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Mercury Occurrence in Crude Oil and Impact on Refineries

Presentation to: Crude Quality Group Houston, Texas May, 2002

Mercury Technology Services

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Outline
Hg in Hydrocarbons

Chemical Properties Operational Speciation Chromatographic Speciation Analysis of Total Mercury Typical Concentrations
Mercury in Refineries

Distillation Products Emissions Catalysts


Regulatory Trends EPA API NPRA Mercury Study

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Mercury in Oil and Gas


Natural Gas

Elemental Hg0 Organic RHgR, R = CH3, C2H5

Oil and Condensate

Elemental Hg0 Ionic HgCl2 Complexed HgK Organic RHgR, R = CH3, C2H5 Suspended HgS, HgX

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Approximate Solubility Mercury Compounds


25 C

Species

Water (ppb)

Oil (ppb)

Glycol (ppb)

HgO XHgX HgCl2 HgS CH3HgCl

50 <1000 70,000,000 <1 very high

2,000 infinite >10,000 <1 1,000,000

7,000 >7,000 >50,000 <1 high

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Solubilities and Volatilities of Mercury Compounds


Formula State Volatility Hg Solubility in H20; 25 C Name

Hg

Boiling Point 357 C Liquid Vapor Pressure 25 mg/m3 (25 C) Solid Solid Solid Solid Solid Boiling Point 302 C decomposes 300 C decomposes 500 C Sublimes under vacuum; decomposes 560 C Sublimes under vacuum, decomposes 800 C

50 ppb 70 g/l 0.03 g/l 0.05 g/l - log Ksp(1) = 52 - log Ksp ~ 100

Elemental Mercuric chloride Mercuric sulfate Mercuric oxide Mercuric sulfide Mercuric selenide

HgCl2 HgSO4 HgO HgS HgSe

(CH3)2Hg Liquid Boiling Point 96 C (C2H5)2Hg Liquid Boiling Point 170 C


(1) Ksp = solubility product

< 1 ppm Dimethylmercury < 1 ppm Diethylmercury

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Primary Separation

Gas Water Condensate

Hg >> RHgR HgS, Hg


2+

>> Hg0

Hg0, HgS > HgCl2

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Mercury in Liquid Hydrocarbons Operational Speciation


Total Hg = Hg0 + (RHgR + HgK) + (HgCl2 + RHgCl) + (HgS + HgX)

Hg

+ O2 Hg

2+

RHgR + HgCl2 2 RHgCl Hg


0

+ HgCl2 Hg2Cl2

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Chromatographic Separation

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Mercury (Total) in Distilled Products

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Mercury in Petroleum Coke

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Analysis of Total Mercury in Crude Oil


Combustion/CVAF Neutron Activation Analysis Digestion CVAA Digestion CVAF

Sampling
Samples must be fresh Must account for all Hg (container walls) Avoid loss of volatile Hg

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Hg in Hydrocarbon Liquids
THg in Alberta Crude Oils (9)

Stratigraphic Era

Number Number High Low Mean* Median of Above (ppb) (ppb) (ppb) (ppb) Samples DL

SD

Detection Limit (ppb)

Upper Cretaceous Lower Cretaceous Jurassic Triassic Carboniferous Devonian Total

21 18 3 4 8 36 86

11 7 0 2 4 13 38

202 138 1 6 19 399 399

DL DL DL DL DL DL DL

17.6 17.1 1 3 5 36 21.9

2.5 1 1 2.5 1.5 1 1

46.0 38.1

2 2 2

2.4 6.3 92.5 63.6

2 2 2

* calculated assuming < DL = 1 ppb

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Reported Total Hg Concentration in Crude Oil Processed in New Jersey Refineries


Type Angola Angola Arab Columbia Columbia Congo Dubai Gabon Mexico Mexico Mixed Newfoundland Nigeria North Sea North Sea North Sea North Sea Venezuela Venezuela Venezuela Venezuela West Africa West Africa Mean THg (ppb) mean 2.7 1.5 5.7 12.3 2 1.8 2.9 1.8 2.7 0.1 3.1 1.9 1.0 3.4 9.3 2.5 4.7 4.8 5.1 0.8 6 3.2 1.5 3.5 Notes Palanca Soyo

Kitina Nemba Rabi

Escravos Ecofisk Gullfaks Norne light

light

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Mercury Estimates in Crude Oil and Refined Products IN


Type (U.S. DOE 2000) Crude Oil (d=0.85) Domestic (40%) Barrel/y (U.S. DOE 2000) (109) kg/y (1011) THg ppb Estimated Total kg/y

Alaska (18%) GOM (20%) Other (62%)

0.4 0.5 1.5 0.5 0.5 0.8 1.8 6.0

0.5 0.7 2.0 0.7 0.7 1.1 2.4 8.1

<10 <10 <10? <10? <10 <10 <10?

500 700 2,000? 700? 700 1,100 2,400? 8,100

Imported (60%)

Canada (15%) Mexico (15%) Middle East (20%) Other (50%)

Total (IN)

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Mercury Estimates in Crude Oil and Refined Products OUT


Type (U.S. DOE 2000) Refined Products d = 0.75 d = 0.80 d = 0.85 d = 0.85 d = 1.10 d = 0.90 d = 0.55 Wastewater (U.S.EPA 1982) Solid waste (U.S. EPA 1996) Air (Table 7.4) Air (fugitive) Total (OUT) (from fuels included in refinery totals) Motor fuels (60%) Naphthas (5%) Residual fuel oil (5%) Distilled fuel oil (21%) Petroleum coke (3%) Heavy oils (3%) Still Gas (3%) Barrel/y (U.S. DOE 2000) 6.2 3.7 0.3 0.3 1.3 0.2 0.2 0.2 1.5 kg/y 7.9 4.4 0.4 0.4 1.8 0.3 0.3 0.3 2.5 0.3 <3? <5 <5 <5 50 50 <30? 1 50? THg Estimated Total 7,000 1,200? 200 200 900 1,500 1,500 1,000? 250 1,500? (1,500)* 250? 8,500

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Petroleum Contribution
Global (anthropogenic to air) - 2,000,000 kg/y (US EPA) US (waste + fuel combustion) - 125,000 kg/y (US EPA) US Coal - 75,000 kg/y (US EPA) US Fuel Oil - 10,000 kg/y (US EPA) US Oil <8,000 kg/y (MTS) US Fuel Oil - 1,100 kg/y (MTS) US Refineries (air) <1,500 kg/y (MTS)

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Mercury In Petrochemical Processes


Catalysts Equipment Contamination Environmental concerns Health and safety Waste Wastewater

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Mercury Removal from Oil ??


Precipitation Conversion Sorbents Filtration

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Regulatory Issues
Water Clean Water Act (CWA, Section 304)

Total Maximum Daily Load (TMDL) Air

Clean Air Act of 1990 (CAA, Section 112) National Emission Standards for Hazardous air Pollutants (NESHAP) Maximum Available Control Technology (MACT) Solid Waste Resource Conservation and Recovery Act (RCRA)

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Toxic Release Inventory (TRI)


Emergency Planning and Community Right-toKnow Act (EPCRA) Persistent Bioaccumulative Toxics (PBT) Report threshold - Mercury 10 lbs. Elimination of the de minimis exemption

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EPA API NPRA Mercury Study


Analytical Issues Variation in Concentration Sample Stability Survey Crude Oils Processed in the U.S. Blind Study

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smw@hgtech.com

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