1. Particle Characterization:Petroleum Applications Mark Bumiller 2010 HORIBA, Ltd. All rights reserved.

2. Range of Applications Exploration ProcessingRefining Completion Drilling fluid Oil in water emulsion Catalysts ProppantsSolid particlesTechniques used: laser diffraction, dynamic image analysis,Acoustic spectroscopy, surface area analysis 2010 HORIBA, Ltd. All rights reserved. 3. Exploration: Drilling Rig1. Mud tanks2. Shale shaker3. Mud suction line4. Mud pump16. Drill pipe20. Rotary table26. Drill bit 2010 HORIBA, Ltd. All rights reserved. 4. Drilling Fluid (Mud)Remove cuttings from wellSuspend and release cuttingsControl formation pressuresSeal permeable formationsMaintain wellbore stabilityMinimizing formation damageCool, lubricate, and support the bit anddrilling assemblyFacilitate cementing and completion 2010 HORIBA, Ltd. All rights reserved. 5. Types of FluidsWater-based mud (WBM) Water, then clays and other chemicals Most common is bentonite Other chemicals for viscosity control, shale stability, enhance drilling rate, cooling, etc.Oil-based mud (OBM) Base fluid is a petroleum product such as diesel fuelSynthetic-based fluid (SBM) Base fluid is a synthetic oil 2010 HORIBA, Ltd. All rights reserved. 6. Particle Size of Drilling FluidsStandard methods include sieves & sedimentationReport residue > 75 m & < 6 mDiffraction can report this, + distribution informationD10, d50, d90Quicker, more reproducibleRecommended practices for barite:RI: 1.64, 0.1 in 1.33 (water)Dispersant: 1 g sodium pyrophosphate in 1000 cm3 waterMix paste of barite powder, dispersantAdd to system, %T not < 90-85%Ultrasound for 60 secMeasure 2010 HORIBA, Ltd. All rights reserved. 7. Particle Size of Drilling FluidComposition:Bentonite 29 g/LXantham gum 2.9 g/LP.A.C. (polymer additive) 2.9 g/LBarite 15 g/LNaOH 0.7 g/LProcedure:RI for barite = 1.64, 0.15 g of barite added to a beaker.Dispersant* added to barite drop wise until smooth paste was created.*Dispersant solution: 1 g of sodium pyrophosphate/1000 cm3 of solution.Sampler was filled with DI water.Barite sample added the sampler using clean spatula to desired concentration: Transmission = 80-90%Sampler circulation setting = 5Ultrasound at level 7 applied to sample for 60 secWait 30 sec after turning off the ultrasoundPerform particle size measurementRepeat these steps for a total of 3 sub-samples from the original paste 2010 HORIBA, Ltd. All rights reserved. 8. Particle Size of Drilling Fluid LA-950 2010 HORIBA, Ltd. All rights reserved. 9. Particle Size of Drilling Fluid LA-930 2010 HORIBA, Ltd. All rights reserved. 10. Particle Size of Drilling Fluid LA-300 Smaller, portable, better for field work 55lb/25 kg 2010 HORIBA, Ltd. All rights reserved. 11. Hydraulic Fracturing Proppant20/40 sand 2010 HORIBA, Ltd. All rights reserved. 12. ProppantsKeep fractures openImproves permeabilityOften sand , specified by sieve sizes 12/20, 16/30, 20/40, 40/70 (95% passes between these sieve sizes)Higher tech proppants, more expensive,higher performance 2010 HORIBA, Ltd. All rights reserved. 13. Ceramic Proppant Patent The resulting pellets have a sphericity of about 0.8-0.9,as determined using the Krumbein and Sloss chart. 2010 HORIBA, Ltd. All rights reserved. 14. Proppant Spec Sheet** 2010 HORIBA, Ltd. All rights reserved. 15. Proppants: CAMSIZER Size and shape from 30 m 30 mm 2010 HORIBA, Ltd. All rights reserved. 16. CAMSIZER Proppant Data* API crush test of proppants: Mechanical forces compresses proppant in cell to desired P PSD is measured after release Crush resistance = wt% of proppant passing smallest sieve of originally specified PSD Only one sieve tray required, entire PSD changes during test Measuring entire PSD reveals more informationAn optical size analyzer can extract more information than physical sieve analysisabout the behavior of proppants under stress while significantly reducing analysis time.*Stephens et. al., Statistical Study of the Crush Resistance Measurement for Ceramic Proppants2006 Annual SPE Meeting 2010 HORIBA, Ltd. All rights reserved. 17. CAMSIZER Proppant Data*PSD before and after crush *Stephens et. al., Statistical Study of the Crush Resistance Measurement for Ceramic Proppants 2006 Annual SPE Meeting 2010 HORIBA, Ltd. All rights reserved. 18. CAMSIZER Proppant Data*50th percentile before andafter crush10th percentile beforeandafter crush *Stephens et. al., Statistical Study of the Crush Resistance Measurement for Ceramic Proppants 2006 Annual SPE Meeting 2010 HORIBA, Ltd. All rights reserved. 19. Production Fluid Separation Gas OilWaterSolids(particles)Oil/water separator 2010 HORIBA, Ltd. All rights reserved. 20. Production Fluid SeparationWant to separate all phasesNeed to measure phase separation Improve by adding surfactantsNeed to measure ppm oil in water Required to measure if pumping water into ocean (off shore rigs) Oil is valuable, separate as much as possiblePossible to differentiate oil droplets fromparticles? 2010 HORIBA, Ltd. All rights reserved. 21. Emulsion Stability Want to promote phase separation Recover oil, discharge water May want to add water to oil to reduce viscosity, easier to transport (orimulsion) 2010 HORIBA, Ltd. All rights reserved. 22. Emulsion Stability: DT1201 Measure particle size & zeta potential w/no dilution Zeta potential (CVI) predicts dispersion stabilityColloid vibration current (CVC) zeta potential 2010 HORIBA, Ltd. All rights reserved. 23. Bitumen Emulsion Stability*Bitumen diluted 1:1 w/tolueneDiluted w/D2O 2-30 wt %Homogenize 125 watt, 30,000RPM*Magual, A., Horvath-Szabo G., Masliyah, J.H. Acoustic and electroacoustic spectroscopy of DT-1200 w/homogenizerwater-in-diluted bitumen emulsions, Langmuir, 21, 8649-8657 (2005) 2010 HORIBA, Ltd. All rights reserved. 24. Bitumen Emulsion Stability* 2010 HORIBA, Ltd. All rights reserved. 25. Crude Oil DemulsificationProblem: Break the crude oil emulsion In the shortest time With less additive Leave an unpolluted water phaseSolution: Find the optimal additive (cost, efficiency) Need to be tested on each oil batchIdentify the best surfactant for demulsificationGeneral Turbiscan presentation 2010 HORIBA, Ltd. All rights reserved. 26. Crude Oil DemulsificationStudy from French Institue of Petroleum (IFP)*Turbiscan testQualitative & Quantitative studySelection of the best additiveOptimization of the additive concentrationCriteria: width of T peak = height of separated water height of T peak = Limpidity of separated water*C. Dalmazzone, C. Nok, Development of New green Demulsifiers for Oil Production , SPE65041General Turbiscan presentation 2010 HORIBA, Ltd. All rights reserved. 27. Crude Oil Demulsification Limpidity (clarity) Height wateroilC. Dalmazzone, C. Nok, Development of New green Demulsifiers for Oil Production , SPE65041General Turbiscan presentation 2010 HORIBA, Ltd. All rights reserved. 28. Crude Oil Demulsification Separation rate => %T = f(time) 300 ppm is the best concentrationC. Dalmazzone, C. Nok, Development of New green Demulsifiers for Oil Production , SPE65041General Turbiscan presentation 2010 HORIBA, Ltd. All rights reserved. 29. Orimulsion: EmulsificationBitumen: sticky, tar-like form of petroleum so thick &heavy must be heated/diluted before it will flowWorlds largest deposit in Orinoco Belt, VenezuelaOrimulsion made by mixing bitumen with ~ 30%fresh water + small amount of surfactantThe result behaves similarly to fuel oilUsed as commercial boiler fuelD50 ~ 14 mOrimulsion droplets LA-950 result 2010 HORIBA, Ltd. All rights reserved. 30. Oil in Water after Separation Flow chambers 50um 1mm 2mm-6 mm 2010 HORIBA, Ltd. All rights reserved. 31. Droplets vs. Particles Oil droplets Iron sulfide particlesDistinguishing between two would be easy if they looked like this 2010 HORIBA, Ltd. All rights reserved. 32. Droplets vs. Particles Agglomerated dropletsSand 2010 HORIBA, Ltd. All rights reserved. 33. Pattern Matching AlgorithmUser selects examplesof droplets, iron sulfide,sand particlesSoftware looks at many ppmsize/shape valuesChooses how todiscriminateBins each particle bytype, countstimeCan calculate ppm oil 2010 HORIBA, Ltd. All rights reserved. 34. Refining: CatalystsSize, shape and specific surface area (SSA)affect catalyst performanceMeasure size using laser diffractionMeasure size/shape by CAMSIZERMeasure SSA using BET: SA-9600Flowing gas BET methodLow price,operating costs, maintenanceEasy to use, fastest measurement timeNo vacuum system requiredSingle or multi-pointUp to three samples simultaneously 2010 HORIBA, Ltd. All rights reserved. 35. Catalysts Size/Shape by CAMSIZERSpherical catalystsEasy, no special effortCylindrical catalystsLength, widthBended extrudatesUse other parametersxlength = ( x Fe max ) 2 ( xc min ) 2Ax stretch =x c min 2010 HORIBA, Ltd. All rights reserved. 36. Catalysts Size/Shape by CAMSIZERTri & quadralobePossible to distinguishQuadralobe catalystsbetween differentdiamteters Trilobe catalystsShorter greendistribution = lengthTaller maroondistribution= width 2010 HORIBA, Ltd. All rights reserved. 37. SummaryParticle size, shape, surface area, otherproperties important from exploration torefiningKey applications:Drilling fluidProppantsOil/water/solids separationCatalystsTalk to HORIBA about all these requirements 2010 HORIBA, Ltd. All rights reserved.