Jordan University of Sciences & Technology

Engineering Faculty Chemical Engineering Department

A report on the POLYMERS: High Density POLYETYLENE PRODUCTION Chemical Industries (CHE 521) course Submitted By: Abdulrahman Abdulkareem Ali Ibrahim Mousa Mahmoud Shanaah Ahmad Fahmi Abdallah Jawabreh Osama Abd Al-Hafeez Hazaimeh 20072022009 20090022062 20090022017 20070022112

TABLE OF CONTENTS

TABLE OF CONTENTS......II List of figures III

Summary ............................................................................1 Chapter One: Introduction Of polymer & polyethylene.......................2 Chapter two: High Density Polyethylene Industry..... 6 Chapter three: Process Technology: .7 Chapter four: Production lines, Main reaction and a Flow sheet 10 Chapter five: Safety Hazards of High density Polyethylene ......... 13
Chapter six: Application of HDPE & Marketing .14

Recommendations: 15. Conclusion.. . 15 References.16

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List of figures:

Figure (1): Pipes Made from Polyethylene. Figure (2): Vessel reactor (Polymerization). Figure (3): Filtration plate Figure (4): Drying air for polymerization process. Figure (5): Ziegler-Natta polyethylene process. Figure (6): Philips catalyst process.

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Summary:
The main objective of this project is to discuss a polyethylene industry, from a raw material through a process technology to a main reaction and the flow chart. Finally a the safety Hazards have been discussed.

Chapter1: Introduction:
1.1: Definition of Polymer:
A polymer is a chemical compound or mixture of compounds consisting of repeating structural units created from a monomer molecule that has a small molecular weight through a process called polymerization. Monomers is a molecule with small molecular weight that may bind chemically to other molecule to form a polymer compound that has a high molecular weight. Such as ethylene (C2H4) is a monomer with small molecular weight to form polymer called polyethylene (C2H4)n H2 with high molecular weight. A monomer molecule is classified into two main categories: 1-Homopolymer: is a polymer which is formed from only one type of monomer such as ethylene to form a polymer Polyethylene. 2-Copolymer: is polymer contains at least two monomers such copolymers of ethylene and an alpha-olefin monomer such as 1-hexene, 1-butene or 1-octene.

Polymers are found in the world either natural such as wood, natural rubber, starch, and cotton or synthetic like plastic and artificial rubber. Polymer are formed from its monomer by two main reaction: 1-Addition polymer: An addition polymer is a polymer which is formed by an addition reaction, where many monomers bond together via rearrangement of bonds without the loss of any atom or molecules as shown below:

2-Condensation Polymerization: are any kind of polymers formed through a condensation

reaction, where molecules join together losing small molecules as by-products such as water or methanol.

. Polymer product from their monomers and its usage are shown below in table 1:Table1.1: Polymer production from their monomers and its usage:

Name(s) Polyethylene low density (LDPE) Polyethylene high density (HDPE) Polypropylene (PP) different grades Poly(vinyl chloride) (PVC) Poly(vinylidene chloride) (Saran A) Polystyrene (PS) Polyacrylonitrile (PAN, Orlon, Acrilan) Poly tetrafluoro ethylene (PTFE, Teflon)

Formula (CH2-CH2)n (CH2-CH2)n [CH2CH(CH3)]n (CH2-CHCl)n (CH2-CCl2)n [CH2CH(C6H5)]n (CH2-CHCN)n (CF2-CF2)n

Monomer ethylene CH2=CH2 ethylene CH2=CH2 propylene CH2=CHCH3 vinyl chloride CH2=CHCl vinylidene chloride CH2=CCl2 styrene CH2=CHC6H5 acrylonitrile CH2=CHCN tetrafluoroethylene CF2=CF2

Properties soft, waxy solid rigid, translucent solid

Usage film wrap, plastic bags electrical insulation bottles, toys

atactic: soft, elastic solid similar to LDPE isotactic: hard, strong solid carpet, upholstery strong rigid solid dense, high-melting solid pipes, siding, flooring seat covers, films

hard, rigid, clear solid toys, cabinets soluble in organic solvents packaging (foamed) high-melting solid rugs, blankets soluble in organic solvents clothing resistant, smooth solid non-stick surfaces electrical insulation lighting covers, signs skylights

methyl methacrylate Poly(methyl methacrylate) [CH2hard, transparent solid (PMMA, Lucite, Plexiglas) C(CH3)CO2CH3]n CH2=C(CH3)CO2CH3 Poly(vinyl acetate) (PVAc) (CH2CHOCOCH3)n vinyl acetate CH2=CHOCOCH3

soft, sticky solid

latex paints, adhesives

1.2: Definition

of Polyethylene (C2H4)n H2:

Its a common plastic manufacturing synthetically from an ethylene monomer C2H4(gaseous hydrocarbons that comes from a petroleum or natural gas after a steam cracking process)by a process called addition polymerization. Polyethylene is a thermoplastic polymer (its a type of polymer that become pliable and moldable at high temperature and return to a solid phase upon cooling). Consisting of long hydrocarbon chains. Depending on the crystallinity and molecular weight.

Figure1: Pipes Made from Polyethylene.

1.3: Classification of Polyethylene:

Polyethylene is classified into several different categories based mostly on its density and branching: 1-High Density Polyethylene(HDPE): Defined by a density of greater or equal to 0.941 g/cm3 . It has a low degree of branching and thus low intermolecular forces and tensile strength. HDPE is used in products and packaging such as milk jugs, detergent bottles, butter tubs, garbage containers and water pipes. In 2007 the global HDPE consumption reached a volume of more than 30 million tons. 2-Medium Density Polyethylene(LDPE): It's defined by a density range of 0.9260.940 g/cm3 . MDPE has good shock and drop resistance properties. MDPE is typically used in gas pipes and fittings, sacks, shrink film, packaging film. 3-Low Density Polyethylene (LDPE): LDPE is defined by a density range of 0.9100.940 g/cm3. It has a high degree of short and long chain branching, which means that it chains do not pack into the crystal structure as well and therefore less strong intermolecular forces and tensile strength. LDPE is used for both rigid containers and plastic film applications such as plastic bags. In 2009 the global LDPE market had a volume of circa US$22.2 billion (15.9 billion.There are many other types of polyethylene but the previous types are more common in industrial.

Chapter 2: High Density Polyethylene Industry:

The first production of polyethylene was discovered in 1933 by ICI chemist, Michael Perrin upon applying an extremely high pressure (several hundred atmospheres) to a mixture of ethylene in a vessel reactor , this high-pressure polymerization created polyethylene that called low density polyethylene(LDPE) with many branches; these branches are created due to intermolecular and intramolecular chain transfer during polymerization, because of high capital cost(equipment needed to withstand high pressure) and operating cost(Power needed to increase a pressure up to required pressure), a Ziegler(German scientist) was trying to create polyethylene at atmospheric pressure and had made the greatest contribution to producing highdensity polyethylene. The production of high density polyethylene is very important today because its use in packaging such as milk jugs , One third of all toys are manufactured from HDPE and also it has a high resistance to the both strong acid and base.

Chapter 3: Process Technology:

3.1: Main Raw materials: High density polyethylene produced by a different process and the two most methods are Ziegler-Natta Catalyst process and Philips process. The two previous methods are different in type of the catalyst that used. The basic raw material for two methods is ethylene (C2H4) monomer that comes from cracking or burning a petroleum or natural gas. In Ziegler-Natta Catalyst process the types of catalyst used are metals, one is called organometallic compound (titanium tetrachloride(TiCl4) and the other is metal alkyl (aluminum triethyl). Beside a hydrocarbons solvent(mainly CH4 ) , and also alcohol are used to deactivate a catalyst. In Philips process the type of catalyst is different and is used chromium oxide on a high surface area on silica, and dry air in a drying process.

3.2: Equipment used in Production of (HDPE): 3.2.1:-Vessel reactor: A vessel reactor was designed to contain chemical reactions, especially in this process a vessel reactor has been used to achieve an active site that necessarily for polymerization to occur by mixing an aluminum triethyl(methyl alkyl) with titanium tetrachoride.

Figure(2): Vessel reactor (Polymerization) 3.2.2: Decativation Catalyst vessel: This type of reactor has been used to deactivate a polymer& especially in our process to deactivate a polyethylene to be grown by using an alcohol solution 3.2.3: Filtration: commonly the mechanical or physical operation which is used for the separation of solids from fluids (liquids or gases) by interposing a medium through which only the fluid can pass. Epically in this process a polyethylene is separated from a slurry solution(Hydrocarbons solvent :CH4 plus metallic catalyst).

Figure( 3 ): Filtration plate

3.2.4:Drying: is a mass transfer process consisting of the removal of water or another solvent by evaporation from a solid, semi-solid or liquid. This process is often used as a final production step before selling or packaging products. A polymer is not dry it contains a significant amount of methane solvent that required to be removed from it by adding a dry air.

Figure ( 4): Drying air for polymerization process.

Chapter 4: Production lines , Main reaction and a Flow sheet

The production of high density polyethylene from a Zigler process is shown below:

Figure( 5 ): Ziegler-Natta polyethylene process. A brief description of the Ziegler process will be explained in the following paragraph. First, the organometallic compound (i.e. titanium tetrachloride) is reacted in a reaction vessel with a metal alkyl at a temperature between 100-130 degrees Celsius in the presence of a solvent. The pressure of the reaction vessel is between atmospheric and 20 atm. Ethylene is introduced into the reactor vessel in the gas phase. The boiling point of ethylene is approximately 100 degrees Celsius. The ethylene reacts with the active site of the catalyst to produce polyethylene. The solvent is used to dissipate heat. The solvent must not vaporize or react with any of the compounds in the reactor (inert solvent). The melting point of high-density polyethylene is approximately 130 degrees Celsius. Therefore, the polyethylene formed is in the solid phase. This type of polymerization is called slurry polymerization or suspension polymerization. The slurry solution is passed to a

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catalyst decomposition bed where the catalyst is deactivated to prevent a chain growth of polyethylene. Catalyst is not completely used in the polymerization process. So its decomposition is achieved with the addition of an alcohol. Polyethylene is then recovered from a slurry solution by filtration process, hydrocarbons (CH4 ) is recycled to a polymerization process. Polyethylene is then entering a dryer column to remove any moisture conent, finally it be processed and manufactured. The polyethylene created by the Ziegler process has a molecular weight 20,000 and 1.5 million. The molecular weight is controlled in a number of different ways: pressure of the reactor vessel (higher pressure, less branches), temperature in preparation of catalyst (too high of temperature deactivates catalyst), chain transfer reagents. The other process for manufacturing of polyethylene is a Phillips process. The only different between a Philips process and Zigler-Natta process is a type of catalyst has been used. Phillips Petroleum utilizes a highly active catalyst, chromium oxide on high-surface area silica, to produce high-density polyethylene. The active site for polymerization, Cr-C bond, is achieved by reacting the catalyst with an olefin. The olefin reduces the valence state of the transition-metal atoms, thus, making it more reactive. The reaction mechanism is similar to the mechanism explained for the Zeigler process. The mechanism is classified as anionic polymerization or "living" polymerization. An alcohol was added to deactivate the catalyst. Many of the polymer processes had in front of the main reactor a special reactor in which the catalyst preparation took place and the viscosity, morphology, control was a very important step. The use of a silica base eliminates this problem. The catalyst is very active and it no longer needs to be removed because all of the catalyst is reacted with the monomer ethylene. The active sites on the monomer are equally accessible to the monomer throughout the particle. Therefore, the polymer chains grow not only outwards but

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also inwards, causing the granule to expand progressively. The polymer particle will be a replica of the catalyst particle if the mechanical strength of the particle is high enough. Because of the complexity and importance of the silica base catalyst, the catalyst is often prepared in a separate production plant. The Phillips process is shown below:

Figure(6 ): Philips process for production of HDPE

The Phillips process creates HDPE with fewer branches than the HDPE created by the Ziegler process. The use of a silica based catalysts greatly reduces recovery and deactivation time.

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Chapter 5: Safety Hazards of High density Polyethylene (HDPE):

In general a release of chemicals associated with plastic products may occur in all phases of the life cycle during production, will affect the exposure for humans and the environment. The physical chemical properties of these substances, e.g. boiling point, vapor pressure, water solubility, and octanol-water partition coefficient, can be used to predict the environmental fate. Especially in polyethylene (HDPE): Eye and skin contact :contact with HDPE or dust may cause irritation or corneal injury due to mechanical action (scratching). Vapor from the heated resin may cause mild discomfort and redness of the eyes. Prolonged skin contact is essentially nonirritating. These materials are often processed as molten polymers at elevated temperatures and skin contact with the heated material may cause burns. Inhalation No adverse effects are anticipated from a single exposure to dust. Vapors or fumes released during thermal processing may cause respiratory irritation. Ingestion These materials have very low toxicity if swallowed. However, the granules may represent a choking hazard. Finally the important thing in high density polyethylene is an environmentally conscious material in that it can be recycled, according to Waste Age. It will not compost or biodegrade, however, making it an environmental hazard if not recycled.

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Chapter 6: Application of HDPE&Marketing:

HDPE is Food and Drug Administration approved for use with all food products, reports Dynalab Corp. Common examples of food use include milk jugs, reusable water bottles and cutting boards. major outlet for HDPE is in blow-moulding applications such as bottles for milk and other non-carbonated drinks, drums, fuel tanks for automobiles, toys and household goods. Because HDPE has good chemical resistance, it is used for packaging many household and industrial chemicals such as detergents, bleach and acids. Also HDPE can be injection moulded into articles including crates, pallets, packaging containers and caps, household goods and toys. It can be extruded into pipes for water, natural gas and irrigation, corrugated pipe for drains and sewers, and conduit for electrical and telecommunication cables.

For Marketing:
Global HDPE markets had been growing steadily at around 5%/year. Eastern and Central Europe, South America, Asia Pacific, the Middle East and Africa have growth rates higher than the global average with Asia Pacific having the highest growth in terms of volume. However, this growth was abruptly halted by an unprecedented demand crash in the second half of 2008 as a result of the credit crisis and its impact on economic activity. With declining polymer prices exacerbated by falling feedstock prices, purchasers withdrew from the market and inventories along the value chain reduced significantly. This resulted in a fall in demand being far beyond that anticipated by the economic downturn. In 2009, global HDPE demand saw a weak recovery with demand growing by 1.1% compared to 2008. Much of the recovery was driven by strong growth in China as a result of the economic stimulus package. HDPE will recover growth in the next few years as the industry restocks the inventory chain and the economic outlook improves. Growth in the 2009-2015 period is 5.5%/year. Bimodal HDPE will continue to be the focus for much of this growth based on an expanding product performance envelope and the potential for single gas phase reactor production which would have lower capital and production costs. While demand growth is expected to be heavily focussed in China, Western Europe and North America will also see growth, which although low in terms of growth rates, it will still be sizeable in terms of absolute demand increment.

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Conclusion &Recommendation:

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References: Websites: WWW.WikiPedia.com WWW.icis.com WWW.Msdssearch.dow.com

Books: Chemicals industrials process.

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