2012 Afpm Hg Management Presentation Final Draft 1203010

Presented by:Brad Hase, FHR Global Turnaround Manager Vic Vickery, PEI Vice President and Technical ManagerRon Radford, PEI Business Development Manager

Mercury in Hydrocarbon Process Streams: Sampling/Analysis Methods, Exposure Monitoring, Equipment Decontamination and Waste Minimization

2012 Annual MeetingAM-12-22

Mercury in Hydrocarbon Process Streams:FHR North Pole Refinery 2010 Turnaround

• Mercury found in extraction unit in 2010

• 2010 turnaround stopped and postponed until mercury management plan developed

• Impact on 2011 Turnaround


Hg in Hydrocarbon Process StreamsImpact On 2011 Refinery Turnaround

• Turnaround planning• Production and schedule• Contractor impacts• Budget impacts

• Health and Safety

• Environmental Compliance

• Waste managementAerial view of the North Pole Refinery


2011 Refinery TurnaroundPlanning Components

• Mass Flux Assessment

• Exposure Monitoring

• Equipment Decontamination

• Waste Minimization


Mercury in Hydrocarbon Process StreamsBackground: Characteristics

AreaAve. Conc. (µg/kg

)

Exceptions(higher conc.)

US 4.3 CA, LA, TX

Middle East 0.8 KSA, Algeria

Asia 220 Thailand

Mercury In Crude Oil• Occurrence of mercury in hydrocarbons

• Volatility and Solubility • Adsorption and chemisorption

dynamics in process equipment

• Occupational Exposure Risks• Measurement and Monitoring


Mercury in Hydrocarbon Process StreamsBackground

Volatility Hgº (Elemental Hg)• Boiling Point: 357º C• Vapor Pressure-Saturation Concentration: 20 mg/m3 25º

C

Solubility (Hgº) in liquid hydrocarbons• 2 ppm at 25ºC

Adsorption – Chemisorption Potential• Carbon Steel: 2-10 grams per square meter


Mercury in Hydrocarbon Process StreamsBackground

Occupational Exposure – Key Points During Maintenance and Turnaround Activities• Neurotoxin (Central Nervous System)• Odorless, colorless, tasteless• Volatility and desorption dynamics increase risk

during vessel entry preparation and hot work• Worker Decontamination• Monitoring interference


Solvent Extraction Process Mercury Assessment

Objectives:• Primary Objective: data to

inform and aid the turnaround planning process

• Assess mercury content of process fluids (feed, intermediates, products)

• Map distribution and mercury mass flux in the solvent extraction process


Naptha 1 Extractor

Naptha 1 Raffinate

Naptha 2 Raffinate

Naptha 1Extract Stripper

Rich Solvent

OVHD Recycle

Naptha 1Extract StripperOVHD Receiver

Naptha FeedSTAB 2 BTMs

Naptha 2 Extractor

Rich Solvent

Lean Solvent

Naptha 1 Raffinateto Blend

Naptha 1 Raffinate Settling Drum

Naptha 1 Extractor

Naptha 2 Extractor

OVHD Recycle

150# Steam

Naptha 2Extract Stripper

Lean Solvent

Refinery Waste Gas


Naptha 2 Raffinate Settling Drum

Naptha 1Wash Tower

V-04314

SolventRecovery Tower

V-04306

V-04312

V-04311

V-04303

Naptha 2Wash Tower

V-04304

Naptha FeedSTAB 1 BTMs

Make Up Steam

V-04305

V-04313

Naptha 2Extract StripperOVHD Receiver

V-04308

SteamGenerator

SG-04305

Steam

Aromatics ToBenzene Removal Unit

Solvent RegeneratorReboiler

V-04307

NC

Waste GasKnock Out Drum

V-04315

Recovery TowerOVHD Receiver

V-04309

SP#32.96

SP#20.66 ppb

SP#1A5.47 ppb

SP#1B0.73 ppb

SP#424.68 ppb

SP#151.93 ppb

SP#15AB2.39 ppb

SP#7892.14 ppb

SP#8205.87 ppb

SP#4AB3.00 ppb

SP#16:Canceled (No Flow)

SP#10B20.31 ppb

SP#1736.19 ppb

SP#9B0.95 ppb SP#12

4.91 ppb

SP#141.06 ppb

SP#110.25 ppb

SP#511.47 ppb

SP#6140.22 ppb

SP#3A0.49 ppb

OVHD Liquid Streams:

OVHD Vapor Phase Streams:

Naptha Feed:

Naptha Raffinate:

Rich Solvent:

Lean Solvent:

OVHD Recycle:

Bz Rich Aromatics:

Water

Steam

Rich Solvent

Sample Point:

Mercury and Chemical Services GroupDrawn by: JHVjr Date: 2/7/2011Revised by: JLB Date: 3/10/2011Checked By:Project No.: 14601Figure B2

V-04400

V-04401

Waste Gas

Waste Gas Knock Out Liquid

F-0

4004

Aromatics Recycle

SP#13:Canceled(unattainable)

P-04316A/B P-04306A/B/C

Lean Solvent

Dashed Process Streams areNegligible

Solvent Extraction Process Mercury Assessment


Mercury Mapping and Mass Flux Assessment: Naphtha Extractor

Results indicated: Increase of

mercury in process fluids

Mercury accumulation in stripper overhead stream and in the overhead receiver recycle stream

• Naphtha Extract Stripper scheduled for turnaround• Mass flux estimate: Hg mass increase rate of 3.4 lbs/yr.


Solvent Extraction Process Mercury Mass Flux Assessment

Potential mercury accumulation rate of 0.00008 lbs per hour or 0.70 lbs per year.

V-04303Extraction Unit

Naptha Feed fromStabilizer 2 Btms

191572 lbs/hr0.0010470 lbs(Hg)/hr

Naptha Feed fromStabilizer 1 Btms

38340 lbs/hr0.0000280 lbs(Hg)/hr

Npatha 1 Raffinateto Blend

117712 lbs/hr0.0001249 lbs(Hg)/hr


75147 lbs/hr0.0003692 lbs(Hg)/hr

Aromatics Recycle23720 lbs/hr

0.0004818 lbs(Hg)/hr

Waste GasKnock Out Liquid

439 lbs/hr0.0000159 lbs(Hg)/hr

Waste Gas1053 lbs/hr

Make Up Lean SolventNegligible Flow

Make Up SteamNegligible Flow


Mercury Mapping and Mass Flux Assessment: Solvent Recovery Tower

Key Points: • Solvent Recover Tower scheduled for turnaround• Mass flux estimate: Hg mass accumulation rate of 14.9 lbs/yr.

• Increase of mercury in process fluids

• Mercury accumulation:• aromatics stream• overhead recycle


Exposure Monitoring for Mercury: Management Program Components

• Occupational exposure limits for mercury

• Hg vapor monitoring program focus areas and methods

• Post Chemical Cleaningverification sampling strategy

• Data managementand results


Exposure Monitoring for Mercury:Hg Vapor Occupational Exposure Limits

• British Columbia, Canada (Work Safe BC) has a one half TLV that activates appropriate mercury management protocols and procedures (exposure control plan).

• Alkyl mercury compounds have a TLV of 1.0µg/m3. (Way more times toxic than elemental Hg)

Exposure limit values used for monitoring worker exposure to mercury vapor.

Occupational Safety and Health Administration OSHA The Federal OSHA has established a PEL for

mercury vapor of 0.1 milligrams per cubic meter (mg/m3).Permissible Exposure Limit PEL

National Institute for Occupational Safety and Health (US) NIOSH NIOSH has established a REL for mercury vapor

of 0.05 mg/m3 expressed as a 10–hour time weighted average for a 40–hour work week.Recommended Exposure Limit REL

American Conference of GovernmentalIndustrial Hygienists

ACGIH ACGIH provides a TLV for mercury vapor of 0.025 mg/m3 expressed as an 8–hourtime weighted average (TWA).

Threshold Limit Value TLV


Exposure Monitoring for Mercury:Focus Areas and Methods

• Process vessels, heat exchangers, and separators• Exclusion Zones and Contamination Reduction Zones • Hot Work: Welding, Cutting and Grinding• Crew break areas and wash areas (transported mercury risks)• Exposure Monitoring Methods: Active, Passive, Real-Time


Exposure Monitoring for Mercury: Process Equipment Verification

• Verify Decontamination Objectives (<50µg/m3)

• Sample locations and frequency• Man-ways• Work areas• Hot work

Pre and Post Chemical Decontamination Mercury Vapor Concentrations

Solvent Recovery Tower Naphtha 2 Extract Stripper

Pre Chem Post Chem Pre Chem Post Chem>50µg/m3 <1µg/m3 >500µg/m3 <1µg/m3


Exposure Monitoring for Mercury:Data and PPE Management

• Data management plan• Field tracking forms• Real-time data

logging• Data comparisons

• PPE management plan• Real-time instruments• Upgrade• Downgrade• Verify control zones

Results of active/passive traps and dosimeters validate real-time Hg vapor concentrations


Process Equipment Decontamination:Management Components

North Pole Refinery Solvent Recovery Tower

Mercury contamination of process equipment

1. Chemical Decon. SystemDesign and Chemistry

• aqueous extraction• precipitive treatments

2. Verification Sampling/AnalysisStrategy

• Know when to stop chem.• Measure performance


Process Equipment Decontamination: Mercury in Steel

Metallographic cross section of pipe scale and atomic density of Hg, Fe, and S

• Hg adsorbs and chemisorbs to steel surfaces

• Thermal desorption test show a substantial amount of Hg is desorbed at 200°C

• Decontamination plans and objectives


Equipment Decontamination:Planning Objectives and Process Flow

Naphtha 2 ExtractStripper

Steam/Chem.Injection


Steam/Chem.Injection

Flare

Compliance Hg Vapor/Liquid Spl Point

Mercury RemovalVapor System

Hg Compliance ChemicalLiquid Effluent Spl Point

Mercury RemovalLiquids System

Compliance HgHydrocarbon Vapor Spl Point

• Hydrocarbon removal (Goal: 0% LEL)

• Post-decontamination Hg Vapor (Goal: <50 µg/m3 monitored continuously)

• Hg Vapor Recover System (Goal: 0 µg/m3 to atmosphere)

• Chemical/Condensates Liquid Treatment System (Goal: <7 µg/L)


Process Equipment Decontamination:Verification Goals and Objectives

Measure mercury in chemical decontamination solutions and condensates • Sample locations:

• In-line filter units• De-Inventory

headers• Instrument detection limitStudy

• Analytical methods• GFAA Spectrometry• EPA 1631


Process Equipment Decontamination: Naphtha 2 Extract Stripper

V-04309

E-04400A

E-04308C

E-04308B

E-04308A

E-04305

E-04400B

E-04308B

E-04308F

E-04308B

E-04308D

E-04308E

20"

Steam/Chem.Injection 225 F

6"

20"


Operating Temp.260°F

Operating Temp.277°FSteam/Chem.

Injection 225 F

SP 04TR 1 MW<1µg/ m3

SP 03TR 10 MW<1µg/ m3

SP

02

TR

20 M

W<

1µ

g/m

3

8" 8"

CascadeChem Inlet165 F

TCV 6,650 GalV 4305 6' ID x 66'6" T/T

Naptha 2Extract Stripper Chemical PFD

SP 01Top 2 Inch Valve<1µg/ m3

Hg mass gain rate: possible 53.6 lbs./year


Process Equipment Decontamination: Solvent Recovery Tower

E-04400A

E-04308C

E-04308B

E-04308A

V-04309

V-0

430

6

E-04306


10"

E-04400B

E-04308B

E-04308F

E-04308B

E-04308D

E-04308E

2"

14"

20"

From 4040Steam/Chem.Injection 225 F

24"20"

Op

era

tin

g T

em

p.

308

°F



TR 1 MW

From 4099Steam/Chem.Injection 225 F Fr

om

404

1S

team

/Ch

em

.In

ject

ion

225

F

Chemical CleaningDENV Header

3"

Cascade RinseFlow Rate 215 GPM

SP

01

<1

µg/m

3SP 02<1µg/ m3

SP 03<1µg/ m3

SP 04<1µg/ m3

SP 05<1µg/ m3

To Chemical CleaningDENV Header


Hg accumulation rate: possible 14.9 lbs./year


Waste Minimization:Management Components

Frac Tank Area: Inlet spl. locations on Chem. Clean and Condensate De-Inventory headers

1. Mercury removal from process systems

Hg Liquids minimization Hg Vapor minimization

2. Sorbent media mgt.

3. Verification sampling strategy• Treatment phase• Measure

performance


Waste Minimization:Process Flow and Objectives

• Hydrocarbon removal (Goal: micro-emulsion)

• De-Inventory Header(s) Inlet Sampling/Analysis Goal: 3 Spls/Frac Tank

• Hg Particulate Removal (Goal: 5 micron)

• Total Hg Removal From Process Liquids (Goal: <7 µg/L)

Chem. CleaningDe-Inventory

Header

Hydrocarbon/Mercury VaporRemoval System

Hg Compliance ChemicalLiquid Spl Point

ParticulateHg Removal

System

Compliance HgHydrocarbon Vapor Spl Point

CondensatesDe-Inventory

Header

Frac Tanks

Hg AdsorptionSystem


Waste Minimization:Verification Goals and Objectives

On site laboratory, Graphite Furnace Atomic Adsorption (GFAA)

QA/QC duplicates/triplicates analyzed using EPA 1631

Treat around 100,000 Gal Hg contaminated TAR liquids to <7 µg/L)

Treat TAR Hg Vapors to 0/m3


Refinery Mercury Management Program:Summary of Conclusions

• Steaming of EQ liberates a significant amount of Hg.• Continuous Hg monitoring required (vessels/work areas) • Scale layers and substrate can hold Hg that will desorb over

time (desorption rates change with temperature and work activities within vessels).

• Chem Decon is effective in reducing Hg vapor concentrations so work can be performed safely with minimal PPE.

• Understanding Hg accumulation in process systems helps develop exposure and chemical decon plans

• Turnaround liquids and vapors can be effectively processed minimizing off-site environmental liabilities.

2012 Afpm Hg Management Presentation Final Draft 1203010

Documents

Transcript of 2012 Afpm Hg Management Presentation Final Draft 1203010