2010 AIChE Spring National Meeting

Welcome
to the
22nd Annual
Ethylene Producers’
Conference
March 22 – 25, 2010
San Antonio, TX
EPC – San Antonio, TX March, 2010
Catalyst Technology for the Removal of
Acetylenes, NOx and Oxygen From
Olefin Streams

M. Sun, Raj Rajesh, R. Zoldak,

S. Blankenship, M. Urbancic

Süd-Chemie

March 24th, 2010

EPC – San Antonio, TX March, 2010

Presentation outline

‰ Applications and process overview

‰ OleMax 100 – multifunctional catalyst system

‰ New development - suitable for high CO feeds

‰ Summary and conclusions

EPC – San Antonio, TX March, 2010

Refinery off gas purification

‰ FCC/DCC off gases contain valuable products such as

Ethylene, Propylene and Hydrogen
ƒ 5-20% Ethylene, 5-10% Propylene, 5-20% Hydrogen
ƒ In most refineries, off gas stream is used as fuel-gas

‰ However, off-gas also contains di-olefins, NOx, oxygen,

water, CO, CO2, arsine, phosphine, heavy metals and
other impurities

‰ Key Question – How can we create value by recovering

useful products from refinery off gas, that otherwise only
has “fuel value”?

EPC – San Antonio, TX March, 2010

FCCU – Typical LPG Recovery

FCC Off Gas

Additional LPG
Propylene

C3 Splitter
Naphtha
Absorber
Amine Caustic
Stripper
FCCU Wash Wash
FCCU LCO
Propane
FCC
HCO Gasoline

Debutanizer C4’s to Alky Unit

Bottoms or MTBE

LPG Splitter
Main Fractionator
EPC – San Antonio, TX March, 2010
Olefins & Hydrogen Recovery

FCCU Off-Gas Acid Gas

Removal
Hydrogen

Fuel Gas

Ethylene
Offgas
Purif OleMax 100 Series
Reactor

C2 Splitter

Dryer Cold
Box
Ethane

LPG
Sour Feed Flow Demethanizer Deethanizer
Sheet
EPC – San Antonio, TX March, 2010
Process objectives

‰ Catalytic selective removal of contaminants to achieve the

following critical objectives
ƒ Safety-critical: Elimination of NOx, O2 accumulation in the cold
box that can otherwise lead to unsafe operation of the cryogenic
processing unit
ƒ Process-critical: Conversion of acetylenes and dienes and
removal of trace amounts of contaminants to meet specification
targets for ethylene & propylene
ƒ Economic-critical: Prevention of excess hydrogenation of
olefins to alkanes to retain full value of the component olefins
and H2

EPC – San Antonio, TX March, 2010

OleMax 100 Series

‰ Single catalyst system to achieve all

the objectives
ƒ Selective hydrogenation of
acetylenes and dienes with very
minimal olefin loss
ƒ Complete conversion of NOx and O2

ƒ OleMax 101, high Ni ƒ Removal of trace levels of arsine,

phosphine, and other contaminants
ƒ OleMax 102, med Ni
from product olefins
ƒ OleMax 103, low Ni
ƒ OleMax 104, V. high Ni
ƒ Resulting in value added products –
contaminant-free H2, ethylene,
propylene, E/P feed to cracker

EPC – San Antonio, TX March, 2010

 Parametric studies of OleMax 102

Typical Feed Composition Test Conditions

CO, ppm 1,000 -10,000
NO, ppb 600 P, MPa 1.8
O2,% 0.3 GHSV,h-1 2500
H2,% 5.5 – 10.5 Temp.,°C 190 - 235
C2H2, ppm 550 PH2,kPa 105 – 202
C2H4, % 18 H2S, ppm 5 - 20
C2H6, % 0.01
C3H6, % 5
C3H8, % 0.03

EPC – San Antonio, TX March, 2010

 Example test results of OleMax 102

PH2, kPa 202 202 202

CO, ppm 1,000 1,000 1,000
H2S, ppm 5 20 5
Temp., °C 232 232 190
Feed Product
NO, ppb 600 7 12 106
O2, ppm 3000 <0.01 <0.01 2339
C2H2, ppm 550 1 4 508

C2H4 loss, %
3 0.5 0
(C2H4 basis)
C2H4 loss, %
0.6 0.09 0
(Total feed basis)

EPC – San Antonio, TX March, 2010

 Test feeds containing MAPD and BD

Components Test Feed A Test Feed B

CO, ppmv 10000 5300

Ethylene, mol% 30 30

Propylene, mol% 5 5

Acetylene, ppmv 174 1000

MA, ppmv 115 350

PD, ppmv 100 250

1,3-BD, ppmv 1500 8500

EPC – San Antonio, TX March, 2010

 Test results of OleMax101 and OleMax104

With Feed A OleMax 101 OleMax 104

Pressure, MPa 0.97 0.97

Inlet: H2, mol% 8 8

Inlet: H2S, ppm 25 25

Average bed T, ºC 202 215 203 214

Reactor outlet C2H2, ppm 0.40 0.06 0.04 0.02

Conversion, %: MA 89 96 99 99

PD 44 61 73 83

BD 39 55 67 76

C2H4 Loss (C2H4 Basis), % 0.00 0.07 0.17 0.25

EPC – San Antonio, TX March, 2010

 Test results of OleMax 101 with Feed B

Temperature, ºC 204 231 230

Pressure, MPa 0.97 0.97 0.97
H2, % 8 8 8
Inlet H2S, ppm 10 25 50
Ethylene Loss, % 0.02 -0.24 -0.28
Acetylene Conv.% 100.0 100.0 99.7
MA Conv. % 100.0 93.8 90.3
PD Conv. % 87.8 53.4 46.9
BD Conv., % 82.4 42.8 37.5

EPC – San Antonio, TX March, 2010

Correlation between C2H2, MA, PD conversions and BD conversion

0 C2H2
C2H2, MA, PD Conversion

0 MA
0

0
PD
0

0 test resuls with Feed B

0 test results for Feed A
0
0 10 20 30 40 0 60 0 80 90 100
BD Conversion

EPC – San Antonio, TX March, 2010

Correlation between ethylene loss and BD conversion

OM104 with Feed B OM101 Feed A

Ethylene Loss

OM101 with Feed B OM104 Feed A

Feed A

Feed B

BD Conversion

EPC – San Antonio, TX March, 2010

OleMax 100 Series – Typical
expectation of performance
‰ Catalyst operates in a cyclical mode with regeneration
ƒ Cycle length varies from 12 – 48 months (design-based).
ƒ Catalyst is regenerable; ex-situ regeneration is possible
‰ Spare reactor configuration recommended for continuous operation
‰ Catalyst life can extend to several years of service
‰ Typical Metrics:
Typical Inlet Expected Outlet
NOx, ppbv 500-600 < 0.05 ppmv
Oxygen, ppmv 1500-3000 < 1 ppmv
Acetylene, ppmv 100-500 < 1 ppmv
Heavy metals, ppm 0.5 – 1 < 10 ppbv
Inlet sulfur, ppm 5 – 50 to control selectivity
Ethylene Loss < 0.5% on total feed

EPC – San Antonio, TX March, 2010

Nickel carbonyl

‰ Ni + 4 CO Æ Ni(CO)4
ƒ 1 ppb Ni(CO)4 in air is the Permissible Exposure Limit (OSHA).
ƒ High CO partial pressure and low temperature thermodynamically favor
Ni(CO)4 formation.
ƒ At typical conditions, the equilibrium concentration of Ni(CO)4 over
reduced nickel is less than 1 ppb when CO concentration is <1 mol%.
ƒ Sulfided nickel has much lower tendency to form carbonyl than reduced
metal
ƒ Follow recommended startup, operation, and shutdown procedures

‰ Typical designs for nickel catalyst involve CO < 1.0% in feed

EPC – San Antonio, TX March, 2010

Developing a new catalyst for
high CO feeds
‰ Single catalyst system to convert acetylenes, NOx and O2 with
minimal olefin loss
‰ No toxic carbonyl issue with feeds containing high CO
‰ Pre-reduction is recommended
‰ Pre-sulfiding is not required
‰ Sulfur addition is not necessary, but the catalyst can tolerate
up to 10 ppm sulfur in feed

¾ Precious metal on alumina - T-2874

EPC – San Antonio, TX March, 2010

 Parametric studies of T-2874

Typical Feed Composition Test Conditions

CO, % 0.5 -2.0

NO, ppm 1.4 P, MPa 1.4

O2,% 0.3 GHSV,h-1 1500 -3500

H2,% 5 – 15 Temp.,°C 190 - 250

C2H4, % 27 H2S, ppm 0 - 20

C3H6, % 5 C2H2 650 ppmv

PD, % 0.03

MA, % 0.05

BD, % 0.2 – 0.5

EPC – San Antonio, TX March, 2010

 Test Results of High CO Study of T-2874

Temperature, ºC 176 188 201

Pressure, MPa 1.4 1.4 1.4
NOx, ppbv < 10 < 10 < 10
O2, ppmv 1.2 < 0.5 < 0.5
Ethylene Loss, % 0.48 0.65 1.09
C2H2 Out, ppmv <3 <3 <3
MA Conv. % 60.7 97.6 100
PD Conv. % 39.9 39.5 48.7
BD Conv., % 20.8 24.2 23.6

EPC – San Antonio, TX March, 2010

 High CO Test of T-2874

Typical Feed Composition Test Conditions

CO, % 4.0

NO 60 – 100 ppbv P, MPa 1.9

O2,% 0.29 GHSV,h-1 2500

H2,% 9 – 10 Temp.,°C 190 - 250

C2H4, % 33 H2S, ppm 0 - 20

C3H6, % 4 C2H2 700 ppmv

PD, % 0.03 C2H6, C3H8 trace

MA, % 0.06

BD, % 0.2

EPC – San Antonio, TX March, 2010

Benefits of recovering olefins
and hydrogen
Ethylene
Ethylene Ethylene
Plant
Plant Propylene

OffGas
Off Gas Dilute
Dilute Styrene
Refinery Purification
Purification Styrene
Refinery Ethylene
Ethylene Styrene
&&Olefins
Olefins Plant
Plant
FCCU
FCCU EB
Recovery EB
Recovery

Propylene
Metathesis
Metathesis Chem. Grade

Recovered H2
To Refinery

EPC – San Antonio, TX March, 2010

Catalytic Options
‰ Unique multi-functional OleMax 100 series catalysts
ƒ First-to-market with multiple commercial experiences
ƒ Decades of experience with sulfided nickel catalysts
‰ Newly developed T-2874 and application technology
ƒ Suitable for low and high CO feeds
ƒ Good selectivity without presulfiding or sulfur addition

EPC – San Antonio, TX March, 2010

 2010 AIChE Spring National Meeting

Thank you very much!

March 22 – 25, 2010

San Antonio, TX
EPC – San Antonio, TX March, 2010