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Janusz Kertynski, Dr Bernhard Schreiner

Budapest, 13-14 October 2015

Increased flexibility of refineries by O2 enrichment.Sulphur recovery and new opportunities.

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The Linde Group

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Actual needs of refining industry Efficiency increase and process excellence

• Low prices of crude oil (sustainable?)

• Growing demand on gasoline in Europe

• Tighter environmental regulations

• Refining capacity growth in Asia and the

Middle East

• Safety

• Flexibility

• Reliability

• Best possible utilization of

existing infrastructure

• Revamps and investments in

new infrastructure

• Need for low CAPEX solutions

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Linde GasApplications for refineries and petrochemical industry

• Inertization of tanks, terminals, railway

tankers, road tankers etc.

• Nitrogen Services – Purging, drying,

pressure testing, temporary sourcing etc.

• Cryogenic condensation of volatile

compounds

• Industrial water treatment – e.g. pH

adjustment with CO2

• Reduction of NOx emission with use of

Ozone

• Oxygen enrichment in Sulphur Recovery

Units

• Oxygen enrichment of Fluid Catalytic

Cracking

• Oxygen enrichment in process fired

heaters (New development)

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Typical gas applications for routine operation of Refinery Processes

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Effect of oxygen enrichment on flow of process air

Overall flow with same amount of oxygen at different enrichment levels

0

10

20

30

40

50

60

70

80

90

100

20 30 40 50 60 70 80 90 100

O2 concentration [%]

Flow

rate

[m³/h

]

Nitrogen

Total flowrate

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Oxygen enrichment in Sulphur Recovery UnitsDescription of Claus Process for Sulphur Recovery

WHB

Thermal Stage Catalytic Stages

BurnerAcid Gas

Air(Oxygen)

RXNFURN

CatalyticConverters

Sulphur pit

SulphurCondensers

Reheaters

To TGTU

incinerator

2H2S + 3O2 2SO2 + 2H2O

Overall Chemistry: 2H2S + O2 2S + 2H2O

2H2S + SO2 3S + 2H2O

2H2S + SO2 3S + 2H2O

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Oxygen enrichment in Sulphur Recovery Units3 Modes

Low level EnrichmentMedium level

Enrichment

High level Enrichment

(Double Combustion)

Enrichment Up to 28 % Oxygen Up to 45 % Oxygen Up to 100 % Oxygen

Add gaseous Oxygen

(GOX)

into existing air

blower discharge

Directly into

combustion zone

Stepwise into

combustion zones

(interstage cooling )

Adjustment at air-

based Claus unit for

revamp by O2

enrichment

Insert oxygen injector

into process air pipe

Substitution of the air-

based burner by new

burner (SURETM type)

Substitution of air-

based burner by new

burner(SURETM type)

&

Various measures like

e.g. installation of a

second waste heat

boiler

Capacity Increase Up to 35 % Up to 75 % Up to 150 %

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Oxygen enrichment in Sulphur Recovery UnitsCapacity Increase

Case example:

3 CUs of same capacity are

operated (max. Sulphur

production 100 tons/day

– routinely all at a load of

80% of design capacity

In case one CU faces shut-

down the two other CUs left

running can take over the

load of the un-operated unit

by applying O2e running at a

load of 120 tpd

Capacity increase for Dp = constant(measured)

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10

20

30

40

50

60

70

80

90

20 25 30 35 40

O2 [vol%]

Capa

city

incr

ease

[%]

90% H2S CW 90% H2S measured

50% H2S CW 50% H2S measured

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Oxygen enrichment in Sulphur Recovery Units Ammonia (NH3) in Claus units

Precipitation of ammonium salts acc. to

NH3 + H2O + SO2 NH4HSO3

Often causes:

• Reduced plant availability

• Less Sulphur recovery efficiency

• Enhanced effort for plant maintenance

• Reduced throughput

Remedy: Improvement of Claus furnace operation

• Increased temperature

• Higher residence time

• Better mixing of the reactants

O2 enrichment to be considered

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Oxygen enrichment in Sulphur Recovery Units Ammonia

(NH3) in Claus units – Measurements

Measured Ammonia destruction effects

Air, 21 vol.-% O2

Enriched air, 27-28 vol. -% O2

Different Claus units

0

300

200

100

NH3

[vppm]

A B C D E

Sampling of

Claus process gas

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Trial results - mode 1: H2 demand *

AG + SWS gas + Air 100 %

AG + SWS gas + Air (less) + O2 (i.e. 26% enriched) 73 %

Trial results - mode 2: H2 demand *

AG + Air 100 %

AG + Air (less) + O2 (i.e. 26% enriched) 62 %

Enhanced H2 partial pressure in the Claus process gas

reduces fuel gas consumption at the tailgas unit

* Amount of H2 to be added up-stream the hydrogenation step

Oxygen enrichment in Sulphur Recovery UnitsHydrogen savings at the tailgas unit (SCOT-type)

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Gaseous

Oxygen

(GOX)

Central process control system

Controller

Air and oxygen toClaus main burner

Air

Gas distributor

Measuringand

controlunit

O2 analyzer

Tank / vaporizer

Equipment to be delivered by Linde

Equipment in refinery

Oxygen enrichment in Sulphur Recovery UnitsHydrogen savings at the tailgas unit (SCOT-type)

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Oxygen enrichment in Sulphur Recovery UnitsTrials with O2 enrichment (Low level): Scope & hardware

Service offer:

• Consulting/Studies – Identification/verification of needs and bottlenecks

• Realisation of field trials out of one hand with low cost

• Tailored hardware solutions for oxygen supply/dosing/injection

• Ammonia services (sampling/analysis)

• Trial report and recommendation of target/fixed solution

OXYMIXTM Flowtrain and controller at the

plant site

OXYMIXTM Injector for safe

and efficient mixing of

oxygen into the process air

Portable tank (ISO Container) and

containerised vaporiser

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1. FCC reactor 2. Regenerator 3. Boiler 4. Fractionation 5. Recycle oil

Gasoil

Gasoline

Crack gas

Steam Steam

Off-gas

Recycle oil

Residue

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5

2

1

3

Vacuum gasoil

Oxygen

Regeneration air

O2 enrichment in FCC Processing

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O2 enrichment in FCC Processing

Oxygen enrichment at the FCC regenerator is typically applied:

• If the air blower of the regeneration is limiting

• If the velocity in the regenerator is too high - abrasive effects and catalyst losses

• For increase of throughput of FCC feed

Oxygen enrichment at the FCC regenerator is proven technology which has the potential to:

• Increase flexibility towards heavier feeds, load changes and light products

• Increase capacity

• Reduce catalyst losses

• Improve economy substantially

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Oxygen enrichment in process furnaces – OPFGeneral process description

Idea

Use Oxygen to improve furnace performances with low CAPEX:

• Higher capacity

• Higher efficiency

• Less NOx

Technology Basis

Injection of Oxygen stream in new burners or existing ones with

specific layout.

When?/Benefits

• Capacity increase

• Better flexibility – reduced influence of fuel composition changes

• Solving draft problems (overpressure issues)

• Improving flame stability - avoid impingement and big flames

• Higher fuel efficiency due to reduced amount of flue gas and

improved exchange in convection section

• Suitable for both natural draft and forced draft systems

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Linde burner design and test center - Italy

Oxygen enrichment in process furnaces - OPFScope and services

• Consulting/Studies – Identification/verification of needs and bottlenecks

• Design review of the furnace (Linde Gas + Linde Engineering)

• Equipment supply (OXYMIXTM Flowtrain + OXYMIXTM Injector , burners)

• Burner testing

• Assistance for start-up

• Performance monitoring

• Gas supply

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Oxygen enrichment in refining processes Summary

Oxygen enrichment comes with

• Increased plant capacity

• Increased flexibility (technically and conceptually)

• Potential fuel savings

• Improved combustion – e.g. NH3 destruction in Claus units

• Low CAPEX

Claus O2 enrichemnt trials – Refinery LOTOS 2014

Thank You

Contact information:

Dr Bernhard Schreiner - Bernhard.Schreiner@linde-gas.com

Janusz Kertynski – janusz.kertynski@pl.linde-gas.com

Thank You

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Back-upOxymix™

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Back-upOPF - Impact on NOx emission

NOx Reduction possible - Induced stratified combustion and induced flue gas recirculation due to specific layoutand burner design

Typic. Heater vs O2 Enriched heater

Typ. O2 Enrich.

H.R. ( MW) 1.43 1.43

O2 in C.A. ( %v) 21 24

NG flow (kg/hr) 108 108

O2 flow (Nm³/h) 0 52

Air flow (Nm³/h) 1600 1200

Pressure drop 100% 75%

NOx emissions 100% 76%