-SABLIN® TECHNOLOGYSTORY OF CHALLENGE AND SUCCESS

SABIC TECHNOLOGY AND INNOVATION

No. 2

A STORY OF SABIC INNOVATION ( LATE 80’S)

No. 3

SABIC JOURNEY TOWARDS INNOVATION

1989First Sabic R&D inRiyadh

1996 Sabic Technology Center Houston

1999 Demonstration

of Sabcat-1 at PK

2005 Start-up of 1st Acetic Acid Plant at Yanbu

2006 Start-up of 1st

LAO Plant in Jubail

Start up with technology licensing-in and JV’s

Maintain and improve Licensed technology

Develop and Innovate new technologies

Started with less than 10 scientists

• 2000 scientists and Research staff

• Developed 10 new technologies

• Developed 150 + new products yearly

• 10000 global patents.

201419th CentersGlobally

2020Global Solution Provider

Global Solution Provider

No. 4

LIVING A CULTURE OF INNOVATION

Predict + Repeat

Minimize Risk

Never Fail

Invention (T&I)

Activities

Learn + Adapt

Manage Risk

Fail Early + Cheaply

Innovation (All)

Results

No. 5

SABIC TECHNOLOGY AND INNOVATION NETWORK

Research CentersApplication CentersSABIC Plastic Application Center at KSU, RiyadSABIC Corporate Research & Innovation Center at KAUST

Geleen

Bangalore

VDDHouston

Riyadh

Jubail

ShanghaiUSA AC

Cartagena

BoZ

Moka

Thuwal

α-SABLIN®Competing LAO Technology

No. 7

SABIC ranks 3rd in world as PE producer

+

Mid 90’s challenge in 1-Hexene supply

SABIC decides to get a license for 1-Hexene production technology

CP and SHELL declines to give license

• 1995 SABIC Management decides to develop in-house/joint technology

-SABLIN® : THE RATIONALE BEHIND TECHNOLOGY DEVELOPMENT

No. 8

• Linear alpha Olefins (LAO’s) are linear hydrocarbon consisting of an even carbon atoms (C4 – C20+)

• Linear alpha Olefins (LAO’s) can be synthesized by catalytic ethylene oligomerization

WHAT IS LINEAR -OLEFINS

Butene-1

Hexene-1

Octene-1

Decene-1

Dodecene-1

Tetradecene-1

Hexadecene-1

Octadecene-1

Eicosene-1

C4 H8

C6 H12

C8 H16

C10 H20

C12 H24

C14 H28

C16 H32

C18 H36

C20 H40

CH3-CH2-CH=CH2

CH3-(CH2)3-CH=CH2

CH3-(CH2)5-CH=CH2

CH3-(CH2)7-CH=CH2

CH3-(CH2)9-CH=CH2

CH3-(CH2)11-CH=CH2

CH3-(CH2)13-CH=CH2

CH3-(CH2)15-CH=CH2

CH3-(CH2)17-CH=CH2

56

84

112

140

168

196

224

252

280

- 6,2 - 185,3

63,5 - 140,0

121,3 - 102,7

170,6 - 66,6

213,3 - 33,6

246 - 13,0

280 + 4,0

308 + 28,5

326 + 36,8

Name Cn H2n Structure Mol. MassBoilingpoint °C

Meltingpoint °C

C4 = Gas; C6 to C18 = Liquid; C20 to C30+ = colorless wax

No. 9

Applications:

• Commoner for polyethylene production HDPE and LDPE (C4 –C8)

• Base stock for detergents(linear alcohols and linear-alkyl-benzenes( C12-C18)

• Base stock for lubricants (Poly-alpha-olefins),C10

• Base stock for plasticizer, PVC (C6-C10) Amines and Surfactants (C16-C18)

GENERAL APPLICATIONS OF LINEAR -OLEFINS

PE Bottles

Detergent

Wax Polish

LubricantShampoo

Polymers, 50%Detergents

, 25%

Plasticizers, 6%

Lubricants, 15%

Others, 4%

No. 10

GLOBAL LAO TECHNOLOGIES

Competitor 3Competitor 3Single Product

CompetitorSingle Product

CompetitorCompetitors 1&2Competitors 1&2

200 - 400 bar200 - 400 bar 50 bar50 bar 140 bar140 bar

200-300 °C200-300 °C 110 °C110 °C 120 °C120 °C

Low productflexibility

Low productflexibility

No flexibility(1-hexene)

Toxic heavymetal catalyst

No flexibility(1-hexene)

Toxic heavymetal catalyst

Expensiveheavy metalcatalyst

Expensiveheavy metalcatalyst

-SABLIN-SABLIN

30 - 40 bar30 - 40 bar

60 - 80 °C60 - 80 °C

High productflexibility

Economicallyattractive

High productflexibility

Economicallyattractive

No. 11

Technologies Product Distribution (wt%)

ProcessProcess

Alpha OlefinAlpha Olefin

C4C4

C6C6

C8C8

C10C10

C12C12

C14C14

C16C16

C18C18

C20+C20+

Competitors 1&2Competitors 1&2

heavyheavy

13,913,9

14,614,6

13,713,7

12,012,0

10,010,0

8,28,2

6,56,5

5,25,2

14,914,9

22,922,9

20,620,6

16,516,5

12,312,3

8,98,9

6,26,2

4,34,3

2,92,9

5,35,3

lightlight

Competitor3

Competitor3

typicaltypical

1212

1313

1212

1212

1010

88

77

66

2020

heavyheavy

6,16,1

6,26,2

14,214,2

15,315,3

13,613,6

12,012,0

10,010,0

8,28,2

13,413,4

24,024,0

27,127,1

13,213,2

11,211,2

8,38,3

5,85,8

4,84,8

2,92,9

2,82,8

mediummedium

40,240,2

28,128,1

14,014,0

8,48,4

5,05,0

2,32,3

1,41,4

0,50,5

0,10,1

lightlight

-SABLIN-SABLIN

No. 12

-SABLIN® - DEVELOPMENT HISTORY

• 1997 LINDE/SABIC LAO cooperation

• Since 1997catalyst development

• 2000 start up LAO pilot plant

• End of 2006 1st commercial unit

• 2001 demonstration -SABLIN®

0 20 40 60 80 100 1200

1

2

3

4

t

y(1)

0 20 40 60 80 100 1200

0.2

0.4

0.6

0.8

1

t

y(2)

0 20 40 60 80 100 1200

1

2

3

4

t

y(1)

0 20 40 60 80 100 1200

0.2

0.4

0.6

0.8

1

t

y(2)

• 2009 Full Tech. commercialization

• 1995 Catalyst concept from ICP and Prove of Reaction

No. 13

Issue1995 1997 2000 2005 2009

x Kg of LAO/g of catalyst

-SABLIN® - THE SUCCESS STORY OF CATALYST

How to make a proper catalyst

3x Kg of LAO/g of catalyst

Surface to volume ratio

A perfect catalyst system

Commercial Scale Catalyst

Stable Zr based Catalyst with modified Al CoCatalyst to enhance catalyst performance

No. 14

-SABLIN® - THE INITIAL RUNS IN PILOT PLANT

Polymers everywhere in the pilot plant

REACTOR

SYSTEM NEEDS THOROUGH CLEANLINESS / Short Run length

BENCH SCALE PILOT SCALE

Almost Clean – Not much signs of polymers

GAS DISTRIBUTORVALVE

No. 15

-SABLIN® - THE LATER REALIZATION IN PILOT PLANT

A team of experts for thorough brainstorming sessions Revamp of pilot plant design / Modified start-up

ot-0

0

0

0

0

0

0

0

0

0

00

SUCCESSFUL RUNS

Results: Extended run length of reactor

No. 16

-SABLIN® - THE CHALLENGES DURING DESIGN

• Selection of Reactor

• Exothermic Reaction Cooling

• Avoiding Polymer Build-up

• In-situ regeneration of the reactor loop

No. 17

- SABLIN® - SELECTION OF REACTOR

Ethylene

Catalyst

Reflux

Ethylene,Light LAO´s

Heavy LAO´s,Catalyst

Solvent0 30 60 90 120 150 180

TOS (min.)

Criteria:

Exothermicity

Polymer Handling

No. 18

- SABLIN® - IN-SITU FLUSHING

Polymer formation – An inherent feature of any oligomerization technology

Also seen in - SABLIN® Technology

Challenge – How to reduce down time Not Avoidable

@ Pilot plant –Mechanical cleaningtakes several days

Distribution Plate after in‐situregeneration with solvent

-SABLIN® - SolutionAn in-situ flushing concept No Mechanical Cleaning – Increases On‐Stream 

factor

No. 19

- SABLIN® - 4 BASIC PROCESS STEPS

LAOReactor

CatalystRemoval

1-Butene

1-Hexene

1-Octene

1-Decene

C12+

Catalyst

C4+

Solvent Recycle

C8+

C2 Make-up

Feedstock and

Catalyst Preparation

Feedstock and

Catalyst Preparation

Reaction and

Catalyst Removal

Reaction and

Catalyst Removal

Primary Separation

Primary Separation

Product SeparationProduct Separation

No. 20

- SABLIN® - START-UP INAUGURATION

No. 21

- SABLIN® - Accelerated Start-up of Commercial Plant

• Highly cross-linked polymers• Not dissolved by any solvent• Caused by metal residue/corrosion

Pre-Commissioning Phase reduced for an accelerated Start-up• Huge amount of undesired polymers• Pluggages of lines

The pain of SHORT CUTS !Ensure thorough cleaning of the system

No. 22

What is the Issue

Spot shot from Chloride base corrosion traces affecting the Separation Train

- SABLIN® - THE PRESENCE OF CORROSION

Catalyst Feed

ReactionSection

Ethylene+

Solvent

SeparationSection

C4 – C8 (Light)Recycle

C10 – C12 (Medium)

C12 – C20+ (Heavy)

DeactivationSection

No. 23

LAO, Solvent, Catalyst

Catalyst killing agent (CKA),water

mixingLAO, Solvent, Chlorides

CKA, water, Metal Oxides

reactor bottoms effluent LAO to separation train

CKA circulation

What is Possible Source of Chloride- SABLIN® - CATALYST DEACTIVATION

The Concept:

Pilot Plant:

Catalyst dosing – y kg/hrChlorides in ppm level – no efforts on detectionNO SIGNS OF CORROSION(Presence of adsorber)

Commercial Plant:

Catalyst dosing – y kg/hr

Chlorides in ppb levelSEPARATION COLUMN BADLY CORRODED (No adsorber, triggered by FeClx , water and high temperature)

triggered by uncompleted catalyst

removalMechanical mixers –

not a solution

No. 24

v vv vvv vv vvv

Reactor

to mixers

To LAO Separation

Dec

anta

tion

from decantation

No OC formation !

Chemical X dosing

- SABLIN® - BENEFITS OF DOSING CHEMICAL X

No. 25

RISK AND CHALLENGES DURING THE OVERALL PROCESS

From a project planning and resource management

perspective, it is important to recognize that higher

risk projects increase volatility of planning and the

potential need for additional resources and

additional schedule. This should be factored into

the project plan and a risk reserve provided in the

form of budget and the resources to address risk

issues.

No. 26

TAKE OUT FROM THE CHALLENGE

• A Technology development route will consist of chemistry discovery, measurement of

kinetic, reactor modeling, conceptual design, pilot plant study, flow sheet optimization

and finally engineering. All these require a seamless workflow that can be achieved

using the group of tools. These tools continuously interact with each other all along

the course of technology development to enhance and speed up the technology

commercialization capability.

• Important to manage Ressource selection , Time prussure , Project planning.

• Identify critical issues at early stages.

• Allow some design felxibility which cost some money but help optimizing alot of

process and product limitation.

No. 2727

• A full-range process

• One-step from Ethylene

• Product Slate Flexibility

• Operator friendly

• Attractive economics

• Strongly covered by Patents

• Proprietary Owned

• License can be offered

LAO Process Team

-SABLIN® - HIGHLIGHTS

All Reflected in 2nd

SabLin plant being constructed now in

Russia and plan to be started Q1 , 2016

No. 28

-SABLIN® - SAFE LAO TEAM

No. 29