The benchmark technology for ultra low

sulfur FCC gasoline

OIL
REFINING
Deep HDS of cracked COMMERCIAL
gasoline in one sweet little EXPERIENCE
process
245 Prime-G and Prime-G+™ units
Deep hydrodesulfurization (HDS) of FCC have been licensed as of January 2015.
gasoline (the largest sulfur contributor in The total licensed capacity exceeds
the gasoline pool) is required to reduce 6,100,000 BPSD making Prime-G+™ the
gasoline pool sulfur content. Technologies leading technology for cracked naphtha
PRIME-G+™

must meet the following challenges: desulfurization. The following shows

• Good octane retention the wide range of application of this
• Excellent gasoline yield retention technology:
• No RVP increase
• Sulfur levels in feed: 100 to 4,000+ wt ppm
• Minimum hydrogen consumption
• Olefin levels in feed: 15 to 45 vol %
• Operational reliability
• Unit capacity: 3,500 to 110,000+ BPSD
• Ability to co-process other sulfur-rich
streams.

The commercially proven Prime-G+™ Although the naphtha splitter may be

technology is the market leader for selective
hydrodesulfurization of cracked naphtha.
Prime-G+™ stems from Axens' extensive
experience acquired in cracked naphtha
HDS and selective hydrogenation of LPG and
gasoline (figure 1).
optional depending on the required HDS
severity, the association of a Prime-G+™
selective hydrogenation unit (SHU) with a
splitter for light naphtha desulfurization
and sweetening ideally complements the
selective HDS on the heavier fraction.

LCN to Pool,
TAME or Alky. Unit
Prime-G+™
1st Step
SHU

Splitter

Prime-G+™
Dual Catalyst Ultra-Low Sulfur
Reactor System Gasoline

FRCN HCN

H
Make-up

ÒÒFigure 1: Prime-G+™ process flow diagram

PRIME-G+™ 1st step: light Prime-G+™ selective Commercial experience at
cracked naphtha selective catalyst system™: the 10 ppm
desulfurization bifunctionaldual-bed HDS
In order to meet future gasoline sulfur
The "Prime-G+™ 1 st Step" produces Prime-G+™ selective HDS outperforms regulations, German refineries have
olefin-rich light cracked naphtha (LCN) all other processes. The unit employs pioneered the implementation of the ultra
and sulfur-rich heavy cracked naphtha operating conditions and catalysts low-sulfur gasoline desulfurization tech-
(HCN). This processing arrangement tailored to maximize selectivity and nology and many of them selected the
provides a number of significant minimize olefin saturation while deeply Prime-G+™ technology to reach less than
benefits: desulfurizing. 10 wppm in the gasoline pool since end 2002.
• Conversion of light mercaptans and
PROCESS FEATURES BENEFITS
light sulfides into heavier sulfur species Since then, 125 units have been put on
Achieves toughest
• Production of low sulfur, mercaptan- Very high HDS level
gasoline pool sulfur
stream with design provisions to meet
(98+ %)
free LCN stream. Prime-G+™   1st  step spec. – 10 ppm 10 wppm (Euro V) sulfur in the reformulat-
outperforms any other technology for Low olefins and no Low hydrogen ed gasoline pool. Prime-G+™ technology
aromatics hydroge- consumption
LCN desulfurization nation Low octane penalty has demonstrated ability to produce ULS
• Diolefin removal from the LCN allows Liquid yield greater (Ultra Low Sulfur) gasoline during periods
direct processing in etherification or No cracking reactions than 100% with no RVP of time exceeding FCC turnaround cycles
increase
alkylation units (more than 5 years) and with low octane
• Diolefin removal from the HCN stream. ÒÒTable 2: Benefits of the Prime-G+™ Sweet loss (figure 3)
These compounds would otherwise Catalyst System 700 70
600 60
cause increased pressure drop and Two catalysts were developed to tackle this
500 50
reduce catalyst cycles in the HDS section problem. The lead catalyst, which achieves 400 40

• No octane loss and low H2 consumption the bulk of the desulfurization reactions, 300 30
200 20
• Co-processing and desulfurization has been tailored to minimize olefin satura- 100 10
of other streams without additional tion reactions while having sufficient activi- 0
0 250 500 750 1000 1250 1,500
0
1,750
Days on stream
hydrotreating (light coker, visbreaker, ty to desulfurize the most refractory sulfur
straight run or steam cracker naphthas). species encountered in the gasoline boiling  Feed Sulfur, wt ppm Product Sulfur, wt ppm

range. The finishing catalyst is a polishing

SHU SHU LCN ÒÒFigure 3: Inlet and outlet sulfur content vs. time
catalyst exhibiting practically no olefin satu-
FEED EFFLUENT (60°C)
ration activity but able to achieve the last Octane Loss
3.0
S, wt. ppm 2015 2015 10
step of the desulfurization while reducing 2.5
2.0
C1 TO C4 RSH,
340 <1 <3 product mercaptans. As a result, extremely 1.5
ppm
low product sulfur levels can be achieved in 1.0
LIGHT 0.5
5 1 a single-stage unit with excellent octane
SULFIDES, ppm 0.0
0 5 10 15 20 25
DIOLEFINS,
1.6 < 0.2
retention and low product mercaptans Product S, ppm
wt.%
(figure 2).  Delta MON  Delta RON
(RON+MON)/2 87.8 88.0
Olefin
Saturation
ÒÒFigure 4: Prime G+™ Octane Retention
4-8 Point
ÒÒTable 1: Example of processing FCC naphtha Road Octane
Difference
in the “Prime-G+™ 1st Step" Prime G+™ technology comforts Axens'
leading position in hydroprocessing
(diesel and kerosene hydrotreating:
Extent of HDS
Prime-D™, Prime-K™ and benzene
hydrogenation: Benfree™) and in
---- Conventionnal ---- Prime G+™
olefins upgrading (etherification
-TAME and TAEE- oligomerisation
ÒÒFigure 2: Octane loss by olefin saturation for
Prime-G+™ process compared to conventional with Selectopol™, OATS™ (BP)
FCC gasoline HDS technology and Polynaphtha™ technologies,
The technology lends itself to the reuse of hydrogenation with Alkyfining® and
idle units (thirty references for naphtha HDT purification with AxSorb® products).
or semi-regenerative reformer revamping).

Axens is a leading global provider of technologies, catalysts, adsorbents,

services and equipment. From oil refining, petrochemicals and gas processing,
to renewable & alternative fuels and water treatment, Axens solutions are used at
axens.net/blog major industrial plants around the world.

2015-02_PrimeG+