Source: Handbook of Petrochemicals Production Processes, 2nd Edition

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

1.6. CHAPTER 1.6: EB-X: A PROCESS FOR

ETHYLBENZENE SEPARATION AND XYLENES
UPGRADE
1.6.1. INTRODUCTION
Ethylbenzene (EB) is a hydrocarbon compound with high commercial utilization and value. It is primarily used to produce
styrene, an intermediate for polystyrene production. EB is commercially produced from the alkylation of benzene with ethylene.
However, the cost and competitive demands of ethylene and benzene prompted new efforts to recover EB from various C8
aromatic feed streams such as pygas and reformate C8 fractions. The removal of EB from the mixed xylenes stream obtained
from naphtha crackers also upgrades the solvent-grade product to isomer-grade product with an upgrade value of up to $150
per ton.

Commercially, almost all EB is produced by alkylating benzene with ethylene. This is an expensive process as polymer-grade
ethylene is required to produce high-purity ethylbenzene, which is a requirement for downstream styrene monomer production.

EB can be separated from the xylene isomers by fractionation. However, with its boiling point around 2.3°C below that ofpara-
xylene (PX), the separation only can be achieved with super-fractionation (Table 1.6.1). Typical EB superfractionators contain
300 to 400 actual trays and require about a 25 to 50:1 reflux-to-feed ratio, which results in very high capital and operating costs.

Table 1.6.1 Difficulties in Removing EB from C8 Stream

Product Boiling Point (°C) Freezing Point (°C)

Ethylbenzene 136.0 −95.0

Para-xylene 138.3 +13.2

Meta-xylene 139.1 −47.9

Ortho-xylene 144.3 −25.2

GTC and SCG Chemicals have jointly developed a new technology using extractive distillation with a proprietary solvent to
separate high-purity EB product from its C8 aromatic isomers, which upgrades the mixed xylene stream from solvent grade to
isomer grade.

1.6.2. PROCESS CHEMISTRY (SEPARATION ENHANCING OF

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1.6.2. PROCESS CHEMISTRY (SEPARATION ENHANCING OF
ETHYLBENZENE FROM PARA-XYLENE BY THE SOLVENT
FUNCTION)
As seen in Fig. 1.6.1, PX is an aromatic hydrocarbon consisting of a benzene ring with two methyl substituents that are located
at the p position. PX has delocalized π-electron around the six-membered ring so the electron confines at the centroid of the
ring, leading to show a slightly negative charge at the center of the PX molecule. At the edge of the ring, there is electron
deficiency, leading to slightly positive-charged electron surface potentials (ESPs). The ESP for EB molecule is quite similar to
the PX molecule, but EB has the ethyl group as the substituent, which has more steric effect than the methyl group in the PX
molecule. From the molecular structure visual analysis of these two compounds, the target solvent for EB-PX separation should
be a slightly polar and partially charged molecule having a partially charged molecule with a slightly positive-charged side
group. Since EB and PX have similar polarity, the steric effect is taken into account as the critical solvent screening criteria. The
polar solvents with high steric effect have a higher affinity to PX than EB as EB has more steric hindrance than PX due to its
ethyl substituent group.

Figure 1.6.1 Electron surface potentials (ESPs) of para-xylene (PX) with XYLUP®-3D (left) and
ethylbenzene (EB) with XYLUP®-3D (right).

In summary, the proprietary solvent makes the separation possible as the steric hindrance for EB is more than for PX.

1.6.3. PROCESS DESCRIPTION

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1.6.3. PROCESS DESCRIPTION
EB-X is a simple process consisting of an extractive distillation column (EDC) and a solvent recovery column (SRC). If the feed
stream contains nonaromatic (NA) compounds, then a NA removal column is installed upstream of the EDC. The C8
hydrocarbon feed stream is sent to the NA removal column, where proprietary solvent enhances the relative volatility of NA
compounds over the aromatics compounds. The NA-rich stream is separated overhead as raffinate (Fig. 1.6.2).

Figure 1.6.2 EB-X process.

The rich solvent containing C8 aromatics is sent to the EDC. In the EDC, the same proprietary solvent enhances the relative
volatility of EB over PX and other C8 aromatic isomers. High-purity EB product is separated as raffinate and is treated through
guard bed to remove any entrained solvent, before being sent as product to the battery limits.

The rich solvent containing EB-lean C8 aromatics is sent to the SRC. In the SRC, EB-lean mixed-xylene isomers are separated
from the solvent at the overhead. The solvent from the bottom of the column is recycled back to the EDC and the NA removal
column. The EB-lean mixed-xylene product is treated through a guard bed to remove any entrained solvent, before being sent as
product to the battery limits.

1.6.4. FEEDS AND PRODUCTS

1.6.4.1. Feed
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1.6.4.1. Feed
The typical feed to the EB-X process unit is the C8 cut from hydrogenated pygas stream (Table 1.6.2). The critical feed
specifications are toluene content and C9+ content, as they affect the product specifications for EB and mixed xylenes (MX)
product, respectively.

Table 1.6.2 Typical Feed Specification of Hydrogenated Pygas C8 Stream

Characteristic Unit Specification

Toluene content wt% 0.1 max.

C9+ content wt% 0.5 max.

Nonaromatic content wt% 3–4

Ethylbenzene content wt% 60–65

Other C8 aromatic isomers wt% 31–37

1.6.4.2. Ethylbenzene Product

The EB-X process will meet the following product specifications for ethylbenzene (Table 1.6.3).

Table 1.6.3 EB-X Product Specification for Ethylbenzene

Property Unit Value

Purity wt% 99.7 min.

Xylenes wt% 0.2 max.

Nonaromatics wt% 0.1 max.

1.6.4.3. Mixed Xylene Product

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1.6.4.3. Mixed Xylene Product
The EB-X process will produce isomer-grade mixed xylenes as shown inTable 1.6.4.

Table 1.6.4 EB-X Production of Isomer-Grade Mixed Xylenes

Property Unit Value

Para-xylene wt% 18 min.

Ethylbenzene wt% 20 max.

Toluene wt% 0.5 max.

C9+ hydrocarbons wt% 1.5 max.

Nonaromatics wt% 1.0 max.

1.6.5. PROCESS DESIGN

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1.6.5. PROCESS DESIGN
Typical material balance and utility requirement to process 120 KTA of hydrogenated pygas C8 stream is shown in following
tables.

1.6.5.1. Material Balance

Feeds MTY Products MTY

Hydrogenated C8 pygas stream 120,000 Ethylbenzene product 65,600

Isomer-mixed xylenes 50,136

Gasoline components 4,264

Total 120,000 120,000

1.6.5.2. Utility Requirement

Utility UOM Consumption

LP steam t/h 3

MP steam t/h 26

Cooling water m 3/h 542

Electricity kWh 288

1.6.5.3. Economics
The total investment cost estimated to construct an EB-X plant processing 120,000 metric ton per year (120 KTA) of
hydrogenated pygas C8 stream is about US$16 million. The capital investment presented is exclusive of off-site costs and
calculated on USGC 2016 basis.

1.6.6. COMMERCIAL DESCRIPTION

EB-X technology has been commercially developed, and is now offered for licensing.

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