Advances in Chloride Guards · Advances in Chloride Guards© XII Foro de Refinación del IMP, 5-6 Sep 2006 Page 3 Süd-Chemie R&D New Technology Development – Our strategic target

Page 1XII Foro de Refinación del IMP, 5-6 Sep 2006Advances in Chloride Guards©

Advances in Chloride Guards©XII FORO DE AVANCES DE LA INDUSTRIA DE LA REFINACIÓN


Süd-Chemie Catalyst Division

SÜD-CHEMIE JAPANJapan

SÜD-CHEMIE CHINA(Shanghai Office)

SÜD-CHEMIE AGC.I.S. (Moscow Office)

SÜD-CHEMIE MT Italy

SÜD-CHEMIE ZEOLITESRSA

SÜD-CHEMIE Sasol Catalysts

RSA

SÜD-CHEMIE INC.USA

SÜD-CHEMIE PROTOTECH INC.

USA

SÜD-CHEMIE India Ltd.India

P.T. Kujang SÜD-CHEMIE Indonesia

SÜD-CHEMIE AGGermany

SÜD-CHEMIE AGSaudi Arabia (Office)

SÜD-CHEMIE DO BRAZIL LtdaBrazil (Office)

BIOCATALYSTSUK

Manufacturing and SalesSales Only

Includes Catalyst R&D Corporate Headquarters

Local Presence - Global Support


Süd-Chemie R&D

New Technology Development – Our strategic target.

Our technological and market competence is based on development of new, innovative products.

R&D - Catalysts RESEARCH

200 Researchers World Wide19 Patents Filed, 17 Invention Disclosures - 2004

CatalystsTechnology


Refining Applications

FUEL GASLPG

Cl -TRAP (liq)

FCC

CATREFORMER

CMG

BTX

N - TRAP

As - TRAPS - TRAP

S - TRAP ISOM

HDT

HDS

HYDROISOM

HDS / MHC

HDT

HDT

GAS OIL

VGO

NAPHTHA

KEROSENEMID DIST.

S - TRAP

CLAY TREAT

DEWAXING

DEEP HDAr

HEAVY OILPROCESSING

VGORESID

Cl -TRAP (vapor)

AROMATICSSATURATION

POLYMERIZATION

C3/C4 COD

RESIN DIMER

METHANOL

CLAY TREAT

ISOM DEHYDRO

AROMATICSSATURATION CLAY TREAT

LPG

OFF GAS

RAFFINATE

C3/C4

C3/C4

C4

ALKYLATION

SMR

HTS

NG

LTS METHANATORPSA

DESULF

HDS

GASOLINE

CPA GASOLINEAROMATICS

DIESEL &GASOLINE

GASOLINE

GASOLINE

GASOLINE

GASOLINE

DIESEL

KERO / JET

GASOLINE& SOLVENTS

BTX

SATURATION CYCLOHEXANE

DIESEL &GASOLINE

H2

H2

OFF GAS

SPA DIMER GASOLINE

GASOLINE

SEL. HYDROAs REMOVAL

ETHYLENE &PROPYLENES -TRAP PURIFICATION

SAT.

SAT.

SULFURTAIL GAS UNITSOUR GAS SRU STACK

As - TRAPS - TRAP

HDT


Continuous Catalytic Reforming

Naptha

HDS Regenerationsystem

Reactionsystem

Separator H2 Chloride Treater

Reformate Chloride Treater

Net Gas

C3,C4 LPG

ReformateDebutanizer

Organic Chloride

Heavy Naptha

LightNaptha


Location

Net GasDraeger TubeInlet HCl 6-8 ppmv

Draeger TubeOutlet HCl = 0.1 ppmv

Al2O3Adsorbent

Chloride Treater Membrane Separator

(2) Fuel Gas

Product H2

(3) Make-up H2

H2 Loop

(1) Gas Turbine

(1) Gas Turbine Corrosion (Chloride SCC)Polymerization (Burner Plugging)Formation of Organic Chloride

Problems

Net Gas (Gas Phase)

(2) Fuel Gas Loop(3) Make-up H2


Adsorbent A-1 A-2 A-3 A-4 A-Zn C12

5-G

Shape S S S S S ESize (mm) 1-2 3-4 3-4 3-4 3-4 4.8Component (%)

Al2O3 32 95 60 60 30 --SiO2 55 -- 30 10 6.5 --

Na2O 8 5 8.5 25 -- --ZnO -- -- -- -- 60 25

Ca(OH)2 -- -- -- -- -- 55Additive -- -- -- -- -- --

Binder -- -- -- -- -- 20Physical Prop.

Bulk Density (kg/L) 0.7 0.9 0.9 1.0 1.1 0.9Crush Strength 91

Surface Area 416 201 137 60 26Pore Volume (ml/g) 0.31 0.43 0.34 0.50 0.32

Commercial Cl Adsorbents


Formation of catalyst

Investigation

Al2O3 + 6HCl 2AlCl3 + 3H2OAlCl3 + HCl HAlCl4AlCln(OH)3n + H2O HAlCln(OH)4n


(a) Formation of organic chloride (Bronsted Theory)Organic chloride resolves into HCl and hydrocarbon

(b) Polymerization (Friedel-Crafts Reaction)+ Cl-(CH2-CH2-CH2)-H

HCl + Fouling and blockage

Corrosion

Forming Organic Chlorides

Catalyst of: HAlCl4 or HAlCln(OH)4n

HCl + nCH=CH2 Cl-(CH2-CH2)n-H

(CH2-CH2)n-1-CH2-CH3

Catalyst of: AlCl3


Alumina Adsorbent (Plant Data)

0

2

4

6

8

10

0 50 100 150

InletOutlet

0

2

4

6

8

10

0 50 100 150Net Gas treated x 1000 [Sm3]

InletOutlet

Net Gas treated x 1000 [Sm3]

Inor

gani

c C

hlor

ide

(mg

Cl/N

m3 )

Org

anic

Chl

orid

e (m

g C

l/Nm

3 )


Testing – Slipstream Reactor

Composition mol %H2 91

CH4 – C4H10 9

Olefin Tr

HCl 6-8 ppmv

Pressure 33.8 BarTemperature 35 ºCGas Flow Rate 50,000 Sm3/hReactor Dimensions 2,000 mm (D)

7,025 mm (H)Gas Hourly Space Vel 2,273 h-1

Linear Velocity 0.14 m/secAdsorbent Volume 22 m3

Test Reactor Dimensions22 mm (D) 400 mm (H)

GHSV 4,546 h-1

Joint Development withJapan Energy Corporation


SlipStream Test

ORGANIC CHLORIDE - SlipStream Test

0

1

2

3

4

5

0 30 60 90 120Net gas treated(Days)

Org

. Cl c

onc.

(mg/

Nm

3)

Inlet conc. JCL-1 Sample-A T-10Sample C-1


SlipStream Test Cl Adsorbed

5

10

15

20

0 20 40 60 80 100

% of Bed

% C

l Pic

kup

JCL-1 Improved JCL Alumina


Contact Time

Contact Time

0%

5%

10%

15%

20%

25%

< 10

11-2

0

21-3

0

31-4

0

41-5

0

51-6

0

61-7

0

71-8

0

81-9

0

91-1

00

> 10

0

Seconds

Num

ber o

f Ves

sels


Cl Pick-up vs. Contact Time

02468

101214161820

0 10 20 30 40 50 60 70 80Contact Time [1/Actual SV]

Cl P

ick

up [g

/100

ml]

Al2O3

ActiSorb Cl


Pore Size Distribution of Catalysts

0.00

0.20

0.40

0.60

0.80

1 10 100 1,000

Pore radius(nm)

�V

/�lo

gD (m

l/g) P

AluminaJCL

C125

Pore Size Distribution


PatentsApplication No. Status JP 97195719 – Priority (22.07.1997)

Publication No. JP 11033396 A (09.02.1999) Request for examination filed. (09.12.1999) Filed an appeal against rejection. (29.07.2002)

PCT/JP98/03281 (22.07.1998) Designated Countries: AU, CA, ID, KR, SG, US, EP

Publication No. WO/99/04899 (04.02.1999)

Australia Patent Granted. (25.05.2000) Patent No. AU 720207 Expiry date: 22.07.2018

Canada Application No. 2266384 Notice for Allowance (10.06.2002). Patent No. to be issued.

Indonesia Application No. W-990111 Publication No. ID 021846 (05.08.1999) Request for examination filed. (05.06.2001)

Korea Patent Granted. (22.03.2002) Patent No. 331349 Expiry date: 22.07.2018

Singapore Patent Granted. (13.12.2001) Patent No. SG 64512 Expiry date: 22.07.2018

USA Patent Granted. (13.08.2002) Patent No. US 6432374 Expiry date: 22.07.2018

EP Designated States (DE, FR, GB)

Application No. 98933896.7 Publication No. EP 0933127 A1 (04.08.1999) Request for substantive examination filed. (29.04.1999)

Taiwan Application No. 87111887 (21.07.1998) Received First Rejection. (28.06.1999) Argument filed. (21.10.1999)

Malaysia Application No. PI 9803349 (22.07.1998) Notice for Allowance (18.06.2002). Patent No. to be issued.

Thailand Application No. 45085 (21.07.1998) Examination not requested yet.


Chloride Adsorbents

Adsorbent A-1 A-2 A-3 A-4 A-Zn C12

5-G

JCL-

1

HC

L-2

Act

iSor

b C

l 3

Act

iSor

b C

l 4

Act

iSor

b C

l 5

Shape S S S S S E P P P P PSize (mm) 1-2 3-4 3-4 3-4 3-4 4.8 4.8 2.5 4.8 2.5 4.8Component (%)

Al2O3 32 95 60 60 30 -- -- -- -- -- --SiO2 55 -- 30 10 6.5 -- -- -- -- -- --

Na2O 8 5 8.5 25 -- -- -- -- -- -- --ZnO -- -- -- -- 60 25 30 30 40 40 30

Ca(OH)2 -- -- -- -- -- 55 -- -- -- -- --Additive -- -- -- -- -- -- 50 50 40 40 50

Binder -- -- -- -- -- 20 20 20 20 20 20Physical Prop.

Bulk Density (kg/L) 0.7 0.9 0.9 1.0 1.1 0.9 0.7 0.7 0.7 0.7 0.7Pore Volume (ml/g) 0.31 0.43 0.34 0.50 0.32 0.45 0.47 0.46 0.47 0.57


Plant Data - HCl

Alumina ActiSorb Cl


Plant Data – Org Chlorides

Alumina ActiSorb Cl


Refinery A – Operating Data

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Months

HC

l (pp

m)

HCL IN HCl OUT Org Cl IN Org Cl OUT

Al2O3 Al2O3 Al2O3 Al2O3 Al2O3 + Zn ActiSorb ActiSorb

Temp = 30ºC, Pres = 21 Bar, GHSV = 4300, Lin Vel = 27 cm/s, Contact = 16 s


Refinery B – Operating Data

0

2

4

6

8

10

12

14

0 50 100 150 200 250 300

Treated H2 Gas (MM m3)

Cl C

once

ntra

tion

(mg/

Nm

3)

HCl InletHCl OutletOrganic Cl InletOrganic Cl Outlet


Reformate Contains HCl and Organic Cl

• Corrosion• Plugging by NH4Cl Formation

Reformate Chloride Treater

C3,C4 LPG

Reformate

Debutanizer

Reformate

Reformate (Liquid Phase)


Liquid Phase Adsorbents

Adsorbent C12

5-L

Act

iSor

b C

l 7

Act

iSor

b C

l 6

Shape E CDS CDSSize (mm) 1.6 1.6 1.6Component (%)

Al2O3 -- -- --SiO2 -- -- --

Na2O -- -- --ZnO 48 48 30

Ca(OH)2 32 32 40Additive -- -- --

Binder 20 20 20Physical Prop.

Bulk Density (kg/L) 0.7 0.5 0.6Pore Volume (ml/g) ,51 0.55 0.60


Condition

Stream ReformateHCl 1.0 – 1.5 mg/kgOrganic Cl 0.2 – 0.5 mg/kg

Analysis Analysis of Cl in reformateHCl Extracted with de-ionized waterOrganic Cl Left in Reformate after

extractionAnalysis of Spent Catalyst

Cl pick-upCarbon content

Reformate - Coonditions

Temperature 35ºCPressure 17 Bar gLinear Velocity 40 cm/min


Plant Performance Liq Phase

0

0.5

1

1.5

2

0 100 200 300 400 500 600 700 800Operation period (Day)

Org

anic

Cl [

mg/

kg]

InletOutlet

0

0.5

1

1.5

0 100 200 300 400 500 600 700 800Operation period (Day)

InletOutlet

Org

anic

Cl [

mg/

kg]


0

0.2

0.4

0.6

0.8

1

0 100 200 300 400 500 600 700 800Operation period (Days)

Org

anic

Cl (

mg/

kg)

C125ActiSorb Cl

Reformate Improvement


• Improved Gas Phase & Reformate Cl Adsorption• No Formation of Organic Chloride• Removal of Organic Chlorides• Increased Pick-up Capacity• Eliminates

– Plugging or deposits– Compressor vibration– Corrosion

Conclusions


Authors:T. Takase – Süd-Chemie Japan, Tokyo, JapanH.Matsuse - Süd-Chemie Japan, Tokyo, JapanA. Birch – Süd-Chemie Inc., Louisville, KY, USA

Contact Information:Alan Birchw +1 502 634-7250, m +1 502 544-1756email: [email protected]

Advances in Chloride Guards

Documents

Advances in Chloride Guards · Advances in Chloride Guards© XII Foro de Refinación del IMP, 5-6 Sep 2006 Page 3 Süd-Chemie R&D New Technology Development – Our strategic target