Praxair’s Oxygen Addition

Technologies for Chemical

Oxidation Reactions

Presented to Customer X
DATE

Copyright © 2006, Praxair Technology, Inc. All rights reserved.

Praxair Oxygen Addition Experience

 Air Enrichment
 Phenol
 TPA
 Acrylonitrile
 Ethylene Dichloride (oxychlorination)
 Maleic anhydride
 Phthalic anhydride
 Direct Injection (Gas Phase)
 Nitric acid
 Caprolactam
 Acrylonitrile
 Maleic anhydride
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 Oxygen Addition Technologies
Praxair offers two technologies:

 Air Enrichment (AE)

Vent
 Commercially Practiced for CHP/Phenol

 Direct Oxygen Injection (DOI)

 Developmental for
Liquid Phase Reactions
Feed Product

Air Oxygen – Direct

Injection
Compressor Reactor

Oxygen – Air Enrichment

3
Air Enrichment - Methodology

 AE Process
 Increase Oxygen conc. in
air feed up to 30% Vent
 Typically 25% O2
 Increase feed flow rate
 Maintain constant oxygen
concentration in
headspace
 AE Installation Feed Product
 Easy retrofit
 Oxygen source Air
 Oxygen flow control skid
 Air line tee Compressor Reactor
 Oxygen injector
Oxygen

4
Air Enrichment -
Typical Hardware Configuration

5
Air Enrichment -
Typical Hardware Configuration
Sparger

Oxygen

Feed Air 6
Air Enrichment -
Typical Hardware Configuration

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Air Enrichment – Benefits for CHP/Phenol

 Increased Productivity
 Phenol capacity increases up to ~20% can be achieved
with feed air enrichment to 25% oxygen
 The specific degree of improvement will depend on the
customer’s equipment configuration and operating
regime
 Mass transfer limited reactors will realize an immediate
benefit
 Kinetically limited reactors could be re-optimized (increased
temperature, increased O2 concentration) to boost rates

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 Formation Rate of Cumene Hydroperoxide
vs. Air Enrichment Level
Simulated Plant-Scale Reaction Rates at Two Reactor Temperatures

Mass
3 Transfer
Control
(Moles x 1000/liter-min)

Kinetic
CHP Formation Rate

Control T = 105oC
2
Average air bubble diameter of 0.50”

1
T = 90oC

0 0.1 0.2 0.3 0.4 0.5 0.6

Oxygen (Mole Fraction at Inlet) 9

 Commercial Plant Simulation (5 Staged Reactors) –
Air Enrichment with Thermal Acceleration
Base Case (Kinetic Limited)
Inlet Gas
Flow Liquid Flow Residence Cumene CHP
o
Reactor Temp ( C) (kSCF/h) % O2 (kGal/h) Time (h) conc. % conc.%
Feed 25 15.6 99.1% 0.7%
1 102 96 21% 14.8 2.1 95.9% 3.8%
2 102 96 21% 14.3 2.2 91.6% 8.0%
3 103 96 21% 13.8 2.4 85.8% 13.6%
4 98 96 21% 13.5 2.7 80.2% 18.8%
5 97 96 21% 13.3 2.7 74.4% 24.4%

Approx. CHP Production Rate: 23.9 k lbs/h 100%

Selectivity to CHP: 95.3%
Faster
Air Enrichment Air Enrichment / Higher Temperature (Kinetic Limited) Rate of CHP
+ Elevated Temp. Inlet Gas Formation
Flow Liquid Flow Residence Cumene CHP
In Reactor #1 Reactor
o
Temp ( C) (kSCF/h) (kGal/h) Time (h) conc. % conc.%
% O2
Feed 25 15.6 99.1% 0.7%
1 109 96 28% 14.8 2.1 93.1% 6.5%
2 102 96 21% 14.3 2.2 88.3% 11.1%
3 103 96 21% 13.8 2.4 81.9% 17.2%
4 98 96 21% 13.5 2.7 76.1% 22.7%
5 97 96 21% 13.3 2.7 70.0% 28.4%

Approx. CHP Production Rate: 28.2 k lbs/h 118% 10

Selectivity to CHP: 94.7%
Air Enrichment – Benefits (cont’d)
 Limited Capital Investment
 Minimal plant modification cost
 Capital avoidance for additional blower capacity

 Operational Benefits
 Reduced gas volume compared with increasing air flow
 Less potential for volatilization losses
 Less potential for entrainment losses
 Reduced gas pressure in plant compared with increasing
air flow

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 Case I – Fixed AE Level
(Enriched Air Volume Set to Theoretical Required for Capacity)
Production Increase Achieved 3% 5% 10%

Air Enrichment Level (% Oxygen in Air Feed) 25% 25% 25%

Nameplate Phenol Capacity 500 500 500 000s MTPY
Actual Phenol Capacity 515 525 550 000s MTPY
Actual Acetone Capacity 318 324 339 000s MTPY
Supplemental Oxygen Used 29.5 30.1 31.5 000s MTPY

Incremental Conversion Margin

Additional Phenol Revenue $19,840 $33,060 $66,120 $ 000s

Additional Acetone Revenue $8,770 $14,620 $29,240 $ 000s

Additional Cumene RMC ($14,220) ($23,690) ($47,390) $ 000s

Supplemental Oxygen Cost ($1,630) ($1,660) ($1,740) $ 000s

NET $12,760 $22,330 $46,230 $ 000s

Assumptions: Yield on cumene – 95.0%

Phenol price - $1320 / tonne
Acetone price – $950 / tonne
Cumene price - $705 / tonne 12
Oxygen price - $55 / tonne (will vary by locality and supply source)
 Case II – Fixed Air Flow
(AE Level Set to Theor. Required for Incremental Capacity)
Production Increase Achieved 3% 5% 10%

Air Enrichment Level (% Oxygen in Air Feed) 21.5% 21.8% 22.6%

Nameplate Phenol Capacity 500 500 500 000s MTPY
Actual Phenol Capacity 515 525 550 000s MTPY
Actual Acetone Capacity 318 324 339 000s MTPY
Supplemental Oxygen Used 5.4 9.0 17.9 000s MTPY

Incremental Conversion Margin

Additional Phenol Revenue $19,840 $33,060 $66,120 $ 000s

Additional Acetone Revenue $8,770 $14,620 $29,240 $ 000s

Additional Cumene RMC ($14,220) ($23,690) ($47,390) $ 000s

Supplemental Oxygen Cost ($300) ($490) ($990) $ 000s

NET $14,090 $23,500 $46,980 $ 000s

Assumptions: Yield on cumene – 95.0%

Phenol price - $1320 / tonne
Acetone price – $950 / tonne
Cumene price - $705 / tonne 13
Oxygen price - $55 / tonne (will vary by locality and supply source)
Past and Current Applications
 Air Enrichment is practiced commercially for cumene
oxidation
 Past and current installations worldwide
 Air Enrichment levels up to 28% oxygen evaluated
 Praxair has experience modeling process performance using
AE, and in the design of oxygen delivery systems
 Safety analysis/HAZOPs
 O2 feed system
 O2 effects on customer process
 Design of oxygen skid
 Design/Construction of oxygen sparger
 Interactions of the oxygen with the process

 Manufacturers must ensure that existing plant equipment,

process controls and procedures are appropriate for the safe
implementation of AE
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Direct Injection - Methodology
 DOI Process
 Oxygen injected directly into the reactor into oxygen-starved zones
 Increase or maintain feed flow
 Maintain constant oxygen concentration in headspace
 DOI Installation
 Requires some reactor modifications
 Special skid and sparger to prevent hydrocarbon backflow
 Good mixing must be maintained to prevent bypassing of pure oxygen

Vent

Feed Product

Air Oxygen – Direct Injection

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Compressor Reactor
Direct Injection - Benefits

 Production Increase
 Increased capacity of up to 32% is possible

 Byproduct Reduction
 Oxygen supplied to oxygen deficient regions of the
reactor
 Decrease reactions associated with oxygen starvation

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Summary
 Air Enrichment is a proven technique for increasing
the productivity of plants making phenol/acetone via
cumene peroxidation
 No reactor modification; modest capital investment
 Direct Oxygen Injection is a developmental
technology that can further enhance the efficiency of
liquid phase oxidations
 Praxair can assist with engineering support for the
evaluation and implementation of AE and DOI
 Safety evaluations
 Plant trial support

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• Oxygen Addition Knowledge
• Oxygen Delivery Technology
• Oxygen Production
• Safety / Materials Compatibility
Customers
Oxygen • Capacity Increase
Addition
• Yield Improvements
• Process Improvements
• Operation Improvements

Next Steps?
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