2006 UOP LLC. All rights reserved.

Extending Molecular Sieve Life in

Natural Gas Dehydration Units
Extending Molecular Sieve Life in
Natural Gas Dehydration Units
Henry (Hank) Rastelli
Julie Stiltner Shadden
UOP LLC
Henry (Hank) Rastelli
Julie Stiltner Shadden
UOP LLC
Mid-Continent Annual GPA
April 17, 2008
2007 UOP LLC. All rights reserved.
UOP 4733-01
Outline
Outline

Introduction
Introduction
-
-
Why molecular sieves for dehydration?
Why molecular sieves for dehydration?
-
-
What are molecular sieves?
What are molecular sieves?
Type (Structure & Cation) Type (Structure & Cation)
Formed Versions Formed Versions

Discussion
Discussion
-
-
Problems encountered in service
Problems encountered in service
Liquid entrainment Liquid entrainment
Regeneration at high temperature and pressure Regeneration at high temperature and pressure
-
-
Solutions
Solutions
Process Process
Product Product
-
- Case Histories Case Histories

Summary
Summary
UOP 4733-02
Molecular Sieves Required for Low H
Molecular Sieves Required for Low H
2 2
O Dew Points
O Dew Points
Introduction
Introduction

Why dehydrate natural gas?

Why dehydrate natural gas?
-
-
Pipeline Transmission
Pipeline Transmission

usually glycol treating is

usually glycol treating is
sufficient
sufficient
-
-
Hydrocarbon Recovery
Hydrocarbon Recovery
Cryogenic Refrigeration (D.P. < Cryogenic Refrigeration (D.P. < - -100 100 C) C)
-
-
LNG production (D.P. <
LNG production (D.P. <
-
-
100
100

C)
C)
Peak shavers (H Peak shavers (H
2 2
O, CO O, CO
2 2
removal) removal)
Base load (H Base load (H
2 2
O) O)
-
-
Helium Recovery (D.P. <
Helium Recovery (D.P. <
-
-
162
162

C)
C)
UOP 4733-03
Introduction

What are molecular sieves

What are molecular sieves
-
-
Microporous crystalline alumino
Microporous crystalline alumino
-
-
silicates
silicates
-
-
Commercially synthesized with uniform properties
Commercially synthesized with uniform properties
-
-
Possess high surface area (500
Possess high surface area (500
-
-
1000 m
1000 m
2 2
/g)
/g)
-
-
Pore aperture controls adsorption
Pore aperture controls adsorption
-
-
Alkaline / alkaline earth cations balance surface charge
Alkaline / alkaline earth cations balance surface charge
-
-
Type of cation affects the aperture size (i.e. 3A, 4A, 5A)
Type of cation affects the aperture size (i.e. 3A, 4A, 5A)
-
-
By using a binder (clay, silica, alumina, etc.), molecular
By using a binder (clay, silica, alumina, etc.), molecular
sieves are produced in different aggregates (beads,
sieves are produced in different aggregates (beads,
pellets, mesh)
pellets, mesh)
-
-
Binder choice critical to performance
Binder choice critical to performance
UOP 4733-04
Linde Type A Zeolite Linde Type A Zeolite Microporous, crystalline, alumino Microporous, crystalline, alumino- -silicate silicate
LTA = Zeolite A LTA = Zeolite A
UOP 4733-05
Introduction
Introduction

Why molecular sieves for NG dehydration

Why molecular sieves for NG dehydration
-
-
Strongly polar surface is selective for polar
Strongly polar surface is selective for polar
molecules (H
molecules (H
2 2
O, CO
O, CO
2 2
, H
, H
2 2
S, et.)
S, et.)
-
-
Non
Non
-
-
polar compounds (i.e. hydrocarbons) are not
polar compounds (i.e. hydrocarbons) are not
strongly adsorbed
strongly adsorbed
-
-
Water dew points of <
Water dew points of <
-
-
100
100

C easily achieved
C easily achieved
Molecular Sieves are I deally Suited for
Molecular Sieves are I deally Suited for
Natural Gas Dehydration and Treating
Natural Gas Dehydration and Treating
UOP 4733-06
Discussion
Discussion

Problems encountered in service

Problems encountered in service
-
-
Liquid entrainment
Liquid entrainment

glycols, amines, heavy

glycols, amines, heavy
hydrocarbons, etc.
hydrocarbons, etc.
-
-
Free water
Free water

pigging operation, etc.

pigging operation, etc.
-
-
Regeneration at high temperature
Regeneration at high temperature
-
-
Regeneration at high pressure
Regeneration at high pressure
UOP 4733-07
Regeneration Regeneration
at high temperature at high temperature
& high pressure & high pressure
Discussion
Discussion

Refluxing condition results in:

Refluxing condition results in:
Accelerated
Accelerated
Breakup
Breakup
Increased
Increased
Pressure
Pressure
Drop
Drop
Channeling
Channeling
Premature
Premature
Water
Water
Breakthrough
Breakthrough
UOP 4733-08
Crust Formation on Vessel Walls
Crust Formation on Vessel Walls
UOP 4733-09
Crust Formation Measured on Vessel Walls
UOP 4733-10
Solid caked layer of Solid caked layer of
adsorbent and salt adsorbent and salt
fused together fused together
Effective diameter reduced Effective diameter reduced
to 1500 to 1500- -2000 mm 2000 mm
Original bed diameter Original bed diameter
3100 mm 3100 mm
Approx Approx
1500 1500 - - 2000 2000
3100 3100
Thermocouple
Thermocouple
Crust Broken up
UOP 4733-11
Crust Formation Top of Bed
UOP 4733-12
Discussion

Solutions
Solutions
-
-
Process
Process
Reduce regeneration pressure Reduce regeneration pressure
Temperature ramping Temperature ramping
-
-
Product
Product
Guard Bed (alumina, silica gel, etc.) Guard Bed (alumina, silica gel, etc.)
More robust molecular sieve adsorbent More robust molecular sieve adsorbent

Case Histories
Case Histories
-
-
1. North African Operator (NGL from natural gas)
1. North African Operator (NGL from natural gas)
-
-
2. Central African Processor (NGL from associated gas)
2. Central African Processor (NGL from associated gas)
-
-
3. North American Producer (cryogenic liquids recovery)
3. North American Producer (cryogenic liquids recovery)
UOP 4733-13
Case 1: North African Operator

5
5
-
-
Train natural gas NGL
Train natural gas NGL
recovery plant
recovery plant

420,000 Nm
420,000 Nm
3 3
/hr
/hr

each train
each train

Feed pressure
Feed pressure

1120 psia
1120 psia

Regenerate with product gas

Regenerate with product gas

Regeneration Pressure
Regeneration Pressure

1062 psia
1062 psia

Re
Re
-
-
inject regenerant
inject regenerant

Regeneration is stripping
Regeneration is stripping
limited
limited
Adsorbent Life Doubled with UI
Adsorbent Life Doubled with UI
-
-
94 Adsorbent
94 Adsorbent
Feed Composition Feed Composition
Mole % Mole %
Methane Methane 85.9 85.9
Ethane Ethane 7.88 7.88
Propane Propane 2.77 2.77
i i - -Butane Butane 0.63 0.63
n n- -Butane Butane 0.68 0.68
i i - -Pentane Pentane 0.25 0.25
n n- -Pentane Pentane 0.17 0.17
C C
6 6
+ +
Balance Balance
Nitrogen Nitrogen 0.61 0.61
Carbon Dioxide Carbon Dioxide 0.78 0.78
UOP 4733-14
UOP
TM
MOLECULAR SIEVE ADSORBERS
Fig 2 - Pressure drop data review July 1999 - April 2006 Pressure drop evolution
0
5
10
15
20
25
30
35
40
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3
Service Life (years)
p
r
e
s
s
u
r
e

d
r
o
p

(
p
s
i
)
First UOP charge loaded in July 1999
Compound bed UI-94
1
/8 +4A-DG
1
/8 +
4A-DG
1
/16
Third UOP charge loaded in November 2004
Compound bed UI-94
1
/8 + 4A-DG
1
/16
Ramped heating
Second UOP charge loaded in July 2001
Compound bed UI-94
1
/8 + 4A-DG
1
/8 + 4A-DG
1
/16
Ramped heating
UOP
TM
MOLECULAR SIEVE ADSORBERS
Fig 2 - Pressure drop data review July 1999 - April 2006 Pressure drop evolution
0
5
10
15
20
25
30
35
40
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3
Service Life (years)
p
r
e
s
s
u
r
e

d
r
o
p

(
p
s
i
)
First UOP charge loaded in July 1999
Compound bed UI-94
1
/8 +4A-DG
1
/8 +
4A-DG
1
/16
Third UOP charge loaded in November 2004
Compound bed UI-94
1
/8 + 4A-DG
1
/16
Ramped heating
Second UOP charge loaded in July 2001
Compound bed UI-94
1
/8 + 4A-DG
1
/8 + 4A-DG
1
/16
Ramped heating
Case 2: Central African Processor
Case 2: Central African Processor
Adsorbent Life Doubled with UI
Adsorbent Life Doubled with UI
-
-
94 Adsorbent
94 Adsorbent
UOP 4733-15
Case 3: North American Producer

Revamped a 3
Revamped a 3
-
-
train cryogenic liquids recovery plant
train cryogenic liquids recovery plant

High pressure regeneration (1050 psig)

High pressure regeneration (1050 psig)

Processing 20% more gas than design

Processing 20% more gas than design

Occasional liquid carryover evident

Occasional liquid carryover evident

Initial adsorbent charge lasted ~6 months

Initial adsorbent charge lasted ~6 months

Some plant modifications but still adsorbent life was

Some plant modifications but still adsorbent life was
< 12 months
< 12 months

Changed over to UI
Changed over to UI
-
-
94 in 2002
94 in 2002

Adsorbent charges now exceed 2 years life.

Adsorbent charges now exceed 2 years life.
Customer very satisfied with UI
Customer very satisfied with UI
-
-
94 Adsorbent
94 Adsorbent
UOP 4733-16
Summary
Summary

MOLSIV
MOLSIV

UI
UI
-
-
94 Adsorbent developed for
94 Adsorbent developed for
challenging natural gas dehydration service
challenging natural gas dehydration service
-
-
Tight designs
Tight designs
-
-
Changing process conditions
Changing process conditions
-
-
Resistant to glycol and amine carryover
Resistant to glycol and amine carryover
-
-
Upsets
Upsets

periodic liquid entrainment

periodic liquid entrainment

UOP MOLSIV UI
UOP MOLSIV UI
-
-
94 Adsorbent is
94 Adsorbent is
a robust product that maintains
a robust product that maintains
its integrity under challenging
its integrity under challenging
operational conditions
operational conditions
UOP 4733-17
UOP 4733-18