinopec 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 INEOS Innovene™ and Lummus Novolen® polypropylene processes can be provided with membrane recovery units.

Improvement Summary The current publication assesses in detail a technology for nitrogen and propylene recovery in a polypropylene plant, having low purity propylene (about 83 wt. %) as its main product. A process similar to MTR VaporSep® is analyzed and employed in the finishing section of the plant. This type of system is often called a propylene recovery unit (PRU).

All the data and figures presented were prepared based on publicly available information. This information was carefully analyzed through a structured methodology

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

Membrane Material The membrane itself usually consists of a multilayered composite structure in which the different materials exhibit distinct functions. In polyolefin production, the vent gas recovery membranes are often described as follows:

 Selective thin layer. Rubbery polymers such as polydimethylsiloxane (also called PDMS or silicone rubber) are chosen to selectively permeate propylene rather than nitrogen.

 Micro-porous support layer. Employed for mechanical support, provides a smooth surface on which the selective thin layer can be coated.

 Non-woven fabric. Also employed to provide mechanical strength, serve as substrate to the membrane. Its pores are too large to be coated directly with the selective thin layer.

Figure 5 shows a schematic of such a structure. The selective layer’s chemical structure is often very simple and similar, regardless of the supplier. Certain gaseous mixtures, however, may demand more specific and complex membranes.

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

Intratec | Process & Economics Overview

The first applications of VOC removal from air were in recovering gasoline vapors or solvents in the early 1990s.

Nowadays, hundreds of larger and smaller systems with applications such as resin degassing vent recovery, gasoline vapor recovery, and MVC recovery have been installed around the world.

The improvement consists of a vapor permeation system combining membrane and cryogenic separation techniques (hybrid process). The membrane components’ characteristics are described in this section, while the other equipment in the system are only discussed in the operation description.

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lower cost hollow-fibers, spiral-wound modules are used.

Moreover, the spiral-wound modules can operate at higher feed flows, unlike hollow-fibers.

Figure 5 – Three-Layer Composite Membrane

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

Feed flow (feed spacer) Selective layer Micro-porous support layer

In essence, spiral-wound module consists of multiple membrane layers, feed and permeate spacers rolled around a permeate collection tube. Spacers are also represented in Figure 5.

Non-woven fabric

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 an assembling possibility for the membrane system.

The use of a membrane more selective to the monomer in the purge bin vent leads to smaller membrane area requirements. Otherwise, the bulk of the vent would have to permeate. Propane contained in the mixture demonstrates similar separation characteristics when compared to propylene.

From 2 to 6 cylindrical modules, arranged end-to-end, can be placed in permanent housings made of carbon steel or stainless steel, which permit the system to operate at pressures other than atmospheric. In order to simplify modules’ replacement, each one possesses its own permeate collection tube, which may protrude beyond the module and be joined by gas-tight connectors. Hence, the permeate gas path is formed, and may be collected by

Modules Since rubbery polymers are not easily fabricated into the

Figure 6 – Membrane Modules Schematic

Membrane housing

Intratec | Process & Economics Overview

Membrane modules

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Residue outlet

Feed inlet

Permeate outlet Permeate pipes

Pressure vessel side view

Source: Intratec – www.intratec.us

Pressure vessel

manifolds, for example.

These tubes are then placed in a cylindrical pressure vessel, which contain a number of parallel tubes. Such arrangements, besides reducing the unit’s footprint, reduce the costs of vessels and associated components (pipes, valves, etc.), which may greatly surpass that of the membrane.

The pressure vessel is composed of two removable heads and a cylindrical shell; their number will depend on the specific area requirement. Size and weight must also be taken 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 axially penetrate the membranes and the permeate can be withdrawn by the collection tube. The residue stream of each module usually suffers little pressure drop when compared to the feed and, due to the annular seals, is forced to enter the next module, gradually reducing the propylene/propane content. On the last section of each tube, an opening is provided for the final residue stream, which then exits the system.

Implementation Assumptions This section describes in which scenario the improvement would be implemented, i.e., both previous characteristics of the plant and expected benefits/performance.

Table 4 summarizes the assumptions supporting the analysis presented in the following sections.

Operation & Block Flow Diagram

The mixture of propylene, propane, and nitrogen from the purge (off-gas) is mixed with recycled streams before compressing. The compressor outlet is sent to a condenser, where streams generated during the process are used for heat integration.

Compression and cooling are employed so as to condensate at least a part of the monomer and minimize membrane requirements.

Intratec | Process & Economics Overview

The process can be separated in three different sections: compression and cooling; flashing; and membrane separation. Figure 7 shows a simplified flow diagram for the process. The blue lines represent the additional streams and equipment associated with the improvement.

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After condensation and flashing, the low temperature liquid, containing mainly propylene and propane, is used for heat integration and, then, sent to a cracker unit for purification.

Table 4 - Implementation Assumptions Plant Under Analysis

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

Initial Scenario Improvement Proposed

The first membrane step generates a residue stream enriched in nitrogen, which is sent to the second membrane step. The permeate is recycled to the inlet of the compressor.

Scenario after Improvement

In the second membrane step, a residue stream containing nitrogen at 99 wt% purity is obtained. This stream is suitable for direct reuse without further purification. The permeate stream, in turn, is not sufficiently pure and is employed as boiler fuel.

OSBL Requirements Source: Intratec – www.intratec.us

Figure 7 – Process Simplified Flow Diagram

Off-Gas

Condenser

Wet Resin

To Boiler

1st Membrane Step Compressor

Resin Degassing Bin

to Compressor Inlet

Fresh Nitrogen

2nd Membrane Step

Flash

Intratec | Process & Economics Overview

Low Purity Propylene to Purification

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Dry Resin

Propylene-Rich Permeate 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

Economic Summary The table below summarizes the main economic indicators of the improvement proposed, including the CAPEX, OPEX, Sales, and EBITDA. All figures are additions to the economics of a suitable existing plant, following a typical improvement design.

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

N2

Propylene/ N2 mixture

Table 5 – Capital Cost & Economic Summary

CAPEX (USD Million)

Propylene concentration

N2 purification

Propylene-enriched permeate

Source: Intratec – www.intratec.us

TFI Other Initial Expenses

Substitute Solutions

Net Product Sales (USD Million/yr) OPEX (USD Million/yr) EBITDA (USD Million/yr) Source: Intratec – www.intratec.us

Alternatives Overview

Intratec | Process & Economics Overview

Different Implementations

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Process Analysis Process Description & Conceptual Flow Diagram This section describes the PRU for separation of a monomer/nitrogen mixture arising from a typical polyolefin plant purge bin in detail. This description refers to a process similar to MTR VaporSep速 system, but some differences may be found, since all the information herein presented is based on publicly available information. For purposes of illustration, a polypropylene plant is investigated, but the analysis could be easily extended to polyethylene manufacturing processes. It is worth mentioning that results presented (equipment required, process consumptions, etc.) are strictly limited to the PRU. The process consists of a gas separation system combining cryogenic separation techniques and membranes. For descriptive purposes, three different sections are considered: compression and cooling; flashing; and membrane separation.

Flashing

For a better understanding of the process, please refer to the Conceptual Process Flow Diagram; the Main Streams Operating Conditions and Composition; and the Major Equipment List, presented in the next pages.

Intratec | Process Analysis

Compression and Cooling

21

Key Consumptions Table 6 - Raw Materials & Consumptions (per ton of Product)

Membrane Replacement

Membrane Separation

Propylene PG 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.

Intratec | Process Analysis

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.

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Table 7 – Design & Simulation Assumptions

Simulation Software Thermodynamic Model

Feed Flow Operating Hours per Year

Nitrogen Propane

The future is just ahead

Propylene

Propylene Purity Propylene Recovery from Feed

Nitrogen Purity Nitrogen Recovery from Feed

Temperature Residue Pressure Permeate Pressure

Temperature

Research Economics Program Guidelines for research and planning within the process industry arena.

Residue Pressure Permeate Pressure

Selective Layer Material Expected Lifetime

The assumed operating hours per year indicated does not represent any technology limitation; it is rather an assumption based on usual industrial operating rates.

Intratec | Process Analysis

Source: Intratec – www.intratec.us

23

Intratec | Process Analysis

Figure 9 - Conceptual Process Flow Diagram

24

Source: Intratec – www.intratec.us

Table 8 – Main Streams Operating Conditions and Composition Name Phase Temperature (°C) Pressure (bara) Mass Flow (kg/h) Propylene (wt%) Propane (wt%) Nitrogen (wt%) Source: Intratec – www.intratec.us

Major Equipment List Table 9 shows the equipment list, besides a brief description and the main materials used.

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

Table 9 – Major Equipment List

Source: Intratec – www.intratec.us

Comp. Intercooler

CS

Intratec | Process Analysis

E-101

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Economic Analysis General Assumptions This study strictly evaluates the earnings, operating and capital expenditures associated with the improvement itself.

All figures are in addition to the economics of a suitable existing plant. Such plants’ operating and capital expenditures are not in the scope of the present publication.

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

Table 10 – Base Case General Assumptions Engineering & Construction Location Analysis Date IC Index

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

Capital Expenditures Fixed Investment Table 11 discloses the breakdown of the total fixed investment (TFI) per item (direct & indirect costs and project contingencies).

Fundamentally, the direct costs are the total direct material and labor costs associated with the equipment (including installation bulks). The total direct cost represents the total bare equipment installed cost.

After defining the total direct cost, the TFI is established by adding field indirects, engineering costs, overhead, contract fees and contingencies.

Nominal Capacity Operating Hours per Year Annual Production Project Complexity Technology Maturity Evaluation Phase Data Reliability Source: Intratec – www.intratec.us

Additionally, Table 10 discloses assumptions regarding the project complexity, technology maturity, data reliability and the evaluation phase, which are of major importance for attributing reasonable contingencies for the investment and for evaluating the overall accuracy of estimates.

Definitions and figures for both contingencies and accuracy

Intratec | Economic Analysis

In Table 10, the IC Index stands for Intratec chemical plant Construction Index, an indicator, published monthly by Intratec Solutions to scale capital costs from one time period to another. This index reconciles prices trends of fundamental components of a chemical plant construction such as labor, material and energy, providing meaningful historical and forecast data for our readers and clients.

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

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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 Contract Fee

Table 12 – Other Capital Expenses (USD Million) Start-up Expenses Operator training

Project Contingency (15% of TPC)

Commercialization costs Start-up Inefficiencies

Other - Scaling Exponent (Lang Factor) Up

Unscheduled System Adjustments Plant Layout Modifications

Down

Intratec | Economic Analysis

Source: Intratec – www.intratec.us

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Source: Intratec – www.intratec.us

Total Capital Expenses

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

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

Fixed Investment Discussion

Table 13 – CAPEX (USD Million) Total Fixed Investment Other Capital Expenses

Source: Intratec – www.intratec.us

Regional Comparison

Figure 10 – CAPEX per Location (USD Million)

Source: Intratec – www.intratec.us

Operational Expenditures Table 14 – Manufacturing Fixed Cost (USD/ton)

Manufacturing Costs Operating Labor Cost Maintenance Cost Operating Charges

Source: Intratec – www.intratec.us

Table 14 shows the manufacturing fixed cost.

Table 15 details the manufacturing variable cost breakdown.

Intratec | Economic Analysis

The manufacturing costs, also called Operational Expenditures (OPEX), are composed of two elements: a fixed cost and a variable cost. OPEX figures presented regard exclusively the operation of the improvement under analysis.

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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.

Intratec | Economic Analysis

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

30

Source: Intratec – www.intratec.us

Table 17 – Depreciation Value & Assumptions Depreciation Method Economic Life of Project Depreciation Annual Value Source: Intratec – www.intratec.us

Regional Comparison An OPEX breakdown structure for three different locations is presented in Figure 12.

Economic Datasheet & Discussion Return on Investment Implementation Benefits

Source: Intratec – www.intratec.us

Intratec | Economic Analysis

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

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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, check our available tools presented in the final chapters of this report:

 Premium Tools: Deepen Your Analysis  Economic Data Bank: Free Economic Updates

Intratec | Economic Analysis

Figure 13 – Improvement Earnings Comparison (USD Million)

32

Source: Intratec – www.intratec.us

Supervisors Required Operating Charges (Percent of Operating Labor Costs) Source: Intratec – www.intratec.us

Table 19 – Technology Economics Datasheet: Polypropylene Plant Vent Recovery

Location

TFI

Nominal Capacity

Other Capital Exp.

Production

CAPEX

Date (IC Index)

Membrane Replacement Propylene PG

Fuel By-product Nitrogen

Cooling Water Electricity

Operating Labor Maintenance Operating Charges

Depreciation

Low Purity Propylene

Intratec | Economic Analysis

Source: Intratec – www.intratec.us

33

Intratec | References

References

35

Acronyms, Legends & Observations AACE: American Association of Cost Engineers

LPG: Liquefied petroleum gas

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

NGL: Natural gas liquids 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 (e.g., E-101 would denote a heat exchanger tag)

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

EBITDA: Earnings before Interests, Taxes, Depreciation and Amortization F: Furnaces, fired heaters (e.g., F-101 would denote a furnace tag)

RF: Refrigerant (Flowsheet) or Refrigeration Unit (e.g., RF801 would denote an equipment 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

Intratec | Acronyms, Legends & Observations

IC Index: Intratec Chemical Plant Construction Index

36

TPC: Total process cost IRR: Internal rate of return ISBL: Inside battery limits K: Compressors, blowers, fans (e.g., K-101 would denote a compressor tag)

V: Horizontal or vertical drums, vessels (e.g., V-101 would denote a vessel tag) VCM: Vinyl chloride monomer

kta: thousands metric tons per year

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

LLDPE: Linear low density polyethylene

WP: Process water

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

Intratec | Acronyms, Legends & Observations

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

37

Methodology of the Analysis General Approach

Assumptions

Intratec | Methodology of the Analysis

General Considerations

38

Source: Intratec – www.intratec.us

Intratec | Methodology of the Analysis

Figure 14 – Methodology Flowchart

39

Start-up Expenses

Intratec | Methodology of the Analysis

Fixed Investment

40

Other Capital Expenses

Manufacturing Costs

Table 20 – Project Contingency

Source: Intratec – www.intratec.us

Table 21 – Accuracy of Economic Estimates

Source: Intratec – www.intratec.us

Intratec | Methodology of the Analysis

Contingencies & Accuracy of Economic Estimates

41

Table 22 – Criteria Description

Source: Intratec – www.intratec.us

Intratec | Methodology of the Analysis

Location Factor

42

Figure 15 – Location Factor Composition

Intratec | Methodology of the Analysis

Source: Intratec – www.intratec.us

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Intratec | Premium Tools: Deepen Your Analysis

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44

 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 userdefined inputs, industrially accepted economic performance indicators for the associated technology.

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Product Description With more than 10 years providing consulting services for Process Industries, we recognize that many times proper decision making relies on up-to-date information. Faulty assumptions and overoptimistic expectations often undermine profitability targets.

 Detailed manufacturing costs (fixed and variable costs)  Detailed capital costs breakdown  Economic indicators (EBITDA, EBITDA margin, EBIT margin)

 Total fixed investment  Working capital and other capital expenses Also, subscribers will have the option to download data in editable Microsoft Excel format. Indeed, Economic Data Bank will give subscribers the information they need to help them to conduct timely assessments on specific technologies and solutions within the process industries arena.

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More specifically, the Economic Data Bank subscription provides full online access to quarterly updated economic data of a specific publication, such as:.

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Intratec | Economic Data Bank: Free Economic Updates

Sure it would, and that is why we offer our publication readers the Economic Data Bank: a yearly subscription service that enables readers to access all economic tables and graphics of a publication, with up-to-date figures.

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Latest & Upcoming Reports The list below is intended to be an easy and quick way to identify Intratec reports of interest. For a more complete and up-to-date list, please visit the Publications section on our website, www.intratec.us.

 Polypropylene Production via Gas Phase Process,

TECHNOLOGY ECONOMICS PROGRAM (TEC)

 Polypropylene Production via Gas Phase Process,

 Propylene Production via Metathesis: Propylene production 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 a process similar to UOP OLEFLEX™.

 Polypropylene Production via Gas Phase Process: A gas phase type process similar to the Dow UNIPOL™ PP process to produce both polypropylene homopolymer and random copolymer.

 Propylene Production from Methanol: Propylene production from methanol, in a process is similar to Lurgi MTP®.

 Propylene Production via Propane Dehydrogenation, Part II (Available Soon): Propane dehydrogenation (PDH) in fixed bed reactors, in a process is similar to Lummus CATOFIN®.

 Propylene Production via Propane Dehydrogenation, Part III (Available Soon): Propane dehydrogenation (PDH) by applying oxydehydrogenation, in a process similar to the STAR PROCESS® licensed by Uhde.

Intratec | Latest & Upcoming Reports

 Polypropylene Production via Bulk Phase Process

46

(Available Soon): PP production of homopolymer and 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.

Part II (Available Soon): A gas phase type process similar to Lummus NOVOLEN® for production of both homopolymer and random copolymer.

Part III (Available Soon): PP gas phase type process to produce polypropylene homopolymer and random copolymer. The INEOS INNOVENE™ and JPP HORIZONE technologies have their main features discussed.

IMPROVEMENT ECONOMICS PROGRAM (IME)

 Membranes on Polyolefins Plants Vent Recovery: The Report evaluates membrane units for the separation of monomer and nitrogen in PP plants, similar to the VaporSep® system commercialized by MTR.

 Impact Polypropylene Production (Available Soon): The Report analyzes additional reactors for impact PP production in a process similar to the Dow UNIPOL™ PP process.

RESEARCH ECONOMICS PROGRAM (REC)

 Researches on Green Butadiene Production (Available Soon): The Report evaluates the production of 1,3-butadiene from sucrose. In the process analyzed, sucrose is fermented to crotyl alcohol, which is then dehydrated to 1,3-butadiene.

 Researches on Green Ethylene Production (Available Soon): The Report analyzes ethylene production via ethanol dehydration in a process similar to the route proposed by BP Chemicals.

Acknowledgments We would like to thank all our readers and clients for sharing their views and expertise with us during the entire development of this issue. It is important that our efforts meet your requirements, so we highly value your feedback to improve future editions. Moreover, if you would like to suggest a new technology, process or product as the subject of a future Publication, please do not hesitate to contact us at support@intratec.us. Your comments and suggestions 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 Publication Programs. We truly thank you!

The Intratec Team PS.: We are eager to hear from you!

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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 evergrowing 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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