Refinery Sour and Flue Gas Treatment Integrated Solution ... · Meets environmental requirements...

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Refinery Sour and Flue Gas

Treatment Integrated Solution from

DuPont Clean Technologies

Presented By: Andrey Glinsky, Business Development Manager O&G,

DSS CT

Friday, 24 April 2015



Sour Oil and Gas Processing – Acid Gas Treatment

2

Oil and Gas Processing Summary

Common Flue and Acid Gas Treatment Technologies and Challenges

DuPont Clean Technologies Flue and Acid Gas Treatment Technologies BELCO® EDV® Scrubbing for FCC Regenerators, Fired Heaters and Boiler DynaWave® Tail Gas Scrubber as TGTU alternative or supplement SULFOX™ Sulphuric Acid Plant as Claus alternative or supplement SolvR™ Regenerative Absorption as alternative TGTU



Oil and Gas Processing Summary

3

Petroleum Refinery Production Goals

Increase depth of refining (Russia political goal), decrease BB

Operate the facility continuously and reliably (4-5 years cycle length as a minimum)

Economically create products meeting the market’s quality standards

Sell the products to the market

Comply with the environmental regulations

Sour Oil Challenges

Increased production from unconventional oil fields - heavy oil fractions

Increased production from unconventional oil fields with

higher Sulphur content



Typical High Conversion Refinery

4

Hydrocracked Distillate (Gasoil)

Coker Heavy Naphtha (Gasoline)

Hydrocracked Heavy

Naphtha (Gasoline)

Coker Heavy

Distillate (Gasoil)

FCC Heavy Cycle Oil

Jet Fuel /

Kerosene

Gasoline

Blending

Diesel

Refinery

Fuel Gas

LPG

To top of page

From bottom of

page

Coke

H2

H2

H2

H2

H2

H2

H2

H2

H2

H2

Straight-Run Heavy Distillate (Gasoil)

Straight-Run Diesel Oil

Atmospheric Distillate (Gasoil)

Atm. Bottoms

Vac. Resid.

Coke

Co

ke

r L

igh

t D

istilla

te (G

aso

il)

Heavy Vacuum Distillate (Gasoil)

Coker Light Naphtha (Gasoline)

Coker Heavy Naphtha (Gasoline)

Light Vacuum Distillate (Gasoil)

Propylene (C3)

Isobutane (C4)

Butylenes / Amylenes (C4 / C5)

FCC Light Distillate (Gasoil)

FCC Naphtha (Gasoline)

Hydrocracker

Hydrocracked Distillate (Gasoil)

Hydrocracked Light Naphtha (Gasoline)

FCC Naphtha (Gasoline)

FCC Gasoline

Hydrotreater or

Sweetener

Dimate

Alkylate

Dimerization

Alkylation

Polymerized GasolinePolymerization

Reformate

Hydrocracked Light Gasoline

or Isomerate

Isomerization

and / or Benzene

Saturation

Straight-Run Light Naphtha (Gasoline)

Straight-Run Heavy Naphtha (Gasoline)

Coker Light Naphtha (Gasoline)

Straight-Run Jet Fuel (Kerosene)

Gas

Jet Fuel (Kerosene)Jet

Hydrotreater

Jet Fuel (Kerosene)

Diesel Oil

Merox

Diesel

Hydrotreater

Fluidized

Catalytic

Cracker

(FCC)

FCC Feed

Hydrotreater

Coker

Vacuum

Distillation

Unit

(VDU)

Atmospheric

Distillation

Unit

(CDU)

Heavy

Gasoline

Hydrotreater

Reformer

Coker Light

Gasoline

Hydrotreater

Gas Processing

& Hydrogen

Plant

Crude

Oil

IsoTherming®

Ultra-Low Sulphur Diesel/Kerosene

IsoTherming®

Ultra-Low Sulphur Diesel/Kerosene

STRATCO®

Alkylate

Sulphuric Acid Loop

MECS® SAR

Clean Exhaust Gas

MECS® SolvR™

Clean Exhaust Gas

MECS® SULFOX™

Sulphuric Acid

MECS® DynaWave®

Clean Exhaust Gas

MECS® AmmSox®

Ammonia Sulphate

BELCO® EDV® Scrubbing

Clean Exhaust Gas



Sour Oil and Gas Treatment

5

Sour Oil and Gas Treatment Supports Production Goals

Removes contaminants to allow sale of end products

Transforms those contaminants into a disposable by-product

Meets environmental requirements for continued operation

Sour Oil and Gas Treatment Technology Challenges

Units are an operating cost only, very little value added

Unfamiliar unit operations and chemistry compared to other units

Reliability, flexibility, capacity may limit operations



Sources of Airborne Emissions at the Petroleum Refinery (H2S, SOx, NOx, Dust)

6

FCC regenerator and Fluid Cokers (SOx, NOx, Dust)

Heaters and Fluid Cokers (SOx, NOx, Dust)

Claus units (H2S, SOx, NOx)

Sulphuric acid units (SOx, NOx)

Power plants and boilers burning FO, coal, petroleum coke (SOx, NOx, Dust)

DuPont offers solutions for all of them



Conversion of Airborne Sulphur Emissions at the Petroleum Refinery (H2S, SO2 )

7

Concentration of SO2 for the further processing

(SolvR™)

Conversion to Sulphuric Acid (SULFOX™)

Conversion to Ammonia Sulphate (AmmSox®)

Conversion to Solid Waste or Liquid Effluent (BELCO® EDV® Scrubber, DynaWave® Scrubber)

DuPont will propose the most efficient solution for each case (economic and technical)



8

Examples of solutions



BELCO® EDV® WET SCRUBBING Reliably Control FCC Regenerator Flue Gas Emissions

SOx, NOx & Particulate Control in a Single Up-Flow Tower



• FCCU (refinery process units) makes $$$ -

gasoline, diesel and other valuable products

• Always keep the FCCU (process units) running

• Always control flue gas emissions

• Always keep emissions control costs as low as

possible

• Always understand that controlling emissions

does not typically make $$$, but costs $$$

BELCO® EDV® WET SCRUBBING We Understand Controlling FCC Regenerator Flue Gas Emissions



BELCO® EDV® WET SCRUBBING Reliably Control FCC Regenerator Flue Gas Emissions

SOx, NOx & Particulate Control in a Single Up-Flow Tower

Extremely Robust – Always Controlling Emissions

Years of Continuous Uninterrupted Operation

Match FCCU Operating Campaigns

• Typically 3 – 7 years continuous operation

• Handles FCC Upsets without shut down

Allows Refiners to Focus on Producing Valuable

Products Without Worrying About Emissions

124 Licensed Units on FCCUs since 1994

5 Units in Russia / CIS

Additional Refinery Units Licensed on Fluid Cokers,

Fired Heaters and Boilers



BELCO® EDV® WET SCRUBBING Low Energy Wet Scrubbing - Years of Continuous Operation

• Open Tower Design - Nothing to Plug or Foul

• Staged Wet Scrubbing Approach

A. Quench/Saturation with water sprays

NOx Oxidation with ozone injection

B. SOx , NOx + PM Removal with water sprays

C. Additional SOx + PM Removal with

gas compression / expansion and filtration water sprays

D. Droplet Removal with cyclonic separation

E. Discharge to Atmosphere with stack

• Flexibility with Different Reagents/Buffers • Typically sodium or magnesium based • Regenerative based systems

• Open Tower Design • Nothing to Plug or Foul

Water

Reagent

Effluent to Disposal

Hot-Dirty Gas Inlet

Clean

Gas

Outlet

A

B

C

D

E



MECS® solutions for SRU/TGTU



Typical Acid Gas Treating Line Up

14

Refinery or Gas Plant Units

Amine Treatment Unit (ATU)

Sour Water Stripper (SWS)

Sulphur Recovery

Unit (SRU)

Tail Gas Treatment

Unit (TGTU)

Clean Tail Gas

Sulphur

Stripped Water

Tail Gas

Acid Gas Recycle Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

Many Claus-type SRU

possibilities

Many different

TGTU technologies



Typical Claus SRU Process

15

Sour Gas

Air

Reaction Furnace

Waste Heat Boiler

Water Steam

Condenser

Water

Steam

Sulphur Water

Steam

Sulphur Water

Steam

Sulphur Water

Steam

Sulphur

Claus Reactor

Reheater

+

↓

+

↓

+

↓

+

↓

+



Claus Operating Complications

16

Weak H2S Feed

• 20 – 50% requires modifications to operating conditions and flow scheme

• High CO2:H2S ratio = low furnace temperature

Ammonia in the feed

• Incomplete destruction = ammonia salt deposition (high pressure drop, corrosive)

Changing of or additional components in the feed (mercaptans, HC’s, COS, CO2, etc.)

• Varying oxygen demands = unstable operation due to control lag

• Unstable operation = soot formation (high pressure drop) = safety concern (hydrocarbon breakthrough)

Reliability

• Dual, redundant systems required to aspire to ~100% on-stream time

Sulphur recovery insufficient to meet current regulatory emission requirements



Typical SCOT TGTU Process

17

+

Air

Reheater

Water

Steam Hydrogenation Reactor

Fuel

Gas Cooler

Quench Column

Absorber

Regenerator

To Claus Unit

Steam

Sour Water to SWS

Fuel



MECS® DynaWave® Tail Gas SO2 Scrubbing

18



MECS® DynaWave® Wet Scrubber Chemistry with Caustic

19

After Incineration to SO2

2NaOH + SO2 → Na2SO3 + H2O Na2SO3 + ½O2 → Na2SO4

Direct Reaction with H2S

NaOH + H2S → NaHS + H2O NaHS + NaOH → Na2S + H2O Na2S + 4NaOCl → Na2SO4 + 4NaCl + Heat

Fast reaction

Small, simple equipment

Flexibility to handle variable flows and concentrations

High pH requirement

• Increases caustic usage and resulting effluent

• Reacts with CO2

Small capacity or emergency use



MECS® DynaWave® Applications

20

SO2 Scrubbing Downstream of SCOT TGTU

Ultra-low SO2 emissions

Minimize caustic consumption and effluent generation

< 5 – 10 ppmv SO2 guaranteed; <1 ppmv actual operation

SO2 Scrubbing as Claus TGTU (<25 TPD)

Ultra-low SO2 emissions

$4.0 MM Order-of-Magnitude Total Equipment Cost

$100,000/yr – $500,000/yr Caustic Consumption ($400/t NaOH)

• Very dependent on flow rate and required removal efficiency

Ability to fully bypass Claus unit to DynaWave® (through incinerator)

Direct H2S Scrubbing

Eliminate emergency flaring

• Specific example at 3,000 Nm3/h at 40% H2S



Generic TGTU and MECS® DynaWave®

21



Sulphur Recovery

Unit (SRU)

Any TGTU + Incinerator + DynaWave®

Clean Tail Gas

Sulphur

Stripped Water

Tail Gas

Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

Liquid Effluent

Acid Gas Recycle

+

↓




MECS® DynaWave® TGTU

22



Sulphur Recovery

Unit (SRU)

Incinerator + DynaWave®

Clean Tail Gas

Sulphur

Stripped Water

Tail Gas

Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

Liquid Effluent

+

↓




MECS® DynaWave® Application Comparisons

23

SO2 Scrubbing Downstream of Extended Catalytic (EC) or Sub-Dew Point Claus SRU

2 Stage

Claus SRU 2 Stage Claus SRU + SCOT-type TGTU

2 Stage Claus SRU + EC / DynaWave®

Savings

Relative Total Installed Cost

100 185 140 ~24%

SCOT-type TGTU EC / DynaWave® Savings

Relative Total Installed Cost

85 40 ~53%

Equipment Count

24 16 -8

Relative Plot Size

(including Claus SRU with 2 reactors)

-40%



Sulphuric Acid Route vs Sulphur

24



SULFOX™ Sulphuric Acid Plant

DynaWave® Tailgas

Scrubber

Clean Tail Gas

Sulphuric Acid

Stripped Water

Tail Gas

Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

Liquid Effluent

↓

↓




Sulphuric Acid and Sulphur (Retrofit / Debottleneck)

25



Sulphur Recovery

Unit (SRU)

Clean Tail Gas

Sulphur

Stripped Water

Tail Gas

Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

SULFOX™ Sulphuric Acid Plant

DynaWave® Tailgas

Scrubber

Liquid Effluent

Tail Gas

Sulphuric Acid

+

↓

↓

↓




SO2 → SO3

SO2 → SO3

SO2 → SO3

MECS® SULFOX™ Wet Gas Technology Sulphuric Acid Process

26

WESP

Tail Gas

Process Gas or Air

Condensation Column w/ Glass Heat Exchanger

Feed Gas SO2 + O2 + H2O

> 390°C

~ 260°C

70°C

Heat Recovery (Steam, BFW, Molten Salt)

Recovered Acid Mist



MECS® SULFOX™ Variations for Oil and Gas

27

SULFOX™ HK – Combustion of Feed Stream

Warm Air

Acid Gas

Fuel

Decomposition Furnace

Waste Heat Boiler

Gas Cooler

Gas to Converter

Water

Steam

Steam

SO2 + O2 + H2O + Inerts Decomposition

Furnace

Waste Heat Boiler



SO2 → SO3

H2S → SO2

MECS® SULFOX™ Variations for Oil and Gas

28

SULFOX™ NK – Catalytic Conversion of Feed Stream

Air

Acid Gas

Fuel

H2S + O2 + H2O + Inerts

Condensation Column w/ Glass Heat Exchanger

Heat Transfer Fluid System

> 275°C

To WESP



MECS® SULFOX™ HK versus NK

29

SULFOX™ HK SULFOX™ NK

Feed H2S (after dilution) 0.1 – 100 vol% <5 vol%

Feed Composition Any HC, NH3 Very low HC, NH3

Feed Contaminants Optional particulate removal Gas scrubbing for very dirty feed to ensure reliability

Sulphur Removal >99% SULFOX™ Only >99.9% paired with DynaWave® tail gas scrubber

Relative Capital Cost * 125% 100%

Relative Operating Costs * 115% Power + HP steam > Operator interface

100% Power - Fuel << Operator interface

Relative Plot Area * 200% 100%

* For equivalent gas flows



MECS® SULFOX™ HK versus Claus SRU + TGTU

30

Claus SRU & TGTU SULFOX™ HK & DynaWave®

Feed Gas (vol%) ~25% H2S, ~70% CO2, ~0.5% HC, ~1.0% other sulphur

Sulphur Recovery 99.83% (as S) >99.9% (as H2SO4)

HP Steam * 100% 300%

Fuel Consumption 13 MW equivalent None

LP Steam Consumption 2.5 t/h None

Reagent Consumption None 0.5 t/h @ 20 wt%

Power Consumption * 100% 200%

Installed Cost * 100% 60%

Operating Cost * 100% -200%

Product Values Sulphur Market Value Sulphuric Acid Market Value

* Relative Values



MECS® SolvR™ TGTU

31



Sulphur Recovery

Unit (SRU)

Incinerator + SolvR™

Clean Tail Gas

Sulphur

Stripped Water

Tail Gas

SO2 Gas Recycle Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

+

↓




MECS® SolvR™ Regenerative SO2 Absorption

32

Tail Gas

Absorber

Stripper

Clean

Tail Gas

Back to

Process

Solvent

Regeneration

Water

with SO2

Interchanger

Stripper

Pump

Rich Solvent

Pump

Condenser

SO2 Reboiler

Lean

Solvent

Pump

Lean Solvent

Pump Tank

Caustic

Effluent



MECS® SolvR™ with Claus Benefits

33

Lower complexity and equipment count versus SCOT

• Reducing gas generator and hydrogenation reactor eliminated

• Incinerator moved upstream of SolvR™ (not required on final tail gas)

Air

Reheater

Water

Steam Hydrogenation Reactor

Fuel

Gas Cooler

Quench Column

Absorber

Regenerator

To Claus Unit

Steam

Sour Water to SWS

Fuel



MECS® SolvR™ with Claus Benefits

34

Lower complexity and equipment count versus SCOT

• Reducing gas generator and hydrogenation reactor eliminated

• Incinerator moved upstream of SolvR™ (not required on final tail gas)

Debottlenecks or reduces size of Claus unit

• SO2 recycle to reaction furnace reduces combustion air requirement

– Less gas volume (N2) through equipment

– Practical recycle limit fixed by minimum furnace temperature

• Theoretically possible to eliminate reaction furnace and one or more catalytic stages with SO2 : 2 H2S recycle rate

Smaller plot space (versus Claus + SCOT)

• Minor to major improvement depending on Claus configuration

– SCOT only comparison

– Elimination of reaction furnace and catalytic stages of Claus



MECS® SolvR™ Solvent – Not Your Typical SO2 Solvent

35

Name Simplified Chemistry Characteristics

Chemical Solvents

Water SO2 + H2O ↔ H2SO3 Low SO2 solubility = energy inefficient

Wellman-Lord Na2SO3 + SO2 ↔ NaHSO3 Solid formation, oxidation to sulphate, high steam use

Amines R-N:SO3 ↔ SO2 Good removal efficiency, high steam use and solvent losses

Physical Solvents

Tetraglyme Need higher SO2 concentrations to be energy efficient

New MECS® SolvR™ Solvent

Na2-R Na2-R-SO3 ↔ SO2 Loads like physical solvent Releases at lower energy Solvent untouched by salt formation

//upload.wikimedia.org/wikipedia/commons/8/80/Tetraglyme.svg



MECS® SolvR™ Solvent Benefits

36

Environmentally friendly, high capacity solvent

• Locally available precursors

• Used in food processing

• Capable of high removal efficiencies

• Generates minimal by-products

• Robust and stable with minimal losses

Reduced energy usage

• Regeneration done at atmospheric pressure rather than vacuum

• Uses low pressure steam

• Energy recovery system under development further reduces steam usage



Summary

37

Sour Gas Treatment Technologies Must Support Oil and Gas Production Goals

Operate the facility continuously and reliably

Economically create products meeting the market’s quality standards

Sell the products to the market




Sulphur Recovery

Unit (SRU)

Tail Gas Treatment

Unit (TGTU)

Clean Tail Gas

Sulphur

Stripped Water

Tail Gas

Acid Gas Recycle Amine Acid Gas

SWS Acid Gas

Stripped Water

Sour Water

Sour Gas

Many Claus-type SRU

possibilities

Many different

TGTU technologies

MECS® DynaWave®

Clean Exhaust Gas

MECS® SULFOX™

Sulphuric Acid

MECS® SolvR™

Clean Exhaust Gas



38

Thank You!

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