Reforming: Update on Catalysts & Technologies

Thierry Leflour

1

Agenda

• Semi-regenerative applications • Reforming catalyst portfolio

• Texicap™: optimum usage of catalyst inventory

• CCR Reforming technology updates • Catalyst breakthrough

• CCR technology

• Adsorbents Selection

2

Fixed Bed Reforming Catalysts : Current products

Re / Pt 0 1 1.6 1.8

Target Unit Cyclic SR SR SR

Stability Good Best

S tolerance Best Good

Low density

Standard density

Family of Multi-Promoted Fixed Bed Catalysts

RG 532 RG 582 RG 682

P 15 PR 15 PR 36 PR 30

P 152 PR 150 PR 156 New

3

Main benefits of new family

• High yields in a wide range of operating conditions

• Same activity as previous generation

• Outstanding stability

• Low cost to fill

Improved Profitability

4

Characteristic of new series (I/II)

490

495

500

505

510

515

520

525

530

0 24 48 72 96 120 144 168 192 216 240 264 288

Time (hours)

Norm T, Deg C PR 15 PR 150

Same activity but higher stability with 20 % less coke production

5

Characteristic of new series (II/II)

PR 15 New

H2 (wt %)

Base +0.1

C5+

(wt %) Base +1.5

Time (hours)

82

83

84

85

86

87

88

48 72 96 120 144 168 192 216 240 264 288

Normalized C5+, wt % PR 15 PR 150

Highly Selective Catalyst 6

Agenda

• Semi-regenerative applications • Reforming catalyst portfolio

• Texicap ™ : optimum usage of catalyst inventory

• CCR Reforming technology updates • Catalyst breakthrough

• CCR technology

• Adsorbents Selection

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B o l t e d m e t a l s h r o u d a n d c o v e r

Catalyst volume increase

With TexicapTM

Catalyst Dead Space

TexicapTM: Optimum Usage of Catalyst

Without TexicapTM

High coke deposit

Low coke High activity

High coke deposit

Low coke deposit High coke

Poor activity

Low coke deposit

Risk of high ΔT during regeneration

8

TexicapTM: What does it look like ?

Engineered refractory composite (Asbestos-free)

Scallops

Texicap

• Strong & Impermeable : withstands regeneration conditions

• First installation operating for more than 20 years

More than 100 references 9

Benefits of TexicapTM

• All loaded catalyst fully active

• Easy option to allow capacity or severity increase

• Possibility of unit short loading

• Easy and safe regeneration

• Shorter time during loading

• Easier inspection

10

Agenda

• Semi-regenerative applications • Reforming catalyst portfolio

• Texicap ™ : optimum usage of catalyst inventory

• CCR Reforming technology updates • Catalyst breakthrough

• CCR technology

• Adsorbents Selection

11

Axens CCR Reforming Catalyst Portfolio

Application Gasoline Aromatics Gasoline / Aromatics

Pt, wt% 0.25 0.30 0.29 0.29

Promoters Sn + Others (Multi-Promoted)

Moving bed density, t/m3 0.65 0.65 0.54 0.54

Main Attributes Yields

Strength

Activity

Strength

Activity

Strength

Yields

Strength

Target Unit All All Competitor

Density High density Low density

CR 600s

AR 700s

PS 40

PS 100

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Multipromoted Series Results

Previous Generation • Bi-promoted • Base Pt content

Axens’ New Series • Multi Promoted • Reduced Pt content

C5+ yields

Pilot testing Time (screening on fixed bed reactor)

With reduced Pt content, C5+ yields increased by 1.5% and 25% coke make reduction

Improved Yields

Improved stability

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Multipromoted Series Benefits

• High selectivity with no penalty on activity

• High hydrothermal stability

• Intrinsically good Cl retention

• Robustness of the catalyst :

Example of a unit loaded with CR 600 and suffering from lack of Cl injection

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Robustness of the Catalyst (I/III)

Catalyst and reformate color during chloride injection issue

After fixing the Chloride injection issue

Pt dispersion ~ 30 %

Pt dispersion 100 %

15

2

4

6

8

80

82

84

86

88

90

92

94

96

98

100

180

190

200

210

220

230

240

250

260

270 +12

+10

+8

+6

+4

+2

Base

-2

-4

-6

-8

+20

+10

Base

-10

-20

-30

-40

-50

-60

-70

Catalyst recovers after strong Pt agglomeration

Impact on Yield & Coke (II/III)

Coke (% wt) DT (°C) C5+ (% wt)

Chlorine injection problem solved

16

Significant activity recovery after Cl injection back on-line

4 days

2 RON

-60

-40

-20

Base

20

40

1-Jan 6-Jan 11-Jan 16-Jan 21-Jan 26-Jan 31-Jan

Actual WAIT, F

-6

-4

-2

Base

2

4 RON

WAIT DEG F

RON

Problem of Cl injection solved

Robustness of Catalyst (III/III)

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Agenda

• Semi-regenerative applications • Reforming catalyst portfolio

• Texicap ™ : optimum usage of catalyst inventory

• CCR Reforming technology updates • Catalyst breakthrough

• CCR technology

• Adsorbents Selection

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0

10

20

30

40

50

60

70

80

90

100

110

0.0

0.1

0.1

0.2

0.2

0.3

0.3

1970 1975 1980 1985 1990 1995 2000 2005 2010

CCR Licensing Cumulative

Capacity, Mbpsd Cumulative Number

of references

as of February 2013

World Total: 107 Licenses

Cumulative Capacity: ~ 2.8 Mbpsd

Over 100 Licensed units ranging from 8,000 to 90,000 bpsd ULP designs

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Axens’ CCR Technology

Regenerator

Reactors and Heaters

Recovery

System

H2 rich

gas

Reformate

to Stabilizer

Feed

Net Gas

Compressor

Recycle

Compressor

Open source, DCS controlled catalyst

circulation and regeneration

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Side-by- Side Arrangement Merits

Easy maintenance

Easy engineered, low-cost technology set-up

2 000 kTPA

Low investment structure

Short transfer lines

21

Primary Burn

Finishing Burn

Calcination

Oxy- chlorination

Spent Catalyst

Regenerated Catalyst

Dry Combustion Gas

Air

Air

Oxychlorination Calcination Gas

Chloriding Agent + water

Optimum catalyst “protection”

Regenerator Section: RegenC-2

Dry Burn Loop Optimum Chlorine Management

22

Regeneration in CCR Units

90

110

130

150

170

190

210

230

0 365 730 1095 1460 1825 2190 2555 2920 3285 3650

DRY BURN LOOP

WET BURN LOOP

Graph developed from catalyst operation in a non-Axens CCR unit

specific surface area

(m2/g)

time on stream (days)

Evolution of Catalyst Specific Surface Area

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Agenda

• Semi-regenerative applications • Reforming catalyst portfolio

• Texicap ™ : optimum usage of catalyst inventory

• CCR Reforming technology updates • Catalyst breakthrough

• CCR technology

• Adsorbents Selection

24

Purification in Reforming

for semi-reg unit 25

Main Contaminants

Stream Reformate downstream

reaction section

Regeneration of

the catalyst

HN upstream reaction section

Origin

During operation the Cl is removed from the catalyst

and goes in the rich gas and reformate stream

Coke burning Naphtha

Impact

Downstream unit catalyst poisoning and Equipment

corrosion

irreversible

Life time reduction

irreversible

Isomerization catalyst inhibition + PtS formation (Reduce unit cycle length

for fixed bed)

reversible

Adsorbents AxTrap 801,

AxTrap 857, AxTrap 858

AxSorb A » Regeneration Gas Drying

» Calcination Air Drying

AxTrap 405

HCl Water Sulfur

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ZnO based

material

Promoted

alumina

AxTrap

858

Reformate stream (180°C)

HCl Removal in Gas & Liquid Phases

Hydrogen stream (30°C)

Molecular sieve

Standard alumina

ZnO

based

material

AxTrap

801

AxTrap

857

Low cost products Promoted alumina High performance

product

Promoted

alumina

Octanizing / Aromizing • 107 licensed units ULP, side by side designs, from

maximum gasoline to BTX mode

• More than 40 awards since 2005

• 2.8 MBPSD cumulated capacity

Superior yields

Stable and robust

Low Pt inventory

Products

Low investment cost design

Superior Regen

C2 concept

Technology

World-class site services Operator training

Web-based optimization and tracking tools

Services

Aromizing / Octanizing • Catalysts

• Adsorbents

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