From Purification to Liquefaction Gas Processing with Axens Technology

Laurent Savary, Axens

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Natural Gas Treatment

Contaminants in natural gas:

CO2 H2S Mercaptans (RSH) Carbonyl sulfide (COS) Carbon sulfide (CS2) H20 Hg

The degree of removal depends on downstream requirements.

Gas Processing with Axens Technology GPA-GCC 2004 2

Natural Gas Treatment

In LNG plants, contaminants must meet the following specifications:

CO2 H 2S H 20 Hg < 100 ppmv (freezing and equipment plugging) < 4 ppmv (sales gas specification) < 1 ppmv (freezing and equipment plugging) <0.01 gr/Nm3 (corrosion in aluminum exchangers)

Gas Processing with Axens Technology GPA-GCC 2004

Gas Processing Chain

LNG
Acid Gas Treatment/Reinjection

Sulfur CO2

Liquefaction Liquefin

Acid Gas Natural Gas

Gas Conditionning Removal of acid gases/ water/mercury NGL Recovery/ Fractionation and Treatment

Liquid Fuel
Gas-To-Liquids Gasel

Reception Separation

NGLs

Water

Condensate Condensate Stabilization and Treatment RAM

Condensate

NG
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Gas Processing with Axens Technology GPA-GCC 2004

Gas Processing Chain (1/3)

Gas Conditioning

Acid Gas
MEG units in Iran - Prosernat

Gas Sweetening AdvAmine Ifpex-2 Sulfint HP Molecular Sieve

Gas Dehydration TEG, Progly, Trimdryer Drizo Ifpex-1 Molecular Sieve

Mercury Removal

Gas Processing with Axens Technology GPA-GCC 2004

Gas Processing Chain (2/3)

Acid Gas Treatment

Clauspol unit Prosernat

Acid Gas Dehydration TEG Mol Sieves

Acid Gas CO2

AGE MDEAmax

Acid Gas Reinjection

H2S

Claus Catalysts Processes

TGTU Clauspol ATGT

Incineration

Sulfur
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Gas Processing Chain (3/3)

NGL Recovery
Dry Gas

NGL Recovery HC Dewpointing Proserpack

NGL Fractionation

C3 C4 C5+

NGL Sweetening Sulfrex Molecular Sieve

NGL Dehydration Molecular Sieve

C3 C4 C5+ products

Gas Processing with Axens Technology GPA-GCC 2004

Combining Sulfrex & Molecular Sieves for LPG Sweetening

Synergy between Process and Adsorbent

Gas Processing with Axens Technology GPA-GCC 2004

LPG Sweetening, Extractive Sulfrex

Sulfrex Process Objectives

Obtaining negative Doctor Test on final product Odor improvement Meet sulfur specifications on LPG or C3/C4 cuts Meet C3/C4 olefinic cuts sulfur specs required for olefins upgrading process (Alkylation, Oligomerization)

Gas Processing with Axens Technology GPA-GCC 2004

LPG Sweetening, Extractive Sulfrex Typical C4 Cut Impurities

Mercaptans - methyl mercaptan: CH3-SH up to 1000 ppm mole - ethyl mercaptan: C2H5-SH up to 5000 ppm mole

H2S: traces COS: traces (*)

(*) : In C3 cut COS content can be as high as several hundred ppm

Gas Processing with Axens Technology GPA-GCC 2004

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LPG Sweetening, Extractive Sulfrex Main Reactions

Extraction
RSH + NaOH RSNa + H2O

Oxidation and Caustic Regeneration

2 RSNa + O2 + H2O
catalyst

2 NaOH + R-SS-R

Global Reaction
2 RSH + O2
Gas Processing with Axens Technology GPA-GCC 2004

R-SS-R + H2O
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Extractive Sulfrex, Extraction Section

Caustic Settler Sand Filter

Extractor

To Caustic C4 Wash Col. Mole. Sieve Dryers

LPG Feed
CW

Dry, Sweet LPG

Caustic from Wash Col. Demineralized Water

Gas Processing with Axens Technology GPA-GCC 2004

To Oxidizer

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Extractive SulfrexTM Caustic Regeneration Section

Sour LPG to Gas Plant Air Purge Disulfides To Storage

Lean Caustic To Extractor From Extractor

Air
LP Steam

Oxidizer
Spent Caustic To Sump-Drum
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Fresh Cat. Inject. Syst.

From Process Air Compressor Sweet LPG Cut Gas Processing with Axens Technology GPA-GCC 2004

CW

LPG Sweetening, Extractive Sulfrex 17 licensed units 6.2 millions tons per year of capacity

Possibility to add molecular sieves to:

- decrease the size/investment of Sulfrex unit
- insure low RSH outlet concentration

Gas Processing with Axens Technology GPA-GCC 2004

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Molecular Sieve Structure

Pore size
MS 3A : 3 angstroms MS 4A : 4 angstroms MS 5A : 5 angstroms MS 13X : 8 angstroms
Gas Processing with Axens Technology GPA-GCC 2004

Pore size selectivity

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Adsorber Configuration

ADSORBENT

Equilibrium Zone

ADSORBENT

Mass Transfer Zone

Gas Processing with Axens Technology GPA-GCC 2004

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Equilibrium Zone (ZE)

The adsorbent is saturated with adsorbate at the operating temperature and pressure, according to the isotherm The adsorbate concentration is constant throughout the equilibrium zone

Gas Processing with Axens Technology GPA-GCC 2004

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Mass Transfer Zone (MTZ)

The adsorbate concentration is lower than in the equilibrium zone - an almost linear gradient between the concentration at the interface with the equilibrium zone and the adsorbent bed outlet (zero).

Gas Processing with Axens Technology GPA-GCC 2004

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Adsorption
Water concentration
Flow

ZE

MTZ

time

Gas Processing with Axens Technology GPA-GCC 2004

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Adsorption
Water concentration
Flow

ZE
Flow

MTZ

time

Gas Processing with Axens Technology GPA-GCC 2004

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Adsorption
Water concentration
Flow

ZE
Flow

MTZ

Flow

water breakthough

time

Gas Processing with Axens Technology GPA-GCC 2004

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Isotherm RSH Adsorption

3 . 2,7 2,4 2,1 1,8 1,5 1,2 0,9 0,6 0,3 0 Inlet RSH (ppm) C2+SH / 13X MeSH / 5A

Low RSH capacity : not possible to remove RSH alone if RSH concentration > 100 ppm RSH
Gas Processing with Axens Technology GPA-GCC 2004 22

Co-adsorption
Concentration water/sulfur
Flow
H 2 O sulfur hydrocarbons

ZE

ZTM

ZE

ZTM

Equilibrium Zone

Mass transfert zone

Bed length
Gas Processing with Axens Technology GPA-GCC 2004 23

Co-adsorption
Concentration water/sulfur
Flow
H 2 O sulfur hydrocarbons

ZE
Flow

MTZ
water

ZE

MTZ
Sulfur
sulfur

Bed length

Gas Processing with Axens Technology GPA-GCC 2004

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Co-adsorption
Concentration water/sulfur
Flow
H 2 O sulfur hydrocarbons

ZE
Flow

MTZ
water

ZE

MTZ
sulfur

Flow

water

Sulfur breakthrough

Bed length

Necessity to remove water before RSH

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Molecular Sieves for Removing Water and Mercaptans

Flow

MS 13X

Soluble Water Mercaptan

Necessity to considere both water and RSH

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Multibed Systems for Removing Water and Mercaptans

Flow

Adsorption of :
Soluble water

MS 3A

MS 13X

Mercaptan

Preferred configuration
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Molecular Sieve vs Activated Alumina

Molecular Sieves Activated Aluminas

cation

cation

cation

Pore size MS 3A : 3 angstroms MS 4A : 4 angstroms MS 5A : 5 angstroms MS 13X: 8 angstroms

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Pore size : 20- 60 angstroms

Multibed Systems for Removing Water and Mercaptans

Flow

Adsorption of:
Spheralite MS 5A MS 13X Soluble Water Mercaptan Soluble water Free water

Gas Processing with Axens Technology GPA-GCC 2004

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Isotherm Water Adsorption

Static adsorption capacity
(Kg of H2O /100 Kg of MS)
40 35 30 25 20 15 10 5 0 0 1 2.5 5 10 20 30 40 50 60 70 80 90 100

Temperature 25C

Molecular sieve

Special alumina

Relative Humidity

Gas Processing with Axens Technology GPA-GCC 2004

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MultibedTM System Dehydration

Static Adsorption Capacity

(Kg of H2O /100 Kg of MS) 35 30 25 20 15 10 5
1 4 5 7 10 12 13

Temperature 25C

Molecular sieve 4ANG

Spheralite 513

15

0,1

0,25

0,5

17

mm Hg
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Conventional Scheme Water Loading Profile

Water Loading

Bed Length Equilibrium Zone Mass Transfer Zone Molecular Sieve

Flow

Molecular Sieve

Gas Processing with Axens Technology GPA-GCC 2004

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MultibedTM Scheme Water Loading Profile

Water Loading

Bed Length Equilibrium Zone Mass Transfer Zone Molecular Sieve

Flow

Spheralite

Molecular Sieve

Real increase of capacity

Gas Processing with Axens Technology GPA-GCC 2004

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MultibedTM System Dehydration

The Spheralite used in the upper section of the equilibrium zone does not increase the co-adsorption of hydrocarbons as compared to a molecular sieve system

Gas Processing with Axens Technology GPA-GCC 2004

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Conclusions (1/2)

Axens complete offer for gas treatment, together with Prosernat Proven technologies that allows optimizing projects economics and performances H2S removal : Amine Treatment & Molecular

Sieves Drying unit : Glycol Treatment & Molecular Sieves

Gas Processing with Axens Technology GPA-GCC 2004

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Conclusions (2/2)

Appropriate solution for any contaminant Efficient adsorbent technologies for drying and purification Wide experience in feedstock purification for petrochemicals, refining, natural gas and chemical industries On-going research and development

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