Crude oil, process performance, and product ... · Crude oil, process performance, and product...

Crude oil, process performance, and

product characterization through FBRM

and PVM process probe technology

implementation

Stephen Pavel

Full Spectrum Consulting LLC

Anjan Panday

Mettler Toledo

Full Spectrum

Consulting LLC

Acknowledgements

ACKNOWLEDGMENTS

In this review, paper and powerpoint references and images are from the public domain.

See paper for power point slide references, use google to get current news.

Authors thank the organizers of the info day.

Authors gratefully acknowledge those that have provided the foundation of knowledge in the public domain

including the Fair Use Rules which have increased the dissemination of knowledge and are used in this

review.

Authors thank those that skillfully reported topics that are frankly difficult to believe occur in developed

counties, especially Canada and US, that required those topics be quoted rather than paraphrased.

Authors acknowledges the US Patent and Trademark Office, with the new America Invents Act which

improves the ability of individuals to pursue patents and to dispute patents that are in process and those

that have been granted.

The author gratefully acknowledges generous support of friends, family and clients.

Contact at [email protected], [email protected]

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mailto:[email protected]





Heavy Oil Basins

See paper for powerpoint slide references

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Bitumen Basins

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Kleme basin types

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Canadian Oil Sands Mining & In-Situ

Projects • “ 1) Producing Projects: 1,853,650 bpd

• Mining - 921,000 bpd

• In-situ - 932,650 bpd

• 2) Under Construction: 714,905 bpd

• Mining - 295,000 bpd: 2projects

• In-situ – 419,905 bpd: 20 projects

• 3) Projects with Regulator Approval 2,199,650 bpd

• Mining-1,390,000 bpd: 12 projects

• In-situ - 809,650 bpd: 35 projects

• 4) Projects Under Regulator Review: 1,981,270 bpd

• Mining - 600,000 bpd: 7 projects

• In-situ-1,381,270 bpd: 55 projects

• 5) Projects Announced / Disclosed: 1,489,500 bpd

• Mining – 100,000 bpd: 1 projects

• In-situ–1,389,500 bpd: 45 projects”

• (Oilsands Developers Group, 2013.03) Full Spectrum

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Oil Sands In-Situ Projects

• Projects continue and are provided for perspective:

• 1) 47 Producing Projects: 937,500 bpd

• 2) 17 Projects Under Construction: 532,000 bpd

• 3) 38 Projects with Regulator Approval: 1,236,000 bpd

• 4) 70 Projects Under Regulator Review: 1,925,270 bpd

• 5) 49 Projects Announced/Disclosed: 1,337,100 bpd

– Total 221 Projects 5,967,870 bpd

• (Oilsands Developers Group, 2013.04)

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Tight oil and gas plays, US

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US domestic oil & gas to 2040

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Basins assessed shale oil & gas,

5/2013

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Methods for Transportable Heavy Oil

• Previous presentation listed alternatives “to choose the best of them, regarding flow assurance and risk reduction associated with heavy oil production” :

• Dilution

• Heating

• Inverse emulsion

• Chemical Flow Improvers

• Upgrading

• Electrical traces

• Lubricated flow

• “Pemex chose to apply the “Dilution at the surface” technique to improve oil density and viscosity. … From the technologies evaluated, Dilution of heavy oil with a lighter one was selected; this one produces better profitability and lesser risks for the Project” Ayatsil-Tekel heavy oil field development.

Peregrino M.D.E., M.R., Mulato E., E.P., Tovilla P., I.C., (2013) Flow assurance Technologies for Ayatsil-Tekel heavy oil field development. Heavy

Oil Latin America 2013. HOLA13-181.

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Methods for Transportable Heavy

Oil: Dilution, Dilution, Dilution. • PEMEX, Shell, ExxonMobil, Cenovus, Canadian Natural, etc. In fact,

all heavy oil or bitumen producers have chosen dilution.

• There are no commercial partial upgraders, no doubt for good reason. For example, plugging has been a major setback.

• No partial upgrader has demonstrated operation of 4 years between turn around, and 96% reliability. One partial upgrader, HTL, has claimed the longest run of 31 hours, and the second longest run of 26 hours. Just need another 349 days to show reliable operation

• No partial upgrading scheme has published enough detail to stand up to a rigorous due diligence of the process, product, emissions, waste disposal, and health costs of the installation.

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Heavy oil, Bitumen Partial Upgrading

In-situ, down hole Technologies • 1. Aquathermolytic

• 2. Brine and supercritical conditions

• 3. Combination processes

• 4. Combined steam and vapor extraction process (SAVEX)

• 5. Downhole catalytic upgrading of heavy crude oil

• 6. Electrical heating elements

• 7. In-situ ethane / propane deasphalting (VAPEX)

• 8. Hot Fluid Injection Process for In-situ Upgrading

• 8. Naphtha / solvent deasphalting,

• 9. Hydrovisbreaking

• 10. Hydrocraking

• 11. In-situ heated annulus refining process

• 12. ICP Shell In-situ conversion process

• 13. ISU In-situ Upgrading with Nanocatalysts

• 14. Microwave down the wellbore

• 15. Natural gas addition to SAGD steam

• 16. Naturfrac

• 17. Paraffinic Froth Treatment, mining

• 18. Radiofrequency assisted gravity drainage

• 19. Others not listed above

• 19. SLP-SAGD Solvent, Low Pressure, low steam use

• 20. THAI Toe to Heel Air Injection

• 21. Upgrading heavy oil using aqueous base

• 22. EM-SAGD with SLP-SAGD and OTHERS

• plus … others not included above

“There’s a new wave of technology

coming. Some people think we can do

all this underground, said Cabrera.”

(Pratt, 2013)

Cabrera didn’t know that

Down hole Technologies are in process

to get oil out or improve oil quality, even

adding hydrogen and upgrading

underground? Appears Down hole

Technologies are in field pilots

apparently the New Wave of Technology

coming not well head partial upgrading.

Upstreamers would rather not have any

of the above ground overhead. Use the

formation as a reaction vessel, save the

money.

Curiously Cabrera listed some of these

in a later presentation. Successful they

will make partial upgrading above

ground irrelevant.

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Above Ground, Field Partial Upgrading Technologies-1/3

• A partial list of partial or integrated above ground, field, upgrading technologies:

• 1. Aquaconversion Process -- PDVSA

• 2. CCU Catalytic Crude Upgrading Process -- UOP

• 3. Canmet – UOP

• 4. Chattanooga Process -- Chattanooga Corp (i)

• 5. CPJ Process- - Wesco Energy Corp.

• 6. Eadiemac Process -- Eadie Oil Inc.

• 7. Ellycrack -- Ellycrack AS

• 8. EST Eni Slurry Technology -- Eni S.p.A. (i)

• 9. Genoil Process – Genoil (i)

• 10. GHU Heavy Oil Desulfurization Upgrader – Genoil

• 11. HCAT Process by Headwaters Technology Innovation (i)

• 12. HI-Q Process -- MEG Energy

• 13. H-Oil RC Process -- Axens North America

• 14. HOU – Ivanhoe Energy, Cabrera’s name for HTL in one publication

• 15. HRH Process (TIPS Process) -- Mobis Energy (i)

• 16. HSC High Conversion Soaker Cracking -- Toyo Eng. Corp

• 17. HTL Process -- Ivanhoe Energy Inc.

• 18. IMP-HDT – Instituto Mexicano del Petroleo Full Spectrum

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Field Partial Upgrading Technologies-2/3 • A partial list of partial or integrated upgrading technologies:

• 19. IYQ Process -- ETX Systems Inc.

• 20. JetShear Process -- Fractal Systems Inc.

• 21. OrCrude Process –- CNOOC (i)

• 22. PCUP Partial Crude Upgrading–-ExxonMobil Upstream Res.

• 23. PetroBeam Process -- PetroBeam, Inc.

• 24. Petrosonic Heavy Oil Process -- Petrosonic Energy Inc.

• 25. Premium Upgrading & Gasification –- OPTI (i)

• 26. ROSE -- KBR

• 27. Selex ASP –- Well Resources

• 28. Sonocracking Process –- SulphCo Ultrasound

• 29. Tarblaster -- Tarblaster AS

• 30. TRU Process -- Rival Technologies Inc.

• 31, Ultrasound and HOG Heavy Oil Upgrader-- NexGen

• 32. Uniflex -- UOP, from Canmet, Unicracking, Etc. (i)

• 33. Value Creation Technology -- Value Creation Group (i)

• 34. Viscositor -- FluidOil Ltd.

• 35. Wildcatter HCU -- Refinery Science

• 36. WRITE Process -- Western Research Institute

• 37. Catalytic Partial Upgrading –-N.I.C.E.

• 38. Upgrading -- N.I.C.E.

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Field Partial Upgrading Technologies-3/3 • A partial list of partial or integrated upgrading technologies:

• 39. Bitumen to Diesel –- Bayshore Petr. with Ultrasonic Desulfurization

• 40. CCC– Cold Catalytic Cracking – Chinese technology through Bayshore

• 41. Ceramatec -- Ceramatec

• 42. MSU –- Molten Salt Upgrading

• 42. FTcrude, FTupgrading, FTetc. -- Expander Energy Fischer Tropsch Claims

• 43. USO orange oil technology -- US Oil

• 44. Epic Technology –- waterless sand oil separation

• 45. Direct Cracking of Raw Oil Sands Bitumen -- NCUT

• 46. Even more not listed above …

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CCU-UOP patent figure

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Viscositor Patent figure

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HTL patent figure

Pavel et al., 2012, USPTO Patent Application Full Spectrum

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HTL – FTF Patent Figure

Pavel et al., 2012, USPTO Patent Application

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Visbreaker patent figure

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IyQ Patent figure

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Partial Upgrader Schemes do not provide enough data

for accurate product evaluation, emissions, so valid

economics are impossible.

• Partial Upgrading schemes not supported under scrutiny

• Need full feed, product, waste, and emission details provided for accurate assessment

• Need full details and physical samples provided for independent analysis of all products

• Partial Upgrader schemes characterized by dialogue:

• The Next Big Thing, Game Changing, New Paradigm, Breakthrough Technology, and Hype Equivalents. e.g., Innovative technology could revolutionize industry

• (Smith, 2013)

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Partial Upgraders: many claim to be the

Next Big Thing, Breakthrough Technology,

Game Changing, Paradigm Shifting e.g. PSON

Tobin Smith, 2013, Petrosonic Partial Upgrading: Promo Material, 20 pages; no hard

data Full Spectrum

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Game Changing, Paradigm Shifting e.g. PSON

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PSON not the only partial upgrader stock with price rising

with hype and falling without performance.



Game Changing, Paradigm Shifting, etc.

• “Large spikes in ... stock price can be traced to a potential major... gas play, exploration progress ..., a

possible ... venture, advancements in unique [sic] ... technology, or an up- tick in reserves. All were

heavily publicized and hyped, but few actually happened4. Others fell far short of expectations after the

fact, ... The fallout from deals gone awry, dry wells, technology yet to be commercialized, or a downward

adjustment of reserve size, took its toll ....”

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http://amazonwatch.org/assets/files/2011-ivanhoe-energy-in-ecuador.pdf







Partial Upgraders: many claim to be the Next Big Thing, Breakthrough

Technology, Game Changing, Paradigm Shifting, etc. with Professional

Promotion, e.g. Thom Calandra, Marketwatch for a high $22.65 after

hype, now $0.22, more dramatic on daily chart

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2827900.php

“[Thom] Calandra resigned Thursday amid investigations into his trading by his employer and the Securities and Exchange Commission. The SEC declined to comment on the probe, but the Washington Post reported that the agency is looking into whether he touted stocks he owned to boost the share price, and then dumped his own shares.The investigation followed an article in November by Forbes magazine, which noted Calandra's enthusiastic endorsement of two obscure small-cap stocks, Ivanhoe Mining and Ivanhoe Energy. In his newsletter, Calandra disclosed that he owned shares in Ivanhoe Energy and accepted a free Ivanhoe- paid trip to China and Mongolia, something other CBS Marketwatch journalists would not be allowed to accept.”

http://www.sfgate.com/business/article/Media-ethics-eyed-Stock-trading-by-journalists-2827900.php















http://www.sfgate.com/?controllerName=search&action=search&channel=business&search=1&inlineLink=1&query=%22Forbes+magazine%22

Upgrading Categories

• Partial Upgrading technologies generally either takes carbon out, or puts hydrogen in, or both. Simple division to three categories: carbon out, hydrogen in, or both.

• More detailed General categories include

• catalytic/thermal cracking (CCU, Ellycrack, Tarblaster, Viscositor),

• thermal cracking (Delayed, Fluid Coking, HTL, CPJ, Eadiemac, HCU),

• thermal cracking coking (ETX, Genoil, HiQ, Write),

• cavitation/impingement (Viscositor),

• electron beams, electromagnetic waves,

• hydrogenation ,

• so-called integrated processes (OPTI, TRU, VCG) shown with an (i);

• SDA (Petrosonic, ROSE, SELEX),

• sonic waves (Sonocracking, Sonic Visbreaking),

• and all forms of hydrogen addition

• plus any combination of categories. Full Spectrum

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Partial Upgraders Promoted,

but no partial upgraders built

• Partial upgrading technologies can be classified to those that have been built and commercialized or those that have not.

• Full Upgrading has been producing since 1967. No Partial Upgraders have been built, evidently for valid reasons.

• One partial upgrader claims no one has bought their technology because of resistance to change. (WHOC, 2014)

• However literature shows there have been many, including majors, Californian and Canadian heavy oil producers, Central and South American national oil companies, and others that have looked at, and tested partial upgrading technology, one spent over 2 million, but none have gone forward after pilot plant or demonstration plant testing. (NewTech, 2005).

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High temperature short contact time partial upgrading, using commercial FCC

resulted in extensive plugging in the field documented in early 1990s.

Certain companies, without operating experience,

make unsupported claims of stable product.

• History shows many technologies did not progress after pilot, demonstration,

or commercial scale trials.

• Major problems were discovered in commercial testing resulting in potential

client rejection of schemes, e.g. full size FCCU converted to short contact time

to test run crudes, atmospheric bottoms and vacuum bottoms. Full scale

failure. Trials were terminated and abandoned after excessive and continuous

asphaltene plugging of reactors, transfer lines, cyclones, overhead systems,

distillation columns, guard beds, etc..

• Despite unsupported marketing claims of stable product, high temperature

short contact cracking is well known for unstable, thermal cracked product.

According to Heavy Oil Process Expert Roger Lott:

• “… produces an unstable, thermally cracked oil that has no market unless with

heavy discount. Moreover the cracked oil will form gum in storage or during

transportation. What a waste of investor money.“

• (Lott, R., Comment (2013.04.04) to “Upgrade heavy oil more cost-efficiently,” Hydrocarbon Processing, 2012.09.01,

http://www.hydrocarbonprocessing.com/Article/3081303/Channel/194955/Upgrade-heavy-oil-more-cost-efficiently.html}

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http://www.hydrocarbonprocessing.com/Article/3081303/Channel/194955/Upgrade-heavy-oil-more-cost-efficiently.html%7D











Only Two Upgrading Product Categories:

Unstable/Stable

determined by testing: Stable or Unstable • Stable, Compatible Product

• Whole crudes are generally self compatible with some exceptions, e.g. YME.

• SCO – Synthetic Crude Oil from Full Upgrading including hydrotreating, e.g. Suncor, Syncrude, etc., then blended to specification. Low sulfur, low resid, high gravity.

• Unstable, Self-Incompatible Product

• Self-incompatible crude difficult to market, some crude production shut in.

• Naphthas, Jet Fuels, Diesels, and Fuel oils with dienes, asphaltene incompatible components, production and reaction solids required test methods to quantify.

• SICPUTCUPs--Self-InCompatible Partially Upgraded Thermal Cracked Unstable Products. Typically high sulfur, low gravity, requires light oil to blend to market of ~20 API.

• All thermal cracked material is and must be assumed unstable and incompatible until irrefutably proven stable, that is without dienes, gum, and asphaltene precipitates, TIOM, and solids by extensive quantitative test results.

• Thermal Cracked vacuum bottoms product has been Self-Incompatible and Unstable, there has not been a single exception, or evidence of any stable property in literature. Full Spectrum

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Stability & Compatibility Tests – 1/3 • Optical Inspection for Self-Incompatibility, Wiehe

• Asphaltene content, Heptane (D3279)

• Asphaltene content, Hexane (D3279)

• Asphaltene content, Pentane (D3279)

• Toluene Insolubles (D4072)

• THF insolubles (D4072_modified)

• Flocculation Ratio, Peptizing Power (D7060)

• Stability and Compatibility (D7112)

• Intrinsic Stability (D7157)

• Automated Heithaus Titrimetry (D6703)

• Asphaltenes by nC7 phase separation (D7061)

• Asphaltenes (D6560)

• SHFT Total sediment (D4870a-96/ISO10307)

• SHFT Total sediment by thermal aging (D4870b)

• SHFT Total sediment by chemical aging (D4870c)

• SHFT Hot Filtration after 7 days, as is (D4870)

• SHFT Hot Filtration after 7 days, Heat (D4870)

• SHFT Hot Filtration after 7 days, Chemical (D4870)

• SHFT Hot Filtration after 28 days, as is (D4870)

• SHFT Hot Filtration after 28 days, Heat (D4870)

• SHFT Hot Filtration after 28 days, Chemical (D4870)

• Thermal Stability Tests (D873)

• Thermal Stability Tests (D3241)

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Stability & Compatibility Tests – 2/3

• Spot test (D4740-95)

• Spot test and residue stability (IFP3024-82)

• Spot test (D102)

• P-Value, Peptization value Shell method

• Wiehe Compatibility Test Methods

• CII, Colloidal Instability Index, Wiehe method

• Coking Index, Wiehe, WRI calculation

• Fouling Test, Alcor Hot Liquid Process Simulator, HotLips

• Fouling Tendency (D3711-95)

• Asphaltene dispersant tests by vendor

• Furnace tube fouling tests by vendor

• Viscosity with and without exposure to air

• Elemental Analysis: COHNS

• SARA, Sat, Arom, Resins, Asph (D2007/D2549)

• SARA Calculations: Asphaltene/Resin Ratio

• SARA Calculation: Saturate/Aromatic Ratio

• CSI Coking Stability Index re: furnace fouling

• Asphaltene Precipitation Onset, various methods

• Compatibility spot tests filter paper methods

• Elemental Analysis by ICP Full Spectrum

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Stability & Compatibility Tests – 3/3 • Conjugated Di-olefins by Exxon Method

• Dienes UOP 326-82

• Dienes by 1hNMR published method

• Olefins by 1hNMR published method

• Bromine Number

• Water by Karl Fisher (D7377/D1744)

• BS&W by Centrifuge (D1796)

• Sediment by extraction (ISO 3735, IP53)

• Sediment content (D473)

• TAN, Total Acid Number (D664)

• Salt in crude (D6470M)

• Existent Gun in Fuel by Jet Evap (D381)

• Oxidation Stability of Naphtha (D525)

• Oxidation Stability of Kerosene (D873)

• Oxidation Stability of Distillate Fuel (D2274)

• JFTOT Thrm Oxyd. Stab. of Av. Turbine Fuel (D2274)

• Distillate Fuel Storage Stability (D4625)

• Endcut distillation published method

• Particle size by Fixed Beam Reflectance Measure

• Particle Vision Measurement, PVM Mettler-Toledo

• OTHER BULK TESTS NOT INDICATIVE OF STABILITY INCLUDE

• Simulated Distillation high temp (D2887)

• Viscosity at 0, 10, 40, 100, 150 C and pipeline specs

• Viscosity (D445, etc.)

• API (D287, etc.)

• ETC. THESE ARE INADEQUATE TO DEMONSTRATE COMPATIBILITY

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Determination of incompatible product

(Wiehe, 2008)

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Determination of self-incompatible

product

(Wiehe, 2008)

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Thermal cracked fuel oils instability

documented from start of delayed coking, very unstable distillates,1932 and catalytic

with thermal cracking at higher temperature temperature,1952

• Laboratory Evaluation of Fuel Oil Stability

• 4. R. RESCORLA, J. H. CROMWELL, AND DANIEL RIILSO3I

• Cities Service Research and Development Co.,JYeu.York,.1’.Y.

• Analytical Chemistry, v24, no12, Dec. 1952

• WITH the introduction of catalytic cracking of the heavier crude oil fractions, the furnace oil produced from these cracked stocks was found to be generally very unstable. The furnace oil produced from the catalytic cracking stocks has a tendency to become more rapidly oxidized in storage to form an insoluble precipitate and a dark colored oil which may have a high soluble residue. Although the fuel oils prepared from straight- run materials are more resistant to oxidation, when this material is mixed with the catalytic fuel oil the precipitation of the insoluble material is greatly accelerated. The consumer’s first experience with the instability comes with the clogging of burner filters, and the dark oil removed from the system when clogging occurs.

• There have been cases reported where fuel oil stored for a period as short as 2 months has caused filter clogging. The cause of this instability has not been definitely established, but various investigators have attributed it to sulfur compounds, particularly thiophenols and thiocresols, unstable nitrogen compounds, such as pyrroles, quinoline, and isoquinoline, colloidal carbenes and carboids, or unstable diolefinic hydrocarbons. Actually the instability may be due to any one or a combination of these compounds resulting from oxidation and polymerization reactions in

• the fuel oil.

Burk, R. (1933) U.S. Patent Application, Patent 2,081,218, May 25, 1932, METHOD FOR.

STABILIZING MOTOR FUEL AGAINST GUM FORMATION. Washington, DC: U.S. Patent and

Trademark Office. assigned to The Standard Oil Company, Cleveland, Ohio.

“In the customary methods of producing motor fuel by cracking petroleum, there is a formation of

unstable gum-forming byproducts which subsequently require particular treatment if their results are

to be avoided.” (Burk, 1933).

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Shale oil naphtha gums, 1953 • Gum Formation in Shale-Oil Naphtha

• G. U. DINNEEN AND JV. D. BICICEL' U. S. BureauofMines,Laramie, Wyo.,

• Industrial and engineering chemistry, vol 43, no 7, 1953.

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High butadiene with high temperature short contact

time

thermal cracking ENSYN RTP EXPERIMENTS shown

patent “FCC to Minimize Butadiene Yields” (Muldowney, 1994)

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High temperature, short contact time high

1,3-Butadiene from Ensyn data

patent “FCC to Minimize Butadiene Yields” (Muldowney, 1994) Full Spectrum

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Well established relationship

Butadiene increase with Temperature

• FCC

Lieberman, N.P. (2009). Troubleshooting Process Operations, Pennwell, Tulsa. Full Spectrum

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Butadiene vs Reactor Temperature

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Highest reactor temperature least stable:

FCC least stable, coker most stable

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Insufficient data for stability determination

Vacuum resid apparently increases from 12.7 to 20.0, and from 12.3 to 21.7. Without accurate

testing using the correct test methods, there is no support for a claim of stability.

Saskatchewan Heavy Oil, not Athabasca Bitumen

Freel, Graham, Patent 7,270,743 “Products Produced From Rapid Thermal Processing of Heavy

Hydrocarbon Feedstocks” provisional application filed on 09/18/2000

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Insufficient data for stability determination,

unsupported stability claim

Freel, Graham, Patent 7,270,743 “Products Produced From

Rapid Thermal Processing of Heavy Hydrocarbon Feedstocks” provisional application filed on 09/18/2000

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Solids in Process Streams

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Solids in crude oil

Solids incorporated during petroleum formation

Solids from area lacustrine or marine environment

Solids from fracking solutions

Solids from production chemicals

Solids from scale, rust

Self-precipitated asphaltenes during production with change of temperature

and pressure

Incompatibility of fluids, precipitation of asphaltenes

Reaction products of production fluids

Heat transfer solid break up to small particles

Residual heat transfer solids in product

Coke reaction product of short contact high temperature thermal reaction

Condensed asphaltenes that did not contact heat transfer solid

METHOD TO DETECT AND QUANTIFY SOLIDS … FBRM, PVM

Solid particle size in Athabasca Bitumen by

FBRM

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Solid particle size in Athabasca Bitumen by

FBRM

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Solids in Bitumen by PVM

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Solid particle size in Athabasca Bitumen

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Solids removed from partial upgrading reactor product,

patent figures

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FBRM note

• FBRM can also be used to for inline

analysis detecting the formation and

presence of asphaltenes and for laboratory

analysis of compatible materials to show

the incipient precipitation point of the

asphaltenes and confirm the presence of

Toluene Insoluble Organic Material, TIOM,

solids.

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Petcoke the end product of asphaltene

53

54 Public domain, Fair Use Guide

S&W by Centrifuge, Water by KF

Accuracy, from COQA

55 Public domain, Fair Use Guide


Vessel Discharges—for reference only

56 Public domain, Fair Use Guidelines Apply


Refinery deliveries – for reference only

Additives In Crude Oil 1/2

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Additives In Crude Oil 2/2

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From COQA

Fracking Fluids In Crude Oil 1/2

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From Cheasapeake

Fracking Fluids In Crude Oil 2/2

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From Cheasapeake

Fracking Fluids In Crude Oil by Haliburton

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Halliburton Delayed Releasing Details on Fracking Chemicals

After Monroe County, Ohio Spill

Jul 22, 2014

(Columbus Dispatch)

A fracking company made federal and state agencies that

oversee drinking-water safety wait days before it shared a list

of toxic chemicals that spilled from a drilling site into a tributary

of the Ohio River.

Although the spill following a fire on June 28 at the Statoil

North America well pad in Monroe County stretched 5 miles

along the creek and killed more than 70,000 fish and wildlife,

state officials said they do not believe drinking water was

affected.

http://insideclimatenews.org/todaysnews/20140722/halliburton-

delayed-releasing-details-fracking-chemicals-after-monroe-

county-ohio-spill

http://www.dispatch.com/content/stories/local/2014/07/21/detail

s-on-chemicals-trickle-in-after-spill.html

http://insideclimatenews.org/todaysnews/20140722/halliburton-delayed-releasing-details-fracking-chemicals-after-monroe-county-ohio-spill





















Fracking Fluids Disclosure

outlawed by North Carolina Senate

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May 22, 2014 - Under the "Energy Modernization Act," a

state geologist would be the custodian of confidential

information about fracking fluids. The information ...

“The North Carolina Senate on Thursday voted to make it

a crime to disclose the chemicals used in hydraulic

fracturing, or fracking, even as big U.S. oil companies

elsewhere consider releasing more information about the

fluids to address public concerns about the environment.”

…

“Oilfield services provider Baker Hughes Inc has said it will

disclose the fracking chemicals it uses, potentially

prompting other companies to follow suit.”

http://www.reuters.com/article/2014/05/22/us-usa-fracking-

secrets-idUSBREA4L0YC20140522

http://www.reuters.com/.../us-usa-fracking-secrets-idUSBREA4L0YC20



NC Outlawing Wikipedia entries? Cheasapeake Disclosure?

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Hydraulic fracturing - Wikipedia, the free encyclopedia

en.wikipedia.org/wiki/Hydraulic_fracturing

Wikipedia

Induced hydraulic fracturing (also hydrofracturing, fracking, and fraccing) is a

well -stimulation technique in which a high-pressure fluid (usually water mixed

with ...

List of additives for hydraulic ...

List of additives for hydraulic fracturing. From Wikipedia, the ...

Radionuclides associated with ...

Radionuclides associated with hydraulic fracturing are man ...

Proppant

Sand used for fracturing, USGS, 2012. Proppants used should ...

Wellbore

A wellbore, drill hole or borehole is a hole drilled for the purpose of ...

Environmental impact

Environmental impact of hydraulic fracturing includes the potential ...

Hydraulic fracturing by country

Hydraulic fracturing by country. From Wikipedia, the free ...

More results from wikipedia.org »

http://en.wikipedia.org/wiki/Hydraulic_fracturing



Wikipedia entries illegal in North Carolina?

Full Spectrum

Consulting LLC

The fracturing fluid varies in composition depending on the type of

fracturing used, the conditions of the specific well being fractured, and the

water characteristics. A typical fracture treatment uses between 3 and 12

additive chemicals.[41] Although there may be unconventional fracturing

fluids, the more typically used chemical additives can include one or more

of the following:

Acids—hydrochloric acid or acetic acid is used in the pre-fracturing stage

for cleaning the perforations and initiating fissure in the near-wellbore

rock.[52]

Sodium chloride (salt)—delays breakdown of the gel polymer chains.[52]

Polyacrylamide and other friction reducers—Decrease turbulence in fluid

flow decreasing pipe friction, thus allowing the pumps to pump at a higher

rate without having greater pressure on the surface.[52]

Ethylene glycol—prevents formation of scale deposits in the pipe.[52]

Borate salts—used for maintaining fluid viscosity during the temperature

increase.[52]

Sodium and potassium carbonates—used for maintaining effectiveness of

crosslinkers.[52]

Glutaraldehyde—used as disinfectant of the water (bacteria

elimination).[52]

Guar gum and other water-soluble gelling agents—increases viscosity of

the fracturing fluid to deliver more efficiently the proppant into the

formation.[49]

Citric acid—used for corrosion prevention.

Isopropanol—increases the viscosity of the fracture fluid.[52]



Wikipedia entries illegal in North Carolina?

Full Spectrum

Consulting LLC

The most common chemical used for hydraulic fracturing in the United States in 2005–

2009 was methanol, while some other most widely used chemicals were isopropyl alcohol,

2-butoxyethanol, and ethylene glycol.[55]

Typical fluid types are:

Conventional linear gels. These gels are cellulose derivatives (carboxymethyl cellulose,

hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose,

methyl hydroxyl ethyl cellulose), guar or its derivatives (hydroxypropyl guar, carboxymethyl

hydroxypropyl guar)-based, with other chemicals providing the necessary chemistry for the

desired results.

Borate-crosslinked fluids. These are guar-based fluids cross-linked with boron ions (from

aqueous borax/boric acid solution). These gels have higher viscosity at pH 9 onwards and

are used to carry proppants. After the fracturing job the pH is reduced to 3–4 so that the

cross-links are broken and the gel is less viscous and can be pumped out.

Organometallic-crosslinked fluids zirconium, chromium, antimony, titanium salts are known

to crosslink the guar-based gels. The crosslinking mechanism is not reversible. So once

the proppant is pumped down along with the cross-linked gel, the fracturing part is done.

The gels are broken down with appropriate breakers.[49]

Aluminium phosphate-ester oil gels. Aluminium phosphate and ester oils are slurried to

form cross-linked gel. These are one of the first known gelling systems.

Solid additive to crude for emulsion manipulation

66


67

Sullivan, A., Kilpatrick, 2002


68


69

FBRM ® & PVM ® Technologies: Superior In-process Tools to Monitor & Quantify

Solid Particulates during/after Process

Executive Summary

- GOAL:

- Prove FBRM & PVM in-process tools can be used to quantify and visualize solid

particulates present in upgraded crude oil in the lab and in pilot/field scale.

- CONCLUSIONS:

- In-process FBRM and PVM technologies enables users to measure undesired solid

particulates present in the crude oil in real time during and after process to quickly screen

and evaluate final product quality.

- Integration of FBRM and PVM tools with process technology will provide quantitative and

qualitative information to rapidly track and adjust process operation – this ability to obtain

real time process information will eliminate lengthy post-upgrade offline measurement.

- FBRM and PVM data will help users to determine effect of thermal cracking technology on

product quality.

- FBRM & PVM are versatile tools and their utility extend beyond detection of solid

particulates in the process products. it can be used to screen initial feedstock, quantify

water content in feedstock, and optimize oil-water separation process of the initial

feedstock.

Experimental Results

72

a

b

- RESULTS:

– FBRM and PVM can be used to measure solid particulates present in the crude oil

during and after demonstration process.

– In situ FBRM and PVM provided quantitative and visual data respectively to track the

addition of increasing amount of Ca(OH)2 to crude oil.

– FBRM and PVM helped quickly screen samples considered to be ‘pretty’ () and ‘ugly’

() and measure the differences in solid particulates.

– FBRM distribution clearly shows the difference between samples obtained under

different fractionation conditions.

– FBRM and PVM were able to measure solid particulates in real time in the crude

circulation line.

3

Experimental Setup & Overview • Lab Experiments:

• 1) Ca(OH)2 addition to ‘ugly’ sample

• 2) Comparison of ‘ugly’ sample and ‘pretty’ sample

• 3) Comparison between fractionation samples

• Lab experiments were carried out in a beaker during

measurement.

• Pilot Plant Experiment:

• Both FBRM and PVM instrument were inserted into

the pipeline at an angle to during tank circulation.

• During both lab and circulation run, samples were

measured at full process concentration using FBRM and

PVM technologies.

FBRM probe installed in a

pipeline

PVM probe in LabMax

crystallizer

74

Ugly ()- Real Time FBRM Data

Sample– Real Time FBRM Trends

• FBRM trends are sensitive to addition of varying amount of Ca(OH)2 solid particulates to the

crude oil.

• FBRM technology can be integrated with HTL technology to monitor and quantify solid

particulates present in the refined crude oil and assess product quality.

Co

un

ts/s

ec

Relative Time

Counts/sec (<10 microns)

Counts/sec (10-100 microns)

300g Crude 1% Ca(OH)2 3% Ca(OH)2 6% Ca(OH)2 9% Ca(OH)2

Sample– Real Time FBRM Trends

• With the exception of 1%, both <10 microns and 10-100 microns chord counts increase steadily as more

Ca(OH)2 is added (arrows at 3, 6, and 9% indicate Ca(OH)2 addition points).

• This simulated experiment shows that FBRM is sensitive and reliable tool to detect and quantify solid

particulates in reaction feed.

Co

un

ts/s

ec


Counts/sec (10-100 microns)

300g Crude

Possibly related to Ca(OH)2

addition method and

subsequent dispersibility

Relative Time

1% Ca(OH)2 3% Ca(OH)2 6% Ca(OH)2 9% Ca(OH)2

Sample– PVM Images at Key Points

77

Before any addition of Ca(OH)2, very few particulates are observed.

Time - 12:17:10 PM


78

After 1% Ca(OH)2 addition, PVM image shows increased number of solid particulates.

PVM can be used to visually assess the extent of solid particulates present in the feed after

heavy to light crude conversion.

Time - 12:37:14 PM


After 3% Ca(OH)2 addition, PVM image shows increased number both fines and coarse solid

particulates.

PVM image complements quantitative FBRM trend information.

Time - 1:33:48 PM


After 6% Ca(OH)2 addition, PVM image shows indicate further increase in particulates.

Time - 1:41:42 PM


PVM technology can take real time images at process concentrations as increasing amount of

Ca(OH)2 to added to the crude.

PVM can enable qualitative assessment of crude oil

Time - 1:53:55 PM

• Consistent with PVM images, both fine (<10 microns) and coarse (10-

50 microns) counts increase with increasing addition of Ca(OH)2.

• FBRM can be implemented as a process tool in the field to detect

solid particulates increase over an acceptable level and implement

process changes to understand and eliminate conditions that lead to

undesired level of solid particulates.

Sample– FBRM Distributions at Key Points

Co

un

ts/s

ec

Chord Length (Microns)

0 %

6 %

3 %

9 %

Statistics 0% 3% 6% 9%

Counts <10

microns 507 1448 2567 3790

Counts 10-

100 microns 357 900 1686 2483

83

Evaluating alternative process conditions

Pretty () vs. Ugly ()

Pretty sample looked contaminant free

Ugly sample appeared to have floating solids

Ugly PVM Images

t = 90mins

• PVM image shows stream

has solid particulates mostly

around 10 microns or higher

in dimensions.

12 11 55 PM

12 15 20 PM

12 16 30 PM

Ugly () PVM Images

• PVM image occasionally captured air bubble that was entrained in ugly sample.

Pretty Images

• Surprisingly, PVM image shows

pretty has higher number of

solid particulates than sample

considered ‘ugly’.

• Large number of particulates

<10 microns observed.

2 25 00 PM

2 25 16 PM

2 25 38 PM

Pretty vs. Ugly - Unweighted

• Pretty sample considered clean but it has significantly high

number of solid particulates than Ugly sample.

t = 332mins

Large crystal

agglomerates

Fines due to attrition

Chord length (microns)

Co

un

ts/s

ec

Pretty

Ugly

Decrease in

solid

particulates

Peak due to

air bubbles

entrained in

the sample

Pretty vs. Ugly - Unweighted

• Consistent with PVM images, FBRM statistics show larger proportion of small solid particulates

(most likely asphaltenes) in pretty compared to ugly sample..

• FBRM technology enables quantification of solid particulate population in different dimensions

range to evaluate crude oil quality and process conditions.

t = 332mins

Large crystal

agglomerates



Co

un

ts/s

ec

Pretty

Ugly

Statistics Pretty Ugly

<10 microns count 2945 507

10-100 microns count 871 357

Mean No Wt (<100 microns) 7.15 11.42

Pretty vs. Ugly - Weighted

• Ugly sample has a bimodal distribution due to solid particulates (peak mode ~20 microns) and air bubbles

(peak mode ~500 microns). FBRM weighted distribution is sensitive to presence of both small solid

particulates and large air bubbles.

• Weighted distribution in <50 microns region shows that pretty has higher proportion of small particulates in

the range of less <20 microns which confirms unweighted results.

t = 332mins

Large crystal

agglomerates



Co

un

ts/s

ec

(L

en

gth

We

igh

ted

)

Pretty

Ugly

Since weighting is sensitive

to coarse chords, this peak

is due to few air bubbles

entrained in ugly sample .

FBRM Benefit – Real Time Statistics Trends

• FBRM trends can be obtained in real time to understand changes in solid particulates – after

the initial dispersion, median remains fairly constant while <5 microns count slightly drop over

the length of experimental duration for pretty sample.

• Relevant statistics can be tracked in real time to monitor the process in the plant and quickly

detect any upsets.

Relative Time


Median (microns)

Co

un

ts/s

ec(<

5 m

icro

ns)

Med

ian

(m

icro

ns)

FBRM Benefit – Real Time Distributions

• Consistent with FBRM trends for Pretty, FBRM distributions at different timepoints nearly

overlay with peak mode of ~6 microns. Slight shift in magnitude is seen due to changes in the

<5 microns trends observed.

• FBRM provides real time distributions (as fast as every 2 seconds) to monitor solid

particulates at process concentrations.

Relative Time

Unweighted Distributions

at Different Timepoints

Co

un

ts/s

ec

FBRM Benefit – Real Time Distributions

• Consistent with FBRM trends for Pretty, FBRM weighted distributions at different timepoints

nearly overlay with each other.

• FBRM provides real time distributions (as fast as every 2 seconds) to monitor solid

particulates at process concentrations.

Relative Time

Weighted Distributions at

Different Timepoints

Co

un

ts/s

ec(L

en

gth

Weig

hte

d)

93

Sample 4 vs. Sample 8


• FBRM technology provides distribution of solid particulates at process concentration in dark

crude oil and depicts similarities/differences in samples from different plant runs.

• Compared to Sample 4, Sample 8 has a narrow distribution with significant decrease in counts

in the range of 10-100 microns.

t = 332mins

Large crystal

agglomerates



Co

un

ts/s

ec

(L

en

gth

We

igh

t)

Sample 8

Sample 4

Decrease in dimension


t = 332mins

Large crystal

agglomerates

Fines due to attrition Statistics Sample 8 Sample 4

<10 microns count 2853 3369

10-100 microns count 154 413

100-200 microns count 0.28 2.34

Median No Wt 3.65 3.90

Mean Lth Wt 8.74 15.39


#/s

ec

(L

en

gth

We

igh

t)

Sample 8

Sample 4

• From the distribution data, statistics can be extracted to quantify differences between samples

fractionated under different process conditions (See Table).

• FBRM is a process tool that enables real time monitoring of process conditions on

fractionation product – FBRM distribution show that Sample 8 is less contaminated compared

to Sample 4.

96

Whole Crude Tank Recirculation Run

PVM Images (4 59 PM)

t = 90mins

• Real time PVM images in the

plant show the presence of solid

particulates mostly around <10

microns with few particulates

that are in the 10-50 microns

range.

4 59 PM

5 00 PM

5 01 PM

Unweighted FBRM Distribution

• Consistent with PVM images, small fines observed in the whole crude tank recirculation with a distribution that has a

mode ~5 microns.

• Unweighted FBRM distribution is sensitive to presence of fines and the real time technology provides statistics to

quantify amount of fines during HTL operation in the field.

t = 332mins

Large crystal

agglomerates

Fines due to attrition Statistics

<10 microns count 2230

10-50 microns count 366

Median (microns) 4.43

#/s

ec


- In-process FBRM and PVM technologies enable new technology users to measure

undesired solid particulates present in the crude oil in real time during and after process to

quickly screen and evaluate final product quality.

- Integration of FBRM and PVM tools with new technology provide quantitative and qualitative

information to rapidly track and adjust process operation – the ability to obtain real time

process information will eliminate lengthy post-upgrade offline measurement.

- FBRM and PVM data help to prove effectiveness of new technology.

- FBRM & PVM are versatile tools and their utility extend beyond detection of solid

particulates in the converted light oil – it can be used to screen initial feedstock, quantify

water content in feedstock, and optimize oil-water separation process of the initial

feedstock.

99

Observations

`

• Langiappe

Full Spectrum

Consulting LLC

Houston Industrial, Shipping, Offshore, etc. Emissions

and consideration of the Houston Airshed

Potential to measure and control

particulate emissions

Full Spectrum

Consulting LLC

Houston Industrial, Shipping, Offshore, etc. Emissions What you don’t know, can’t see, and can’t smell can kill you

Houston Cancer Map by Census Tract; Port Arthur on right side

• (EPA, 2014) Full Spectrum

Consulting LLC

EPA Emission Factors do not show the elements and

compounds poisoning local and distant downwinders

• Life in the shadow of an oil refinery.

• On the blocks surrounding Calumet Specialty Products’ Shreveport Refinery the stench of rotten eggs is nearly constant. It’s a sign that hydrogen sulfide is in the air, and residents say the chemicals they’ve come to associate with that smell are responsible for a host of health issues — from cancers to lung disease to nerve damage — that plague families in the area. Al Jazeera America


http://www.environmentalhealthnews.org/t/8112162486588138426

http://america.aljazeera.com/

Houston Industrial, Shipping, Offshore, etc. Emissions

What you don’t know, can’t see, and can’t smell can kill you

Houston Cancer Map by Census Tract

Full Spectrum

Consulting LLC

Industrial Point Source

Particulate Matter less than 2.5 microns,

PM2.5s, are known as invisible killers.

• (EPA, 2014)

Full Spectrum

Consulting LLC

Particulate emissions, ozone impact on Houston public health:

Out of hospital cardiac arrests: 90% fatal, each dot a life

• Cardiac Arrests match and correlate to PM2.5s and Ozone

Particulate matter less than 2.5 microns, PM2.5s,

are known as invisible killers.

There is no safe level of PM2.5s for any air breather.

Premature death from PM2.5s cuts ~12 years off life.

PM2.5s are easily measured and seen in the air, often labeled

as haze. Higher PM2.5s, lower visibility.

Full Spectrum

Consulting LLC

Particulate emissions, ozone impact on Houston public health: each dot a

cardiac arrest, 90% fatal

Out of hospital cardiac arrests: 90% fatal, each dot a life;

knew three of the dots


• (Ensor, Raun, 2013) Full Spectrum

Consulting LLC

Particulate emissions, ozone impact on Houston public health:

Out of hospital cardiac arrests: 90% fatal, each dot a life


Particulate matter less than 2.5 microns, PM2.5s,

are known as invisible killers.

There is no safe level of PM2.5s for any air breather.

Premature death from PM2.5s cuts 12 years off life.

Personally at Funerals of 3 of the out of hospital cardiac arrest dots:

1. High School football coach, massive funeral, college players

2. Father of five children all headed to college.

3. Colleague from API Chapter 17.2 committee

Full Spectrum

Consulting LLC


PM2.5s cause premature deaths, avg 12 yrs early,

distributed far from industrial point source emitters

to poison, sicken and kill downwinders

Full Spectrum

Consulting LLC


a very bad air day in Houston

Full Spectrum

Consulting LLC


a bad air day in Houston

Full Spectrum

Consulting LLC


“good day” by TCEQ misleading AQI,

still PM2.5s contributing to early deaths

Full Spectrum

Consulting LLC


PM2.5s cause children pain, cost billions

PM2.5s are also associated with Otitis Media, the ear infection that parents

know from the whimpers and screams of their children in the middle of night.

Full Spectrum Consulting

LLC

Otitis media is one of the most common childhood infections in young children. Three of four children experience otitis media by 3 years of age,

with most infections occurring before age 2 (Bluestone and Klein 2001). Otitis media is one of the leading causes of doctor’s visits in childhood

(Freid et al. 1998) and the main reason for children to consume antibiotics or undergo surgery in developed countries (Rovers et al. 2004). Otitis

media with effusion (OME), in which fluid and mucus stay trapped in the ear after infection, may lead to conductive hearing loss that, if persistent,

may lead to delays in the development of speech, language, and cognitive abilities (Klein 2000; Teele et al. 1990). Recurrent acute otitis media

leads to decreased quality of life measurements in children and is also stressful to their caregivers (Brouwer et al. 2005). In addition, the direct

and indirect costs associated with otitis media are high: In the United States, annual health care costs were estimated at $3–5 billion (Bondy et al.

2000).

“Indirect costs due to caregiver work loss are also substantial and may in fact exceed direct costs. In 1994, the total yearly cost for otitis media in

Canada was estimated to be $611 million—60% of the total economic cost associated with all forms of diabetes (Coyte et al. 1999). Evidence

also indicates a steady increase in the incidence of diagnoses (Bluestone and Klein 2001; Lanphear et al. 1997). Consequently, identification of

potentially preventable risk factors for otitis media, such as air pollution exposure, would have significant implications for health care costs.

Because air pollution is not typically considered a risk factor for otitis media, this illness is also not considered in air pollution health impact and

cost–benefit assessments (Kunzli et al. 2000 and Brauer et al. (2006). Air Pollution and Otitis Media. Environmental Health Perspectives.

(ref: Edmonton, Zemek, R., Szyszkowicz, M., Rowe, B., (2010). Air Pollution and Emergency Department Visits for Otitis Media: A Case-

Crossover Study in Edmonton, Canada , 2010.07.21 http://ehp.niehs.nih.gov/0901675/ . Accessed 2013.09.21)

http://ehp.niehs.nih.gov/0901675/











• http://www.tceq.state.tx.us/assets/public/compliance/monops/air/sigevents/01/011002hou-ani.html

Houston Ozone Event:

VOCs, NOx, PM2.5s from Texas City, Ship Channel Industrial

Point Sources combine to create ozone plume and clouds.

This one heading northwest to the Woodlands, more usual

path is to the west below I-610.

Thousands of ozone track charts were removed from the TCEQ, Texas Commission of Environmental Quality Website,

This one from a saved file page.

http://www.tceq.state.tx.us/assets/public/compliance/monops/air/sigevents/01/011002hou-ani.html



EPA Emission Factors drastically underestimate

Methane released at drilling sites, etc.

• Texas freezes agency's funding after air pollution data released

• By Lisa Song Center for Public Integrity, Inside Climate News, Weather Channel,23 April 2014

• The early release of some scientific data have cost the San Antonio region state funds to battle its growing air pollution problem. The misstep, which appears to have been unintentional, highlights the sensitivity of studying oil and gas pollution in business-friendly Texas.

• San Antonio’s air quality has been deteriorating since 2008, the same year drilling began in the nearby Eagle Ford Shale, site of one of the nation’s biggest energy booms. The air pollution is now so bad that metropolitan San Antonio could soon be declared in nonattainment with federal standards for ozone...

Song, L. (2014.04.23) Texas freezes agency's funding after air pollution data released. Center for Public Integrity.Inside Climate News, Weather Channel. http://www.publicintegrity.org/2014/04/23/14622/texas-freezes-agencys-funding-after-air-pollution-data-released. Accessed 2014.04.23.


http://www.environmentalhealthnews.org/t/-5621816660579065889



http://www.publicintegrity.org/2014/04/23/14622/texas-freezes-agencys-funding-after-air-pollution-data-released

















Texas freezes agency's funding after air pollution data released. Texas Commission of Environmental Quality is not required to, and does not protect public health.

• “San Antonio’s air quality has been deteriorating since 2008, the same year drilling began in the nearby Eagle Ford Shale, site of one of the nation’s biggest energy booms. The air pollution is now so bad that metropolitan San Antonio could soon be declared in nonattainment with federal standards for ozone, the main component of smog. If that happens, it could be subject to sanctions from the U.S. Environmental Protection Agency, including increased EPA oversight for new development projects. ...

• InsideClimate News and the Center for Public Integrity have been reporting on air quality problems in the Eagle Ford for the past year. The initial group of stories stemming from the investigation, published in February, showed that state regulators and politicians are more focused on protecting the industry than protecting the public.

• "This is among the more petulant, childish and vindictive things I've seen TCEQ do," said Al Armendariz, a former EPA regional administrator who now works for the Beyond Coal campaign at the Texas chapter of the Sierra Club. "It's cheap, it's schoolyard bullying … to go after a local government whose sole mission is to protect public health." ... “AACOG is "an agency that's really there to help manage air quality in the region," she said. "I don't know what benefit there is to keeping information out of the hands of the public."”

• Song, L. (2014.04.23) Texas freezes agency's funding after air pollution data released. Center for Public Integrity.Inside Climate News, Weather Channel. http://www.publicintegrity.org/2014/04/23/14622/texas-freezes-agencys-funding-after-air-pollution-data-released. Accessed 2014.04.23.

• Song, L. (2014.04.23) Texas freezes agency's funding after air pollution data released. Center for Public Integrity.Inside Climate News, Weather Channel. http://www.publicintegrity.org/2014/04/23/14622/texas-freezes-agencys-funding-after-air-pollution-data-released. Accessed 2014.04.23.





http://eagleford.publicintegrity.org/

https://www.publicintegrity.org/environment/big-oil-bad-air

https://www.publicintegrity.org/environment/big-oil-bad-air

http://eagleford.publicintegrity.org/





































EPA Emission Factors drastically underestimate

Methane released at drilling sites, etc.

• EPA drastically underestimates methane released at drilling sites.

• Drilling operations at several natural gas wells in southwestern Pennsylvania released methane into the atmosphere at rates that were 100 to 1,000 times greater than federal regulators had estimated, new research shows. Los Angeles Times






http://www.latimes.com/

DIAL Measurements of Fugitive

Emissions • DIAL Measurements of Fugitive Emissions from Natural Gas

Plants and the Comparison with Emission Factor Estimates

• Allan K. Chambers, Mel Strosher

• Alberta Research Council Inc., 250 Karl Clark Rd., Edmonton, AB, Canada T6N 1E4 [email protected]

• Tony Wootton, Jan Moncrieff and Philip McCready

• Spectrasyne Ltd., Suite 22, Worting House, Church Lane, Basingstoke, Hampshire, RG23 8PX, U.K. [email protected]

• http://www.epa.gov/ttnchie1/conference/ei15/session14/chambers.pdf



DIAL Measurements of Fugitive Emissions

Used at Canadian Gas Processing Plants

• ABSTRACT

• Natural gas processing is a major industry in Alberta, Canada, and a significant source of fugitive emissions of both methane and volatile organic hydrocarbon (VOCs). This project investigated fugitive emissions at natural gas processing plants in Alberta using two complementary optical measurement methods. At five gas plants, the fugitive emissions of methane and hydrocarbons ethane and larger (C2+ hydrocarbons) were measured and quantified using Differential Absorption Lidar (DIAL). The DIAL was also used to measure emissions from process flares at two of the gas plants. At two of the plants, a gas leak imaging camera was used to locate individual hydrocarbon leaks.

• For the five gas plants surveyed in Alberta, DIAL measured methane emissions ranged from 100 to 146 kg/hr and C2+ hydrocarbon emissions ranged from 38 to 342 kg/hr. Compressors and condensate storage tanks were two significant emission sources at all of the gas plants. Process flares operating on pilot were typically responsible for 10 to 15% of the total methane emissions.

• At two gas plants the DIAL measured emissions of methane, VOCs and benzene were compared with values calculated using emission factor methods. Measured emissions of methane and VOCs were four to eight times higher than the emission factor estimates. The largest differences between measured values and estimates were for the flares and storage tanks. DIAL measured values gave a more realistic evaluation of revenue lost as fugitives than the industry accepted estimation methods, leading to an increased incentive to improve leak detection and repair.



DIAL Measurements of Fugitive Benzene Emissions, shows

fenceline meters 2m high useless, in the case of coker benzene

emissions, actual were 9780 times permit



Text

Typical Distribution of Refinery VOC

Emissions Based on DIAL Measurements

• Typical location of emissions from a refinery

based on a report from Spectrasyne who has

completed over 30 refinery studies.

• Results will vary significantly depending on

refinery design.

• All calculations using emission factors are wrong

vastly understating emissions.


Typical Distribution of Refinery VOC Estimate versus

Actual Emissions Based on DIAL Measurements

• http://www.epa.gov/ttnchie1/conference/ei20/session7/acuclis.pdf


http://www.epa.gov/ttnchie1/conference/ei20/session7/acuclis.pdf



Typical Distribution of Refinery VOC Estimate versus

Actual Emissions Based on DIAL Measurements

• Examples of carcinogenic benzene emissions include:

• Refinery Delayed Coker, measured up to 9780 times “Texas Flexible permit.”

• Measured….3.3 to 48.9 lbs/hr Texas Flexible Permit….0.005 lbs/hr

• Chemical plant pyrolysis gasoline storage tank, measured up to 18 times permit

• Measured….1.2 to 32.5 lbs/hr Texas Flexible Permit….1.83 lbs/hr

• Benzene emissions also appeared to originate from an unpermitted tank

• Refinery Wastewater Treatment Basins measured up to 13 times permit.

• Measured….2.6 to 10.3 lbs/hr Texas Flexible Permit…0.82 lbs/hr

• The results were consistent with other DIAL campaigns showing that emissions can be much greater than permitted or expected

• (Secrest, 2008)


`

Thank You

Full Spectrum

Consulting LLC

126

Appendix :

FBRM (Focused Beam Reflectance Measurement)

PVM (Particle Video Microscope) Technologies

Typical FBRM® applications include:

-Crystallization

-Fluidized Bed

-Precipitation

-Polymerization

-Emulsification

-Microencapsulation

-Dissolution and disintegration

-Flocculation

-Fermentation

1

2

7

Mettler Toledo FBRM® in-situ Probe-Based Instruments

Mettler Toledo FBRM® is a quantitative measurement enabling chemists or engineers to

quickly link particle system dynamics to processing conditions.

Track the rate and degree of change to particles and droplets as they actually exist in

process

FBRM® measurement tracks changs to particle dimension, shape, & count

FBRM® is controlled by a new state of the art software which integrates with most Mettler

Toledo tools

No Sampling Required

At process concentrations to 70% solids

In lab or plant environments

In opaque or translucent slurries

Submicron to 3mm

-80°C to 150°C *

* Standard (other options available)

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How does FBRM® work?

FBRM®

Probe Tube

Sapphire

Window

Optics

Rotating optics

Sapphire

Window

Return Light

Outgoing Light

Focused beam

Cutaway view of

FBRM® In-process Probe

Image illustrating the view

from the FBRM® Probe Window

Probe installed in

process stream

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What is FBRM® Technology? Image illustrating the view

from the FBRM® Probe Window Enlarged view

Probe detects pulses of Backscattered light

And records measured Chord Lengths

Path of Focused Beam

This core patented technology is called Focused Beam Reflectance Measurement [FBRM®]

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What is FBRM® Technology ?

Path of Focused Beam

Enlarged view

Thousands of Chord Lengths are measured each second to produce the FBRM® Chord Length Distribution :

Typical FBRM® applications

include:

-Crystallization

-Fluidized Bed

-Precipitation

-Polymerization

-Emulsification

-Microencapsulation

-Dissolution and disintegration

-Flocculation

-Fermentation

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PVM® In Situ Probe-based Instruments

PVM® is a probe based vision tool which gives an instantaneous, information rich, insight into particle system behavior

Light weight with quick setup, PVM® is easily moved from one vessel to another

No sampling, sample preparation, or dilution required

No calibration needed

Detect particles from 2μm to 1mm

Save a “particle sequence movie” at 10 image per second

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What is PVM® Technology?

No external illumination required

Chemically resistant probe materials (Alloy C22 and Sapphire Window)

Tight focal plane for high resolution with little influence of background particles

Crisp Images without blurry in fast moving slurries

Temperature -80˚C to 120˚C

Sapphire

Window

Illumination

Lens system

Objective

Lens

CCD

Conduit

CCD Camera

Date post:	08-Sep-2018
Category:	Documents
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