Вы находитесь на странице: 1из 10

7th Pipeline Technology Conference 2012

Crude Oil Refinery Impact Testing with LiquidPower Flow Improvers Ray Johnston ConocoPhillips Specialty Products Inc. USA Abstract CSPI has been treating pipelines with LiquidPower Flow Improvers for over 17 years with no reported adverse effects to refinery operation and finished product quality. CSPI has verified these results with full-scale refinery testing and lab scale testing. ConocoPhillips Specialty Products Inc. (CSPI), a wholly-owned subsidiary of ConocoPhillips Company, is the global leader in the science and application of drag reduction. CSPI has provided solutions that allow pipelines to maximize their flow potential, increase operational flexibility, and increase bottom-line profit potentials. DRAs are hydrocarbon-based materials which reduce frictional pressure loss during turbulent flow in a pipeline, enabling companies to strategically reduce or avoid capital expenses, improve pipeline operating costs and/or expand their pipeline system capacity. CSPI has a range of products to drag reduce crude oil, refined products, heavy oil, and multiphase. 1.0 Product Characteristics and Testing Summary

LiquidPower Flow Improvers consist of very fine particles of polymer suspended in an aqueous carrier. This aqueous carrier may contain some glycol for freeze protection and small amounts of surfactants and additives to maintain the stability of the suspension. When the LiquidPower Flow Improver is injected into a pipeline (typically at 10 to 80 ppm), the product disperses throughout the crude oil with the polymer going into solution in the crude oil to create the drag reduction effect. The aqueous portion of the carrier remains dispersed. Once the treated crude oil reaches the refinery and, eventually, the desalter process, the polymer remains in solution in the crude oil along with some oil-soluble components of the DRA and the carrier components partition largely to the effluent wastewater from the desalter. With this in mind, in terms of refinery impact testing, the following observations and tests were conducted: 1.1 Real life applications 1.2 Full-scale refinery test with monitoring of the desalters and the finished product quality 1.3 Desalter mimicking tests to evaluate the dewatering rates of crude oil treated or untreated with LiquidPower Flow Improvers 1.4 Crude oil distillation (pilot plant) of crude oils treated with LiquidPower Flow Improvers followed by quality testing of the product cuts from the crude oil 1.5 Fouling propensity tests to evaluate for any effect of LiquidPower Flow Improvers on preheat train fouling.

1.1 Real Life Applications LiquidPower Flow Improvers have been used for increasing the flow rate of crude oil pipelines for over 17 years since their development in the 1990s. Today, LiquidPower Flow Improvers are used to treat over 1 billion barrels of crude oil worldwide per year and CSPI has sold flow improvers in 45 countries. The majority of the refineries in the United States are processing crude oil treated with LiquidPower Flow Improvers. Treatment levels at some refineries have been approximately 250 ppm in the crude oil feed for over a 5 year period. In Europe, a refinery has been processing crude with CSPI flow improvers containing a cumulative DRA concentration exceeding 200 ppm for over 15 years. During these periods, there have been no mechanical or operating problems, no catalyst effects, and no finished product issues reported by the refineries related to the use of these flow improvers. 1.2 Full-scale Refinery Test The purpose of the full-scale refinery test was to evaluate the effect of LiquidPower Flow Improvers on refinery operations by treating the majority of crude oil feeding a Midwest refinery over a multi-day period. Two pipelines representing 85% of the crude oil feeding the refinery were simultaneously treated with 25-40 ppm of LiquidPower Flow Improver for a five day period. The refinery operations were monitored closely for a time period prior to the arrival of the treated crude oil and during the processing of the treated crude oil. The refinery operators reported no observed changes outside of standard operating conditions during the test period. All daily operational logs showed no significant variations in operating parameters. Because any effects of the aqueous form of LiquidPower Flow Improvers would most likely be observed in the desalters, these units were most closely observed. All logged operating parameters of the desalters were consistently within the normal operating range during the treatment period, as reflected in Table I.

Table I. Desalter Observations during Treatment Period PARAMETER POTENTIAL NEGATIVE EFFECT Rag Layer Thickness Increased if surfactant effects occur Demulsifier Injection Rate Increased rate to decrease or control rag layer Voltage and Power Draw Change; indicates differences in separation Salt Content Increased values OBSERVED EFFECT At or below acceptable levels; no increase No increases required or made Voltage and amperage were constant Values ranged from 1.0 to 2.0 lbs/1000 bbl before, during, and after testing Clear; no change

Effluent Water Color

Discoloration or cloudiness

The refinery ran very smoothly during the test period and all products from the refinery during the test period met all quality standards as reported by the refinery control laboratory. Tables II and III in the Appendix show refinery control lab release data for refined product samples pulled during the untreated and treated portions of the test period. 1.3 Desalter Mimic Tests The desalter mimic tests were conducted with a desalter simulator apparatus similar to a portable electrostatic dehydrator unit. The unit consists of a heated block and wells for the placement of sample tubes which have electrodes to generate voltage difference within the tubes. The experimental tests involve obtaining a raw crude oil sample and a desalter wash water sample from a refinery, forming emulsions with the samples, and then monitoring water breakout rates in the samples with or without the presence of various additives. The test parameters for the desalter simulator were established to mimic refinery desalter operation as much as possible. The unit and samples were heated to 280F (138C) for testing. The wash water was added to the crude oil at a 6% level; emulsion breaker was added to the mixtures at 12 ppm. High speed mixing occurred for 5 seconds, followed by separation and monitoring with an applied voltage to the tubes. Three series of tests were conducted in the desalter simulator utilizing three different crude oils: Alaska North Slope, Norsk Hydro and West Texas Intermediate. In these tests, LiquidPower Flow Improvers were added to the crude oil at 0, 100 and 200 ppm levels. In all test results, the separation rate and volume for water from the treated crude oil was equal to that of the untreated crude oil. Water quality following separation was not affected by addition of the flow improver.

1.4 Crude Oil Distillation Product Cuts Laboratory tests were conducted on drag reducer treated crude oil samples pulled from pipelines. These tests were conducted to analyze for any potential effects on quality of the refined products distilled from the crude oil. Crude oil samples, representing four different oil batches (two sweet and two sour) were pulled from the pipelines during drag reduction performance testing. The flow improver treatment rate of the crude oils ranged from 25 ppm to 40 ppm. At a ConocoPhillips downstream operations control laboratory, these samples were fractionated into cuts, treated to mimic refinery treatment, and then analyzed for critical quality parameters. Tables IV and V in the Appendix show results of the analyses. All measured parameters of the finished product samples met the required specifications. Of special note, Water Separation Index numbers were typical, showing that the water soluble components present in LiquidPower Flow Improver had no adverse effect. 1.5 Fouling Propensity Tests Prior to entering the first distillation tower, crude oil will typically pass through a series of heat exchangers to heat the crude oil. A series of laboratory tests was run on crude oil treated with LiquidPower Flow Improvers, to ascertain whether the presence of the DRA affected the potential for fouling of these preheat train heat exchangers. For these tests, a North Sea crude oil was treated with 1000 ppm LiquidPower Flow Improver (an excessive level) and compared to the same crude oil without treatment. The crude oil asphaltene stability was tested using an automated flocculation titrimeter (AFT). The test results yielded similar asphaltene stability values for both the untreated and the treated crude oil, with both being stable. The flow improver showed no affect on crude asphaltene stability. Fouling propensity was tested using a hot liquid process simulator (HLPS) unit. The testing conditions were 500 psig (34.5 bar) with a 370C heater. The resultant temperature traces were identical for the treated and untreated crude oil. The test results showed that the flow improver had no effect on the crude fouling rate. Based on these lab test results, LiquidPower Flow Improver was not expected to alter fouling characteristics of treated crude oil in refinery preheat trains. 2.0 Conclusion CSPI has been treating pipelines with LiquidPower Flow Improvers for over 17 years with no reported adverse effects to refinery operation and finished product quality. CSPI has verified these results with full-scale refinery testing and lab scale testing. During the full-scale refinery tests, the refinery reported the following results; no observed changes outside of standard operating conditions during the test period,

no significant variations in operating parameters, and all products from the refinery during the test period met all quality standards as reported by the refinery control laboratory.

The labscale desalter tests demonstrated the following results; no decrease in the water separation rate was observed, no change in the volume of water separated, and the wastewater quality was not affected. In pilot plant crude oil distillation, the following results were reported; flow improvers had no effect on finished product quality, and all crude oil cut samples met the required specifications, The fouling propensity tests demonstrated flow improvers did not increase the characteristics for fouling rate in the crude oil preheat train. Extensive research and testing indicate that there is no adverse impact to refinery operations or finished product quality from the use of LiquidPower Flow Improvers. Decades of expertise and industry leadership in DRA formulation allow ConocoPhillips Specialty Products, Inc. to match products with specific applications for maximum benefit, while alleviating concerns on the impact to refinery operations.

APPENDIX Table II. Refinery Control Lab Results on Gasoline Product Release Table III. Refinery Control Lab Results on Diesel and Jet Fuel Product Release Table IV. Test Results on Distillation Product Cuts Sour Crude Table V. Test Results on Distillation Product Cuts Sweet Crude

Table II. Refinery Control Lab Results on Gasoline Product Release Refinery Control Laboratory Product Release (COA) -- Lab Test Results Unleaded Gasoline Untreated Treated 58.9 60.0 58.9 60.0 58.9 60.0 58.9 60.0 Super Gasoline Untreated Treated 59.0 58.6 59.3 58.8 58.9 58.5 59.3 58.5

Product Parameter API @60F Composite API @60F Top API @60F Middle API @60F Bottom Distillation - ASTM D86 Deg F IBP 10% EVAP 50% EVAP 90% EVAP End Point Recovery, Vol% Residue, Vol% Sulfur Wt% Reid Dry VP v/l of 20 Deg F CST 3hr, @122 Deg F Sulfur, mercaptan, Wt% Exist Gum mg/100ml Induction Period Min Research Octane Motor Octane Road Octane MTBE Vol %

90 111 193 313 410 96 1.0 0.03 9.8 129 1 0.0016 1 300 91.8 82.3 87.1 <0.1

82 110 188 313 415 96.4 1.0 0.02 9.8 128 1 0.0016 1.6 300 91.8 82.2 87 <0.1

85 123 210 297 389 95.9 1.0 0.01 9.8 135 1 0.0023 1.6 300 95 87 91 1.1

87 126 206 298 384 96.9 1.0 0.01 9.8 135 1 0.0019 0.6 300 95.7 86.8 91.3 3

Table III. Refinery Control Lab Results on Diesel and Jet Fuel Product Release Refinery Control Laboratory Product Release (COA) -- Lab Test Results
DIESEL Product Parameter Untreated API @60F Composite 32.9 API @60F Top 33 API @60F Middle 32.9 API @60F Bottom 32.8 Distillation - ASTM D86 Deg F IBP D86 Deg F 347 10% REC 426 20% REC 461 50% REC 533 90% REC 619 95% REC 642 End Point 666 Recovery, Vol% 98.4 Residue, Vol% 1.5 Colonial Haze 1 Vis @ 40C 3 Pour Point, Deg F 0 Cloud Point, Deg F 12 Flash PM Avg Deg F Rams CR 10% Btms Wt% 16 Hr. Oxygen Bomb Stability 16 Hour Color Soluble mg/100ml Insoluble mg/100ml Thermal Stability, 90 min 300 Deg F DuPont Scale Pad Rating Sulfur Wt% Ash Wt% Cetane Index Color CST 3hr, @ 122 Deg F BS, Vol% 148 0.12 L4 17.8 0.2 JET FUEL A Product Parameter Untreated Acidity, total, mg KOH/gm 0.02 Aromatics, Vol% 18 Sulfur, mercaptan, Wt% 0.0023 Sulfur, Total Wt% 0.14 Distillation, IBP, Deg F 332 10% REC 364 50% REC 414 90% REC 484 Final Boiling Point, Deg F 516 Distillation Residue, % 1 Distillation Loss, % 1.5 Flash Point, Deg F 122 API @ 60F 42.3 Freezing Point, Deg F -42.7 Viscosity @ 4F, cSt 5.48 Net Heat of Comb., BTU/lb 18551 Smoke Point 22.9 Napthalenes, Vol% 2.5 Copper Strip Test, 2 hrs @212 1 Thermal Stability: Filter Pressure Drop, mmhg 0 Tube Rating 1 Existant Gum, mg/100ml 0.8 Water Reaction: Interface Rating 1 Separation 2 Aniline Point Deg F 141 Water Separometer Index Mod. 85 Particulate matter, mg/gal 0.53 Saybolt Color 20

Treated 33 33.2 33.2 32.8 345 403 425 537 627 653 679 98.2 1 1 3 10 16 157 0.06 L4 12.8 0.7

Treated 0.02 19 0.0029 0.15 328 367 415 487 517 1.5 1.4 128 42.2 -42.3 5.69 18548 23.7 2.6 1 0 1 0.4 1 1.1 141 95 0.4 16

2 0.39 45.7 L2 1 Trace

2 0.42 46.7 L2 1 Trace

Table IV. Test Results on Distillation Product Cuts Sour Crude ConocoPhillips Downstream Operations Control Laboratory Lab Blends of Refined Products from Treated Pipeline Samples Sour Crudes Vasconian ANS Product Parameter Naphtha Kerosene Diesel Naphtha Kerosene Diesel Distillation 10% REC, Deg F 180 316 408 107 296 381 50% REC, Deg F 240 406 495 220 459 534 90% REC, Deg F 327 529 611 319 557 626 JFTOT (Pressure/Tube) 0/1 0/1 ----0/1 1 ----WSIM 98 98 ----99 98 ----Water Reaction 0.5/1/1 0.5/1/1 ----0.5/1/1 0.5/1b/2 ----Cold Test, Deg F ---------5 ---------10 TR BS&W --------- TR water --------water Haze --------1 --------1 Carbon Residue, wt% --------0.03 --------0.02 16 Hr. Stability: Color --------<2 --------<2 Insoluble gum, mg/100ml --------0.7 --------1.1 Soluble gum, mg/100ml --------4.6 --------7.8

Table V. Test Results on Distillation Product Cuts Sweet Crude ConocoPhillips Downstream Operations Control Laboratory Lab Blends of Refined Products from Treated Pipeline Samples Sweet Crudes
Product Parameter Distillation: 10% REC, Deg F 50% REC, Deg F 90% REC, Deg F JFTOT (Pressure/Tube) WSIM Water Reaction Cold Test, Deg F BS&W Haze Carbon Residue, Wt% 16 Hr. Stability: Color Insoluble gum, mg/100ml Soluble gum, mg/100ml Induction, Hours Potential Gum, mg/100ml Existant Gum, mg/100ml Naphtha 126 229 319 0/1 99 0.5/1/1 ------------------------------------0.8 WTI-Scurry Gasoline Kerosene 120 231 380 ----------------------------------------5 24.2 26.4 306 377 503 0/1 99 0.5/1/1 ----------------------------------------Diesel 410 500 604 -------------10 Trace 1 0.03 <1.5 1.4 9.0 ------------Naphtha 124 236 327 0/1 98 0.5/1/1 ----------------------------------------WTI Gasoline Kerosene 128 245 411 ----------------------------------------5 12.2 14.8 323 420 544 0/1 98 0.5/1b/2 ----------------------------------------Diesel 430 539 615 -------------2 Trace 1 0.05 <1.5 0.4 7.4 -------------

Вам также может понравиться