Source: Handbook of Petrochemicals Production Processes, 2nd Edition

ISBN: 9781259643132
Authors: Robert A. Meyers Ph.D.

1.3. CHAPTER 1.3: BP PARA-XYLENE PROCESS

1.3.1. INTRODUCTION
The BP para-xylene process, which is licensed by McDermott's Lummus Technology, is an unparalleled, energy efficient method
employing crystallization for para-xylene recovery. This technology was developed by Amoco (now BP) in the 1960s for use in
their own plants. For more than 50 years, BP has continually improved both process performance and technical design of this
technology producing a highly optimized and cost-advantaged route to para-xylene separation. In 2000, BP commercialized an
innovative crystallization system, dramatically reducing energy requirements by 50 percent. In 2010, BP and Lummus
Technology, formed a partnership to license the BP para-xylene process. This strong collaboration pairs an operating company
well versed in para-xylene production, vendor relationships, and plant maintenance with an industry leading
licensing/engineering firm.

In 2012, this technology was selected for a 2,250,000 metric tons per year (MTA) para-xylene grassroots aromatics complex,
the largest in the world. Moreover, the BP para-xylene process can achieve capacities in excess of 4,000,000 MTA with a single
fractionation column.

Para-xylene (pX) is a C8 aromatic hydrocarbon primarily used in the production of purified terephthalic acid (PTA), a precursor
to polyethylene terephthalate (PET). PET, a polyester, is a worldwide commodity used to make fibers, film, and packaging
materials. Para-xylene, its isomers (ortho-xylene (oX), meta-xylene (mX), and ethylbenzene), are produced via a variety of
petrochemical processes including naphtha reforming, toluene disproportionation (TDP), transalkylation, and as a by-product of
ethylene plants. For all production routes, a mixture of C8 aromatics isomers, termed “mixed xylenes,” is generated from which
para-xylene must be separated into a high-purity product to meet commercial requirements for downstream process units.

All C8 isomers boil within a few degrees of each other (Table 1.3.1). Thus traditional fractionation is not a practical method to
separate para-xylene from the other mixed xylenes. Para-xylene, however, has a significantly higher freezing point than the other
C8 aromatics isomers.

Table 1.3.1 C8 Aromatic Isomer Physical Properties

C8 Aromatic Isomer Boiling Point (°C) Freezing Point (°C)

Para-xylene 138 +13

Ortho-xylene 144 −25

Meta-xylene 139 −48

Ethylbenzene 136 −95

The BP para-xylene process exploits the large differences in freezing points of the C8 aromatic isomers to separatepX from the
mixture via crystallization. Refrigeration is utilized to crystallize para-xylene from the other components. Ortho- and
meta-xylenes are isomerized via a fixed-bed reaction system to increase the overallpX yield.

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Figure 1.3.1 depicts a simplified configuration of the BP para-xylene process. Since feed sources to the para-xylene unit can
contain light (C7−) and heavy material (C9+), upstream fractionation is often required to ensure a C8 aromatic-rich stream
enters the recovery section.

Figure 1.3.1 BP para-xylene process overall configuration.

1.3.2. PARA-XYLENE RECOVERY IN AN AROMATICS

COMPLEX
A para-xylene unit is often imbedded within an aromatics complex that produces both commercial grade pX and benzene (Fig.
1.3.2).

Figure 1.3.2 Typical aromatics complex.

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For a typical aromatics complex, fresh mixed xylenes enter the para-xylene unit. This feed is often sourced from an upstream
reformer following fractionation of the reformate to light reformate (C7− material) and heavy reformate (C8+ material). Mixed
xylenes can also be produced from a variety of process units including toluene/selective toluene disproportionation
(TDP/STDP), methanol to aromatics, and bio-based pX technology. In addition to fresh mixed xylenes, the para-xylene unit
receives mixed xylenes from a transalkylation unit. Within the para-xylene unit, pX is removed from the xylene mixture via
crystallization, oX and mX are recycled within the unit through the isomerization section and converted to pX. Ethylbenzene
(EB), part of the mixed xylene stream, is converted to valuable by-products. For the BP para-xylene process, EB is hydrogenated
to benzene and ethane.

Benzene-rich light aromatics (C7−) are sent to benzene fractionation to produce commercial grade benzene and a toluene
recycle stream. Heavy aromatics (C9+) are sent to the transalkylation unit.

Within the transalkylation unit, toluene and C9+ material are transalkylated to produce mixed xylenes which are sent back to the
para-xylene unit to increase overall pX product yield. Heavy material (C11+) is rejected to OSBL. A benzene-rich stream
produced in the transalkylation unit is also sent to benzene fractionation for by-product recovery.

Light reformate is processed in an aromatics extraction unit for removal of nonaromatics. The benzene/toluene-rich extract is
sent to benzene fractionation for benzene recovery.

1.3.3. DEVELOPMENT OF CRYSTALLIZATION PROCESS

There are many different versions of crystallization processes that have been commercialized.

BP (previously Amoco) first developed their process for para-xylene recovery in the 1960s. The process utilized two stages of
low-temperature refrigeration to preferentially remove pX from a mixed xylene stream via crystallization (Fig. 1.3.3). Solids from
the first stage were separated with centrifugation and remelted before entering the second stage of crystallization for final
purification.

Figure 1.3.3 Amoco conventional two-stage crystallization process (1967).

During the 1970s, the selective adsorption (SA) process was developed and quickly became the primary method forpara-xylene
recovery. Conventional crystallization was considered highly energy intensive due to the large refrigeration requirement and lost
market share for pX production.

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BP used crystallization for pX recovery solely in their own pX units since the inception of the technology. For the past 50 years,
they have continued to refine and improve this process (Fig. 1.3.4). Pairing this development with Lummus Technology's
extensive cryogenic experience has produced a highly optimized system using only one stage of refrigeration and an innovative
double reslurry system to produce para-xylene at the commercial quality of 99.8+ wt%. These BP/Lummus innovations have
reduced refrigeration compressor power by over 50 percent. The relative energy advantage between the BP para-xylene process
improvements and the SA process is seen in Fig. 1.3.4 as well.

Figure 1.3.4 BP para-xylene process technology progression.

This latest BP crystallization configuration, paired with enhanced energy integration throughout the entirepara-xylene unit and
improved isomerization catalyst performance, is highly energy efficient and easily expandable. Additional capacity for a BP
para-xylene unit can be accomplished simply by adding crystallizers and/or centrifuges via modular placement into the existing
recovery section structure without the need for increased plot space or significant infrastructure upgrade.

In 2010, BP and Lummus Technology entered into a partnership to license the BP para-xylene process, with Lummus
Technology as the exclusive worldwide licensor. This collaboration formed a strategic alliance joining BP, one of the world's
largest producers of pX with about 7 percent market share, with McDermott's Lummus Technology, a company with over 90
proprietary processes for license. Many of the Lummus incorporate enhanced refrigeration systems. This know-how coupled
with BP's operation of para-xylene units has led to the highly optimized process being licensed today.

The BP para-xylene process is demonstrated in seven commercial units (Table 1.3.2). At the time of this printing, this process
has been licensed to Reliance Industries Limited (RIL) India for an aromatics complex producing 2,250,000 metric tons per
annum pX, to GS Caltex Korea and to two confidential clients in Asia all for world-scale capacity para-xylene units. The pX unit
located at RIL's Jamnagar Refinery started up in 2016 and is currently the world's largest operating pX plant.

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Table 1.3.2 BP Para-xylene Plant Locations

Plant Site Capacity, KTA Start-up Date

Jamnagar, India RIL 2,250 2016

Geel, Belgium BP 675 2000

Texas City, USA #3 BP 390 1996

Decatur, USA #2 Indorama 720 1978

Texas City, USA #2 BP 530 1975

Decatur, USA #1 Indorama 380 1968

Texas City, USA #1 BP 350 1967

Total 5,295

1.3.4. COMPARISON OF CRYSTALLIZATION TO SELECTIVE

ADSORPTION
The two major methods of pX separation used in petrochemical complexes worldwide are crystallization and selective
adsorption. Since the 1970s, the SA process has been the primary method for pX production. Crystallization predates the SA
process. However until 2010, BP used this technology solely in their own units and did not license to third parties.

The SA process uses a solid adsorbent to selectively separatepX from the mixed xylene pool. Due to stringent feed
specifications, the entire mixed xylene volume must be severely fractionated and taken from the top of the xylene splitter to
ensure C9+ hydrocarbon content is at ppm levels before entering the recovery section of the SA unit. The heat of vaporization of
xylenes is 0.081 MMkcal/metric ton.

In crystallization, the bulk of the energy input results from lowering the temperature of the mixed xylene pool to the point where
para-xylene crystallizes out of the mixture. Thus this process employs the heat of fusion of xylenes, 0.038 MMkcal/metric ton,
less than half the heat of vaporization.

From a purely thermodynamic perspective, by using the heat of fusion instead of the heat of vaporization for xylenes forpX
separation, crystallization inherently consumes less energy than selective adsorption. However, in actual operation, the SA
process requires multiple times that of the heat of vaporization of xylenes since significant reflux is needed to meet recovery
feed specifications. Additional vaporization is required to separate mixed xylenes from the desorbent used to remove
para-xylene from the adsorbent. To recover heat from the highly energy intensive fractionation section of the SA process, the SA
recovery section is heavily integrated with the main tower utilizing steam generation from the overhead condenser to reboil
many of the downstream columns.

A significant difference between selective adsorption and crystallization is the per pass recovery ofpX from the mixed xylene
pool. For selective adsorption, recovery is around 97 percent while for crystallization the optimum value is about 65 percent.
Consequently, less para-xylene can be recovered with each pass in the crystallization technology, resulting in larger recycles to
the isomerization section of the unit.

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Even with a lower per pass recovery, the overall integrated crystallization process exhibits lower overall energy usage than
selective adsorption. Fundamentally, the lower heat of fusion is less than half of the heat of vaporization of xylenes, which
implies a process crystallizing pX from mixed xylenes would be advantaged over one that boils xylenes. Coupling this fact with
the severe, multiple steps of fractionation required for selective adsorption, the energy advantage for crystallization further
increases. Figures 1.3.5 and 1.3.6 illustrate the relative difference in energy consumption between apara-xylene unit employing
selective adsorption and crystallization.

Figure 1.3.5 Relative energy for a crystallization-based para-xylene unit (standard oil basis).

Figure 1.3.6 Relative energy for a selective adsorption-based para-xylene unit (standard oil basis).

Figure 1.3.5 depicts the typical energy breakdown for each section of a mixed xylene-based unit using crystallization forpX
recovery (1 kWh = 0.26 kg of standard oil, 1 MMkcal of fuel = 100 kg of standard oil).

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Figure 1.3.6 shows the energy breakdown for selective adsorption. Due to the intensive heat integration between the
fractionation and recovery sections of this unit, a single energy value is shown. A comparison of these two processes
concludes that the high energy required in the integrated section of the SA unit significantly outweighs any savings due to the
lower recycles in isomerization leading to a 53 percent increase in utility requirement for this process compared with
crystallization.

1.3.5. PROCESS FUNDAMENTALS

1.3.5.1. Feedstocks
Typical fresh feeds to a para-xylene unit, consisting of a mixture of xylene isomers, benzene, toluene, heavier aromatics, and
light ends, can vary significantly depending on the upstream processing unit. Table 1.3.3 shows several different feedstocks
from which para-xylene is recovered.

Table 1.3.3 Typical Feeds to a Para-xylene Unit

Component Reformate (Fractionated) wt% Conventional TDP wt% Selective TDP wt% Treated Pygas* wt%

Paraffins and naphthenes 0.5–8 – – –

Benzene 0 – – –

Toluene 0.5–2.0 – – –

Ethylbenzene (EB) 16–19 <<2 5 53

pX 16–18 23 >>81 12

mX 39–46 53 11 24

oX 19–23 22 3 11

C9A+ 0.5–2.0 – – –

*Treated Pygas is assumed to have been processed in upstream two-stage hydrogenation system for removal of primarily diolefins, sulfur, and
nitrogen.

Reforming creates hydrocarbon rings and dehydrogenates them to aromatics, thus producing an aromatic-rich reformate feed
stream. Toluene disproportionation (TDP) reacts toluene to produce benzene and xylenes. Selective TDP (STDP) preferentially
produces para-xylene in the mixed xylene stream. Both the TDP and STDP streams shown inTable 1.3.3 reflect the xylene
stream produced after fractionation. Pygas, a by-product from an ethylene cracker, is often very high in ethylbenzene. In
addition, when a complete aromatics complex is in place, mixed xylenes produced from a transalkylation unit are also sent to
the para-xylene unit.

All of the streams listed above can be easily processed in the BPpara-xylene unit without significant feed pretreatment and
with no risk of final pX product contamination.

1.3.5.2. Impurity Tolerances

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1.3.5.2. Impurity Tolerances
The BP para-xylene process is very robust in that it can handle high level of impurities with no permanent detriment to the
isomerization catalyst system or to final para-xylene product quality. The catalyst system readily recovers from exposure to
sulfur or other potential poisons. High levels of nonaromatics in the feed to the para-xylene unit can be easily tolerated and are
ultimately cracked across the reaction system. High levels of heavy aromatics and other impurities are allowable in the
crystallization feed since no easily contaminable chemical agents such as adsorbent or desorbent are required for this
process.

1.3.5.3. Product Quality

Table 1.3.4 depicts a typical production specification for para-xylene.

Table 1.3.4 Typical Para-xylene Product Specification

Property Specifications

pX Purity 99.8 wt% min.

Meta-xylene 0.2 wt% max.

Ortho-xylene 0.1 wt% max.

Ethylbenzene 0.2 wt% max.

Nonaromatics 0.2 wt% max.

Toluene 0.1 wt% max.

Sulfur 1.0 mg/kg max.

Appearance Clear liquid free of sediment and haze

Current commercial market quality for para-xylene ranges from 99.7 to 99.8 wt%. The BP para-xylene process can produce any
commercial grade para-xylene product with only slight modifications to operating conditions in the recovery stage. Although
not required for downstream PTA production, para-xylene product quality at 99.9 wt% can also be easily achieved with no
additional equipment or significant utility requirement. This operation mode has been evidenced at BP's own plants.

1.3.6. PROCESS DISCUSSION

The BP para-xylene process consists of three main sections: isomerization, fractionation, and recovery (crystallization).

Figure 1.3.1 depicts a simplified arrangement of these three sections. More detail is found in Fig. 1.3.7.

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 Figure 1.3.7 BP para-xylene process.

1.3.6.1. Isomerization
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1.3.6.1. Isomerization
Any feedstock to a para-xylene recovery unit contains significant ortho- and meta-xylene isomers that must be isomerized to pX
in order to achieve high product yield. Ethylbenzene, also present in such feeds, must be converted to by-products then
removed from the system. The BP para-xylene process uses a proprietary high selectivity deethylation (HSDE) catalyst system
to achieve both goals.

The main reactions of the isomerization section of the BP para-xylene process are as follows:

In addition to the reactions above, C9 paraffins and naphthenes are also converted to lower molecular weight hydrocarbons.

The BP para-xylene process converts ethylbenzene to benzene, a valuable by-product, with some fuel gas generation. High-
purity benzene is produced via this reaction mechanism, requiring only fractionation for the by-product's final purification. Other
competing isomerization technologies often produce significant hydrocarbons that co-boil with benzene. More elaborate
downstream separation methods such as extractive distillation or liquid-liquid extraction are needed to remove benzene from
these co-boilers.

The isomerization catalyst system has the following advantages:

Non-noble metal formulation

More than a 10-year catalyst life

Can be regenerated in situ, thus reducing turnaround time

Low xylene loss that is constant from start-of-run to end-of-run operation

Robust design that readily recovers from sulfur and other poisons

Xylene-rich effluent closely approaches xylene equilibrium, leading to maximum pX concentration

In the isomerization section, the pX-lean reject filtrate from the recovery section is combined with hydrogen, vaporized and
heated to reaction temperature, and fed to the isomerization reactor for isomerization and ethylbenzene conversion. Reactor
effluent is cooled and separated in a series of exchangers and separators. The vapor from the separators is recycled to the
suction of isomerization recycle gas compressor. The liquid is fed to the fractionation section.

1.3.6.2. Fractionation
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1.3.6.2. Fractionation
The SA process requires stringent separation of light and heavy aromatic by-products from the mixed xylene feed to the
recovery section of the plant. The typical fractionation section of a SA plant contains a stabilizer, where benzene, toluene, and
lights are taken overhead, and a xylene recovery column (XRC) where C8s are boiled overhead and C9+ hydrocarbons are taken
as the tower bottoms. Significant energy is required to operate both of these towers.

Crystallization is much more tolerant of these impurities. The fractionation section of the BP para-xylene process consists of a
single XRC. Reboiling is provided via fired heater or steam reboiler, depending on available steam and overall unit capacity. The
tower operates at low (atmospheric) pressure and no upstream treatment such as an oxygen stripper or clay tower is needed
to meet feed specifications for the stream to the recovery section.

Fresh mixed xylenes including fractionated reformate and/or transalkylation xylenes are fed to the column along with reactor
effluent from the isomerization section. The column separates these feeds into four distinct streams:

1. Fuel off-gas (ethane rich) used either as fuel or sent to a cracker for the production of ethylene

2. Light aromatics (benzene rich) sent to benzene fractionation for by-product recovery

3. C8 aromatics (primarily xylenes) sent to crystallization for para-xylene recovery

4. Heavy aromatics (C9+) sent to a transalkylation unit or OSBL for gasoline blending

C8 aromatics are taken as a sidedraw from the XRC, thus reducing overall energy consumption. Allowing for less stringent
fractionation of the C8 aromatics keeps tower size small and permits low-pressure operation, ultimately lowering tower design
pressure and equipment weight.

Thus, even with this simplified fractionation configuration, capacities in excess of 4 million metric tons ofpara-xylene per year
can be realized with a single XRC.

1.3.6.3. Para-xylene Recovery via Crystallization

C8 aromatics from the XRC are fed to the recovery section of the para-xylene unit. This stream is primarily cooled via heat
exchange with a pX-lean stream, termed reject filtrate, and then enters a single stage of crystallization. Exploiting the large
differences in freezing points of the C8 aromatic isomers, pX is crystallized out from the other components via a closed loop
refrigeration system that lowers the xylene mixture temperature to an optimized point for pX recovery. Recovery of pX in a
crystallization process is optimized to around 65 percent in consideration of the pX/mX or pX/oX eutectic, the point where other
xylene isomers will start to crystallize out of the C8 aromatic mixture.

Crystallizers, refrigerated vessels, provide the residence time needed to freeze thepara-xylene out of the xylene mixture. The pX
product is additionally purified via subsequent reslurry steps that require no additional refrigeration. Final purification is
achieved by washing the para-xylene crystals with pX product.

Centrifuges in this section separate the pX crystals from a mother liquor containing other xylene isomers. The two main
streams leaving the centrifuge are a high-purity pX product and the reject filtrate, a stream rich in mX and oX isomers.

1.3.7. ENVIRONMENTAL IMPACT

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1.3.7. ENVIRONMENTAL IMPACT
1.3.7.1. Gaseous Emissions
For a typical para-xylene unit, the main source of gaseous emissions is the fired heaters. The XRC of the BPpara-xylene process
operates at low pressure. Furthermore, the feed specification for the downstream recovery section is not extremely stringent.
Both factors lead to lower column reboiler duty, one-third (1/3) that of a same capacity SA unit. In addition, this reduced reboiler
duty leads to a smaller flare size.

Low reboiler duty reduces gaseous emissions from the plant. For a small capacitypX unit, the XRC reboiler can be replaced with
a steam reboiler, effectively eliminating gaseous emissions from this service and further reducing the BP para-xylene unit's
carbon footprint.

1.3.7.2. Liquid Effluents

The BP para-xylene process does not expel any continuous liquid effluent. Water introduced to the system through imported
feedstocks can be intermittently purged through the fractionation section of the plant to the appropriate drainage system.

1.3.7.3. Solids Disposal

The catalyst system for the isomerization section of the BPpara-xylene process is fully regenerable in situ with a 10-year life.
Thus frequent catalyst handling and disposal is not required, reducing potential for particulate emissions and limiting solid
waste processing.

1.3.8. CASE STUDY

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1.3.8. CASE STUDY
A case study for a 1,000,000 MTA para-xylene unit incorporating the BP para-xylene process is found in Table 1.3.5. This
evaluation is based only on a mixed xylene feed. Utility usage is indicative of only the ISBL para-xylene unit (see Fig. 1.3.7).

Table 1.3.5 Case Study

Para-xylene capacity, MTA (4) 1,000,000

Para-xylene product quality, wt% 99.8

Utility consumption

Electricity, kW 28,500

Fuel fired, MMkcal/h (1) 37

Cooling water, m 3/h (2) 3,400

Estimated total installed cost, MM$US (3) 200

Notes:

(1) Fuel fired is based on 92 percent efficiency.

(2) Cooling water amount reflective of plant location and cooling water availability. Air cooling can be used for some services to reduce cooling
water amount if air temperature is adequate.

(3) 2Q 2016 USGC basis.

(4) On-stream factor = 8400 h/yr

1.3.9. BIBLIOGRAPHY
Commissaris, S.E., “UOP Parex™ Process for p-Xylene Production,”Handbook of Petrochemicals Production Processes, McGraw
Hill Education, New York, 2005.

Pavone, A., “BP's PX Crystallization Process Offered by CB&I Lummus,” PEP Review 2015–12, IHS Chemical.

Roberts, S. et al., “BP's Energy Efficient Technology for the Production ofPara-Xylene,” Petrotech International Oil and Gas
Conference and Exhibition, New Delhi, Oct. 31, 2010.

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