Post on 08-Sep-2018
transcript
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 pavel@full-spectrum-consulting.com, skpavel@gmail.com
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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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Partial Upgraders: many claim to be the
Next Big Thing, Breakthrough Technology,
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.
Partial Upgraders: many claim to be the
Next Big Thing, Breakthrough Technology,
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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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.”
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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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 in- soluble 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
S&W by Centrifuge, Water by KF
Vessel Discharges—for reference only
56 Public domain, Fair Use Guidelines Apply
S&W by Centrifuge, Water by KF
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
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
Fracking Fluids Disclosure
outlawed by North Carolina Senate
NC Outlawing Wikipedia entries? Cheasapeake Disclosure?
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Hydraulic fracturing - Wikipedia, the free encyclopedia
en.wikipedia.org/wiki/Hydraulic_fracturing
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http://en.wikipedia.org/wiki/Hydraulic_fracturing
Fracking Fluids Disclosure
outlawed by North Carolina Senate
Wikipedia entries illegal in North Carolina?
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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]
Fracking Fluids Disclosure
outlawed by North Carolina Senate
Wikipedia entries illegal in North Carolina?
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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
Solid additive to crude for emulsion manipulation
67
Sullivan, A., Kilpatrick, 2002
Solid additive to crude for emulsion manipulation
68
Solid additive to crude for emulsion manipulation
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 microns)
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
Sample– PVM Images at Key Points
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
Sample– PVM Images at Key Points
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
Sample– PVM Images at Key Points
After 6% Ca(OH)2 addition, PVM image shows indicate further increase in particulates.
Time - 1:41:42 PM
Sample– PVM Images at Key Points
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
Fines due to attrition
Chord length (microns)
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
Fines due to attrition
Chord length (microns)
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
Counts/sec (<5 microns)
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
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
Fines due to attrition
Chord length (microns)
Co
un
ts/s
ec
(L
en
gth
We
igh
t)
Sample 8
Sample 4
Decrease in dimension
Sample 4 vs. Sample 8
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
Chord length (microns)
#/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
Chord length (microns)
- 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
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Houston Industrial, Shipping, Offshore, etc. Emissions
and consideration of the Houston Airshed
Potential to measure and control
particulate emissions
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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
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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
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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
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Industrial Point Source
Particulate Matter less than 2.5 microns,
PM2.5s, are known as invisible killers.
• (EPA, 2014)
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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.
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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
• Cardiac Arrests match and correlate to PM2.5s and Ozone
• (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
• 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.
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
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Particulate Matter less than 2.5 microns,
PM2.5s cause premature deaths, avg 12 yrs early,
distributed far from industrial point source emitters
to poison, sicken and kill downwinders
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Particulate Matter less than 2.5 microns,
a very bad air day in Houston
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Particulate Matter less than 2.5 microns,
a bad air day in Houston
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Particulate Matter less than 2.5 microns,
“good day” by TCEQ misleading AQI,
still PM2.5s contributing to early deaths
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Particulate Matter less than 2.5 microns,
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.
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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://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.
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.
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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.
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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
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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 allan.chambers@arc.ab.ca
• Tony Wootton, Jan Moncrieff and Philip McCready
• Spectrasyne Ltd., Suite 22, Worting House, Church Lane, Basingstoke, Hampshire, RG23 8PX, U.K. info@spectrasyne.ltd.uk
• http://www.epa.gov/ttnchie1/conference/ei15/session14/chambers.pdf
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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.
• http://www.epa.gov/ttnchie1/conference/ei15/session14/chambers.pdf
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DIAL Measurements of Fugitive Benzene Emissions, shows
fenceline meters 2m high useless, in the case of coker benzene
emissions, actual were 9780 times permit
• http://www.epa.gov/ttnchie1/conference/ei15/session14/chambers.pdf
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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.
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Typical Distribution of Refinery VOC Estimate versus
Actual Emissions Based on DIAL Measurements
• http://www.epa.gov/ttnchie1/conference/ei20/session7/acuclis.pdf
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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)
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`
Thank You
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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