Wang Dengfei1,2, Wang Jian2, Guo Feng1, Gao Yuxin1, Du Wei3 Yang Guoxing1,
1. PetroChina Daqing Petrochemical Research Center of Petrochemical Research
Institute; Daqing City; Heilongjiang Province, 163714; China;
2. College of Chemistry and Chemical Engineering, Northeast Petroleum University,
Daqing City; Heilongjiang Province, 163318; China;
3. PetroChina Daqing Oilfield Design and Research Institute, Daqing City; Heilongjiang
Province, 163712, China.
E-mail: duwey@163.com
Abstract: Polyethylene is one of the most widely used polymers in industry as fiber, film and bottle because
it has many advantageous properties such as easy of processing, high chemical resistance, flexibility, low
density and adequate mechanical properties and low cost. There are various commercial technologies
available to produce all the range of polyethylene grades including high pressure PE processes, low pressure
PE processes and bimodal or multi-modal PE processes. In principle, swing units PE plant is able to produce
HDPE, MDPE and LLDPE; even if cost-wise it is better to avoid frequent switches between the PE grades
with different densities. The gas phase polyethylene production process is the most recently developed low
pressure PE process and boasts many distinct advantages when compared with the commercial slurry and
solution processes. There are three major kinds of gas phase polyethylene production processes: single
fluid-bed reactor configuration, dual cascade reactor configuration and hybrid process. Some of the most
important licensors which produce swing units polyethylene are Unipol (Licensed by Univation), Innovene
G (Licensed by Ineos), Spherilene (Licensed by Lyondell-Basell) and Borstar (Licensed by Borealis
Chemical). These famous licensors and their proprietary processes will be reviewed in detail. This paper also
reviews the historical development of swing-unit gas phase polymerization technology as well as the
development of catalyst from Ziegler-Natta catalyst to metallocene-based catalyst. A critical review of the
challenges and opportunities from an industry view-point is presented. In the end, some suggestions on
domestic LLDPE/HDPE Polyethylene development were also given.
Keywords: Polyethylene; PE Swing Units; Gas Phase Process; Catalysts
1. Introduction
Polyethylene (PE) is the most widely utilized thermoplastic polymer today, which is a homopolymer of
ethylene or copolymer of ethylene with up to 20% of other comonomers like 1-butene, 1-hexene, and
1-octene and other vinyl monomers[1-3]. Today, polyethylene can be made by four groups of processes, such
as gas phase, slurry phase, solution, or high-pressure processes. Polymerization process has a major effect on
the properties of the PE and thereby exerts a direct impact upon the satisfaction of all those involved in the
transformation and use of PE in industrial and domestic artifacts.
Due to its simple process design, no liquid hydrocarbons, and wide product range with respect to
co-monomer (butene-1, hexene-1, and potentially octene-1), gas phase processes have gained many
advantages over other processes. In this paper, production of swing units polyethylene in gas phase and their
catalysts were emphasized. Some of the most important licensors are Univation, Ineos and Lyondell-Basell.
Historically, the Unipol process (licensed by Univation) has dominated licenses for gas phase processes for
linear polyethylene, but Innovene G (licensed by Ineos) and Spherilene S&C (licensed by Lyondell-Basell)
processes have attracted a significant number of licensees in recent years.
2. Processes Description
Univation, formerly named Union Carbide and now part of Dow Chemical, was the first company to
commercialize the technology for polyolefin production using fluidized-bed gas-phase reactors[4]. Since
polymerization occurs in the gas phase, separation of the unreacted monomer from the polymer product is
achieved simply by flashing off the monomer. Any low molecular weight polymer formed remains in the
polymer particles and no further separation is necessary. The process only requires a fluidized-bed gas-phase
25
8:1 (2016) Advances in Sciences and Engineering
reactor, a product discharge system to get the polymer out of the reactor and flash off the monomer, and a
purge column to remove any residual monomer and to deactivate the catalyst. The Unipol plant requires the
least capital investment among the major polyolefin production processes. Both HDPE and LLDPE can be
made using the Unipol process, although this process has found broader acceptance for the production of
LLDPE. Some Unipol plants were designed and operated in the swing mode between HDPE, MDPE and
LLDPE, but most plants are designed only for LLPDE production[5]. Several other companies have
developed and are licensing gas-phase polyethylene technologies. They include the Innovene from BP (now
Ineos), and the Lupotech G process (now licensed as Spherilene S process), and Spherilene C process from
Basell, and Borstar process from Borealis Chemical. All of them are based on the same principle of using a
fluidized-bed gas-phase reactor, although the operating mode and conditions differs among these different
processes. Table 1 details the main characteristics of fluidized-bed processes for ethylene polymerization[6-8].
Table 1 Typical reactor conditions for fluidized-bed processes
Process Unipol Innovene G Spherilene S&C Borstar
Licensors Univation Inoes Basell Borealis Chemical
1 or 2 1 loop and 1
Reactor type 1 or 2 fluidized-bed 1 fluidized-bed
fluidized-bed fluidized-bed
Condensed/Super
Mode of operation Condensed
condensed
Reaction Loop: 75-100
90-110 70-95 70-95
temperature(℃) fluidized-bed: 88
Reaction Loop: 55-65
20-25 20-25 20-25
pressure(bar) fluidized-bed: 20
Residential time(h) 2-4 2-4 1-2 1-2
Z-N, Cr,
Catalysts types Z-N, Cr, Z-N, Post
Metallocene, Only Z-N
thereof Metallocene metallocene
Bimodal
2.1 Single fluid-bed reactor configuration
2.1.1 Unipol Ι Process
Vent
Recovery
Reaction
System
Catalyst
Resin
Purging
Additive
Addition
Pelleting
Raw
System
Material
Handling
26
Advances in Sciences and Engineering 8:1 (2016)
removed. The ethylene and co-monomers are fed to the reaction system. The reaction system consists of a
fluid bed reactor, a cycle gas compressor and cooler, and product discharge tanks. Ethylene, co-monomers
and a recycle stream from the vent recovery system are fed continuously to the reactor. Polyethylene is
removed from the reactor by the discharge tanks and sent to a purge tank where unreacted monomer and
dissolved hydrocarbons are stripped from the resin and are sent to the vent recovery system. The purged
resin is sent to the pelleting system. The vent recovery system recovers as much hydrocarbons as possible
from the streams sent to it. The condensed components are returned directly to the reaction system and the
light gases are used as a conveying gas to reduce nitrogen consumption. Solid additives are metered and sent
to the pelleting system. The resin, solid additives and liquid additives are mixed, melted and pelleted in the
pelleting system. The pellets are dried, cooled and sent to product blending and storage [9].
As is known, reactor capacity increases depend primarily on the ability to remove the heat of
polymerization. The traditional non-condensation phase operation has a low space time yield (STY) of
fluidized bed reactor because of the limitation of recycle gas stream’s capacity of reaction heats removal.
Since the condensation phase operation is applied, there exists condensed liquid in recycle stream,so the
polymerization heat is removed both by the temperature rise of recycle stream gas phase and the evaporation
of the liquid phase,which leading to increasing of the STY. However, the content of liquid phase in recycle
stream is limited,so the reactor’s production capacity can’t be improved furthermore. To solve this problem
and increase the liquid phase content,the super condensing process is necessary. At present the super
condensing process is not mature yet,and the influences of liquid phase content increasing in recycle stream
on fluidized bed operation,resin degassing unit and vent gas recovery unit are lack of deep research, the
super condensing technology is not applied widely[10].
2.1.2 Innovene G Process
27
8:1 (2016) Advances in Sciences and Engineering
28
Advances in Sciences and Engineering 8:1 (2016)
29
8:1 (2016) Advances in Sciences and Engineering
4. Conclusion
Each process has its advantages depending on the producer and their product goals and intellectual
property considerations. Though every process production of polyethylene varies for various possible
catalyst combinations, comonomers selection, transfer agents and polymerization post-treatments, at the
heart of all industrial polyethylene processes is the system used to initiate polymer chain growth. Latest
findings in polymer science are used to introduce new catalyst and process innovations for producing the
required PE, and in many cases also resulted in better production economy. Examples of these new findings
were single-site catalysts, condensed mode technology in the gas phase process, which allows retrofitting a
reactor and increasing the production capacity up to 60%, use of supercritical propane in a loop reactor, and
several new multi-reactor processes (e.g. Unipol II, Spherilene, Advanced Sclairtech, Borstar). It is believed
that catalyst and process innovations will go hands by hands and the control over the polymer structure and
the ability to tailor material properties will be increased.
30
Advances in Sciences and Engineering 8:1 (2016)
5. Reference
[1]. Andrew J Peacock. Handbook of polyethylene: structures, properties, and applications (Plastics
Engineering) [M]. Marcel Dekker, Inc., 2000, pp 1-10.
[2]. Hilkka Knuuttila, Arja Lehtinen, Auli Nummila-Pakarinen. Advanced polyethylene
technologies-controlled material properties [J]. Adv Polym Sci, 2004, (169): 13-27.
[3]. Dennis B. Malpass. Introduction to industrial polyethylene properties, catalysts, and processes [M]. John
Wiley and Sons, Inc., 2010, pp 85-98.
[4] Tuyu Xie, Kim B. McAuley, James C. C. HSU, and David W. Bacon. Gas Phase Ethylene Polymerization:
Production Processes, Polymer Properties, and Reactor Modeling[J]. Ind. Eng. Chem. Res. 1994, 33:
449-479.
[5] Frederick J. Karol. Catalysis and the Unipol process in the 1990s[J]. Macromolecular Symposium, 1995,
89: 563-575.
[6]. Yury V. Kissin. Olefin Polymers, Introduction [M]. John Wiley and Sons, Inc., 6th edition, 2005.
[7]. Rajen M. Patel, Pradeep Jain, Bruce Story, Steve Chum. Polyethylene: An Account of Scientific
Discovery and Industrial Innovations In Innovations in Industrial and Engineering Chemistry [M]. American
Chemical Society, 2008, Chapter 4, pp 71-102.
[8] Han-Tai Liu, Chris R. Davey, Pradeep P. ShirodkarBimodal polyethylene products from UNIPOLTM
single gas phase reactor using engineered catalysts[J]. Macromolecular Symposia, 2003, 195(1):
309-316.
[9]. P. Steve Chum, KurtW. Swogger. Olefin polymer technologies-History and recent progress at the Dow
Chemical Company[J]. Progress in Polymer Science, 2008, 33: 797-819.
[10]. Ashuraj Sirohi, Sundaram Ramanathan. Design Issues in Converting to Super-Condensed Mode
Operation for Polyethylene[C]. AIChE Spring 98 Meeting, New Orleans.
[11] Daftaribesheli, Majid. Comparison of catalytic ethylene polymerization in slurry and gas phase[D].
University of Twente, 2009.
[12] Jenkins, I.J.M., Jones; Russell L., Jones; Thomas M., Beret; Samil. Method for fluidized bed
polymerization[P]. US. 4588790, 1986-05-13.
[13] Pei Xiaojing,Wang Xiuli,Liu Shaocheng,Cheng Zhiling. Spherilene Gas Phase Polymerization
Process for Polyethylene[J]. ,Petrochemical Industry Technology, 2012, 19(4): 46-50.
[14] Massimo Covezzi. The spherilene process: Linear polyethylenes[J]. Macromolecular Symposia,
1995, 89(1): 577-586.
[15] Tham Chee Mun. Production of Polyethylene Using Gas Fluidized Bed Reactor [EB/OL].
[2002-14-12]. http://kolmetz.com/articles/Article-040.htm
[16] Argimiro R. Secchi, Gustavo A. Neumann, Rossano Gambetta. Gas Fluidized Bed Polymerization
in PASSOS, M. L; BARROZO, M. A. S.; MUJUMDAR, A. S. Fluidization engineering: practice[M].
Quebec: Laval University, 2013. chapt.2: 59-95.
[17] Pål V. Hemmingsen. Phase Equilibria in Polyethylene Systems[D]. Norwegian University of
Science and Technology, 2000.
[18] Larsson, Per-Ola, Åkesson, Johan, Carlsson, Niclas, Andersson, Niklas. Model-Based
Optimization of Economical Grade Changes for the Borealis Borstar Polyethylene Plant[J]. Computers
& Chemical Engineering, 2012, 46: 153-166.
[19] Zhou Tian, Ke-Ran Chen, Bo-Ping Liu, Na Luo, Wen-Li Du, Feng Qian. Short-chain branching
distribution oriented model development for Borstar bimodal polyethylene process and its correlation
with product performance of slow crack growth[J]. Chemical Engineering Science, 2015, 130(7):
41-55.
31