Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90110

APPLICATIONOFNANOMATERIALBASEDHYBRIDPOURPOINTDEPRESSANT FORLONGDISTANCEWAXYCRUDEPIPELINE

DongminZhang PrimaryAuthor PetroChinaR&DCenter LangfangCity,HebeiProvince,PRC LianfengHuo PetroChinaR&DCenter LangfangCity,Hebei Province,PRC BoXu PetroChinaR&DCenter LangfangCity,Hebei Province,PRC JiantingLi PetroChinaR&DCenter LangfangCity,Hebei Province,PRC

LixinZhang PetroChinaR&DCenter LangfangCity,HebeiProvince,PRC

ShujieZhi PetroChinaR&DCenter LangfangCity,Hebei Province,PRC HuiXiong PetroChinaR&DCenter LangfangCity,Hebei Province,PRC ShuaiWang ChinaPetroleumPipeline EngineeringCorporation LangfangCity,Hebei Province,PRC

XinOuyang PetroChinaR&DCenter LangfangCity,Hebei Province,PRC BaoliangJiang PetroChinaR&DCenter LangfangCity,Hebei Province,PRC

ABSTRACT A new type of nanomaterial based hybrid pourpoint depressant withsignificant efficiency has been developed and successfully used in industrial application. For Daqing crude oil, a typical high waxy Chinese crude, with 80100g/t new pourpoint depressant and 5865 thermal treatment temperature, the wax appearance temperature of the Daqing crude oil can be decreased by 34 The viscosity/pour . point reduction,shearingresistance, and fluidityatlow temperature ofthemodifiedcrudewithnewtypeofpourpointdepressantis muchbetterthan the effect of using traditional ethylenevinyl acetate ((hereinafter referred as EVA). Therefore the safe shutdown time for a pipeline is dramatically increased which notonlyenhancesthe safety ofthe pipeline operationbutalso

significantly saves the energy consumption of the pipeline company. Besides, the reheating temperature can only be greatly reduced to 35 The relationship between the crystal . structureofthenanomaterialbasedpourpointdepressantand the type ofthe waxy crude, togetherwith its influence on the crystalform/waxappearancetemperatureofthewaxycrudeby using X ray diffraction(hereinafter referred as XRD) and Polarizing microscope (hereinafter referred as POM)are studied. Key Words: WaxyCrude Nanomaterial based Hybrid Pour Point Depressant Longdistance Pipeline Wax Appearance Temperature Crystal Form Fluidity at Low Temperature EnduranceShearingResistance

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1.INTRODUCTION Inorderto improve the lowtemperature fluidityof waxy crudeoilforthepurposeofpourpointdepressantandviscosity reduction, a high efficient nanocomposite pourpoint depressant (hereinafter referred as NP) was developed. NP wascomposedoforganicandinorganicnanohybridmaterials. Apilotproductionlinehasbeen setup with an annualoutput of400tonsofNP,andthe industrialpilottestofNPhasbeen carriedout in QinJing Pipeline, ChinaNorth Korea Pipeline and ShiLan Pipeline. The results showed that NP could decreasethepourpoint in the range of more than 15 and the viscosity reduction rate was more than 90%. Through applying in the Huludao Pipeline and Fengrun Pipeline, for thefirsttime,thecoldcommissioningofDaqingcrudeoilwas achieved with the employment of nanotechnology agents of NP,whichprovidesasecurity,economicandtechnicalsupport forthetransportationofwaxycrudeoil. 2.EXPERIMENTALSECTION 2.1APPARATUS Themainapparatusesinvolved in this work are listed as follows:Leicahotstagepolarizingmicroscope,XPertPROof MPDXraydiffraction, Agilent6890 gas chromatograph, TA DSC differential scanning calorimeter, TA2000 rheometer, VT550viscometerSYP10022 condensationpoint instrument, Julabo F32 thermostat water bath, Euroslar IkaWeroe governorblenderandsomesimulationdevices. 2.2METHODS 1)Testoftheviscosityandpourpointofcrudeoil The viscosity of crude oil was tested according to SY/T75492000standard, and the pour pointof crude oilwas testedaccordingtoSY/T05412009standard. 2)Testofcarbonnumberdistributionanddifferentialscanning calorimeter(hereinafterreferredasDSC) The carbon number distribution of wax was tested according to ASTMD5442 standard and the Paraffin precipitation distribution was tested according to SY/T0545 1995standard. 3)Microscopicobservationofwaxcrystalsincrudeoil Topackdownadropofcrudeoilsampleontheslide,and thenputthesample slide on the microscopehot stage.Witha magnification times of 500, the crystal morphology of the sampleswasobservedandphotographed. 4) Temperature programmed X ray diffraction of paraffin crystalincrudeoil Temperature programmed X ray diffraction was carried out on XPert PRO of MPD Xray diffraction with Cu K radiation,andis0.154nmwithatubevoltageof40kVand o a tube current of 40mA. The scan rate is 4 / min and the o temperaturerangeis65~25 Cwitha1 /mincoolingrate. o o Thescanninganglerangeis2 ~40 .

2.3EXPERIMENTALCONDITION 1)Fortreatmentofindoor pour pointdepressanttreated crude oilandDaqingdistillateoil AddNPtoaconcentrationof1%,stirtheminsimulation experimental device by 300rpm/min till the treatment temperature reaches 65,60,58and remains for 5 minutesandthendynamicallyreducesthetemperatureto25 or 35 by 0.5/ minutes before testing viscosity and pour pointofthesamplesat25. 2)Foronsitetreatmentofpour pointdepressanttreated crude oil Atthefirststationofexperimentalpipeline,addcrudeoil satisfying required temperature 65, 60, 58with 10% diluted NP and inject them into the inlet of oil transfer pumpby 0.8kg/t1kg/tcrudeoilandNPareinjectedintothe pipelineafterblendinginhighspeedbyoiltransferpumpget oil sample at the inlet of downstream experimental pipeline andtestitsviscosityandpourpoint. 3.RESULTANDDISCUSSION In view of modification of the Daqing crude oil, typical high waxy Chinese crude, field test of adding NP into industrial pipeline was finished. Moreover, according to the standingpropertiesofcrudewithNP,Shutdownandrestartby addingNPwasconductedontheBaodiindustrialtestbed. 3.1 FIELD TEST RESULTS OF DAQING CRUDE OIL WITHNP Laboratory experiment and field test results of Daqing crudeoilwithNPunderdifferentthermaltreatmentconditions and secondarytreatment temperature are shown in Table 31 andTable32,respectively. From Table 31, it is noted that if the treatment temperature of Daqing crude oil with NP is between 58 and 65, , the effect of modification is approximately same by 1 differenttreatmentsatatemperatureof25,30 s ,whilethe performance of field test was obviously better than that in laboratory.Thepourpointofcrudedecreasesmore than 15 , and the viscosityreduction is above 94%, indicating that the injection process, cold pipeline and shear condition may be beneficial to NP performance. When the comprehensive treatment temperature is 60 the modification performance , of crude is basically same when NP addition decreases from 100to80g/t.

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Table31LaboratoryexperimentandfieldtestresultsofDaqingcrudeoilwithNP addition underdifferenttreatmentconditions viscosity 25apparentViscosity Treatment NP Pour decreasing mPa.s Decrease temperature addition Point Sample rate 1 1 1 1 1 g/t 30s 20s 30s 40s 50s % Untreated / / 33.5 / / 2202 1668 1340 1210 65 100 95.4 18.0 15.5 94.3 165. 163. 161. 159. Lab 60 100 19.0 14.5 90.2 1 1 2 2 experiment 184. 172. 161. 153. 58 100 19.5 14.0 89.7 8 4 8 6 65 100 82.0 17.0 16.5 95.1 60 100 87.0 18.0 15.5 94.8 Fieldtest 58 100 90.0 18.5 15.0 94.6 60 80 89.0 18.0 15.5 94.7 Table32FieldtestresultsofDaqingcrudeoilwithNP additionunderdifferentsecondarytreatmenttemperature viscosity 28apparentViscosity Treatment NP Pour decreasing mPa.s Decrease temperature addition Point Sample rate 1 1 1 1 1 g/t 20s 30s 40s 50s 30s % Untreated / / 2202 1668 1340 1210 33.5 / / Secondary 60/38 100 257 240 227 219 23.5 10.0 85.6 treatment 60/35 100 287 252 232 220 24.0 9.5 84.9 Table33Standingexperimentsunder25resultsofDaqingcrudeoilwithadditionby65treatment Standing Test Pour 25ViscositymPa.s Addition period temperature Point 1 1 1 1 20s 30s 40s 50s d 0 25 127.4 124.2 120.6 117.7 23.0 EVA 10 25 184.3 177.8 172.4 168.6 24.5 0 25 95.4 18.0 NP 11 25 125.0 18.0 From Table 32, it is found that when the treatment O temperature of Daqing crude oil with NP is 60 C, and downstream instation crude is secondaryheated up to 38OC and 35 OC, the pourpoint of crude decreases about 9.5 10, and the viscosity decreases between 84.985.6% at 1 28, 30 s , indicating that the modification effect continues tomeetthedemandoffieldapplication.Crudesecondaryheat up temperature decreasing greatly which can make sure that addingNPisaneconomic process, and it is more suitable for fullyloadedwaxycrudeoilpipeline.

3.2STATICSTABILITYOFDAQINGCRUDEOILWITH NP AND SHUTDOWN ANDRESTARTON BAODI INDUSTRIALLOOP The results of static stability test of Daqing crude oil by adding EVA and NP respectively in thermostat at 25 are shownintable33. Table33showedthatDaqingcrudeoilisstillNewtonian fluidafterstandinginthermostatat25for11days, thepour pointwithoutchange,andtheviscosityincreased less than31 %.AllofthosearebetterthanEVA.Itmeansthattherecovery time of crude gel structure is prolonged after modification by

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adding agent [1] and the crude keeps low temperature fluidity andstaticstabilitylong. 3.3 SHUTDOWN AND RESTART AT BAODI INDUSTRIALTESTBED Shutdown and restart of Daqing crude oil with NP at Baodiindustrial testbed wasdone, while the Baodi instation crude oil was led to loop for test. The diameter, length and groundtemperatureofthetestpipelineare150mm,300mand 13respectively.

Tomakethetemperaturefieldofsurroundingsoilandin stationpipelineapproximatelyidentical,theBaodiinstation crudeoilhadbeenledtotestbedfor15daysbeforethe beginningofshutdownandrestart.Shutdownandrestartof withandwithoutNPwasnotbeginuntilthesurroundingsoil temperaturefieldwascomparativelystable.Theconditionsand resultsofshutdownandrestartareshowninTable34and Figure31.

Table34TestresultsforshutdownandrestaronBaodiindustrialtestbed(150,300m) underdifferentconditions Preceding Inlet Restart Shutdown Restart Restart outstation Addition temperature temperature period throughput pressure temperature g/t 3 h m /h kPa 58 35 0 30 5.0 50 438.25 30 5.0 50 276.46 58 35 100 25 18.5 50 464.86 20 99.0 50 518.19

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NPCrudeoilat30 From Table 34 and Figure 31, we found that the maximum of startup pressure of crude oil without agent was 3 438.25kPa(thesecondpeakcorrespondingto100m /h)when 3 the startup throughput and temperature was 50 m /h and 30 3 ,respectively.Thethroughputreached50m /hin2minutes. Along with time, the pressure was decreased and tended to become stable. At the same startup conditions, the maximum ofstartuppressureofcrudeoilwithNPwas276.46kPawhich was 36.9% smaller than the one without agent. And the 3 throughputreached 50m /h in 16 seconds. Thus, thestrength ofcrudegelstructurewasdecreasedafteraddingNP. When the startup temperature of Daqing crude oil with NP was25shutdownfor18.5hand20shutdownfor

20and25 99 h, the maxima of startup pressure was 464.86 kPa and 518.19kPa,andthethroughputhadtaken1.5and2minuteto 3 reach50m /h,respectively. The results of shutdown and restart offered technical supportforcoldcommissioningplanofHuludao and Fengrun pipeline.Accordingtotheresults,theinstationtemperatureof Daqing crude oil can be decreased by at least 5 with , prolonged safeshutdowntime anddecreased startup pressure. Temperaturedroptransportationofwaxycrudeoilcomestrue. 3.4 COMPATIBILITY RELATIONSHIPS BETWEEN NP AND WAXY CRUDE OIL AND INFLUENCE TO WAX CRYSTALLIZATIONCHARACTERISTICS

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Ideal pourpoint depressant for Daqing crude oil which containsmuchwaxhasnotbeendevelopedsofar [2,3].Because of NP as a kind of nanomaterial with four effects, Daqing crude oil crystallization character was changed, and the pour pointwasdecreasedgreatly. 3.4.1COMPATIBILITYRELATIONSHIPSBETWEENNP ANDWAXYCRUDEOIL The compatibility relationships experiments was done by using different distillate under atmosphere and vacuum and NP.ThepourpointsofdistillatewithNPareshowninTable3 5. FromTable35, itis noted that the pour point decreased performance of vacuum cut 2nd distillate by adding NP was the most obvious one whose pour point decreased by 20(from 49.5 to 29.5). Meanwhile the performance of

treatment at 85was investigated, and decrease of pour point was not enhanced by increasing treatment temperature. The second and third best distillates are atmosphere cut 4th and Vacuum cut 3rd, and their pour point decreased by 7and 12, respectively. The pour point of atmosphere cut 3rd, vacuum cut 1st, and vacuum cut 4th distillate decreased by 3.5,3and4.5,whichwerenotobvious.Theworstoneis residue,whosepourpointwasnotdecreasedbyaddingNP,but increasedby 2.5. The pour point of waxy crude oil, dependent on the content of wax and carbon number distribution of paraffin n alkanes.Thepourpointandwaxcontentof Daqingcrudeoilare 33.5 and 37.65%, respectively. The carbon number of paraffin nalkanesin Daqing crude oil and the melt point was showninFigure32.

Table35ComparisonresultsofdistillatepourpointbeforeandafterNPtreatment Treatment Test Addition Pourpoint Decrease Distillate temperature temperature Sample g/t Atmosphere / untreated / 28.0 / cut3rd 65 100 25 24.5 3.5 Atmosphere / untreated / 35.0 / cut4th 65 100 25 28.0 7.0 Vacuumcut / untreated / 19.5 / 1st 65 100 25 16.5 3.0 / untreated / 49.5 / Vacuumcut 65 100 35 29.5 20.0 2nd 85 100 35 30.0 19.5 Vacuumcut / untreated / 44.0 / 3rd 65 100 35 32.0 12.0 Vacuumcut / untreated / 38.5 / 4th 65 100 35 34.0 4.5 / untreated / 30.5 / Residue 65 100 35 33.0 2.5

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Fig32B Vacuumcut2ndDifferential ScanningCalorimeter Curve

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FromFigure32A,wefoundthatthenalkaneswhichnis less than 28 account for 70.5% in Daqing crude oil , and the [4,5,6] crystalstructuresareorthorhombicandtriclinic . The experiment results show that the difference of pour point decreasing performance of distillate is related to the contentandcarbonnumberdistributionofnalkanes. differentialscanning calorimeter testresultof vacuum cut 2nd was shown in Figure 32B, the wax precipitation temperature is54.8 and the temperature of peak crystallize is 51.3 . The paraffin carbon number concentrates in 23 to 28,andthecontentreaches 67.1%. The nalkanes inwhich n is lessthan28areallergic toNP so that obvious performance ofpourpointdecreasecanbefoundinvacuumcut2nd.

Having analyzed the above experiments results, we concluded that NP changed the orthorhombic and triclinic crystalline characters of nalkanes which n is less than 28. Along with the increasing of nalkanes content, the performanceofpourpointdecreaseisbetter. 3.4.2 CRYSTALLINE CHARACTER INFLUENCE OF WAXYCRUDEOILBYNP TheresultsofXraydiffraction anddifferentialscanning calorimeter testswereshowninFigure33.Dynamiccooling X ray diffraction tests of Daqing crude oil before and after addingNPresultswereshowninFigure35.

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Fig33A NP XRayDiffractionCurve From Figure 33A, we found that at under room temperaturealotofsmall angle crystalline peaks appear with wide halfpeak width which is 0.40.5(much bigger than crystal diffraction peaks minimum width 0.10.2 ), long interplanar distance. These all indicate that NP is a kind of microcrystallinestructure,whosediameterissmallerthan300 nm. ComparingFigure32Bwith33B,thecrystaltemperature rangeofNPisneartothatofDaqingcrudeoilvacuumcut2nd

Fig33B NP DifferentialScanningCalorimeter Curve distillate and covers that of Daqing crude oil paraffin. Therefore NP have joined the whole crystallization process of crudeoilafteraddingtoDaqingcrudeoil.Meanwhile,smaller particles of NP crystal may penetrate into paraffin nuclei to inducecrystallizationduringcrystallizationprocess. Crystal morphology Polarizing microscope of distillate beforeandafteraddingNP wasshowninFigure34.

Fig34A UntreatedVacuumcut2ndPolarizing Microscope500

Fig34BTreatedVacuumcut2ndPolarizing Microscope500

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From Fig34A and Fig34B, we found easily that wax crystals of vacuum cut 2nd distillate without NP at room temperature were big, dense and reticulate. After adding NP, thewaxcrystalswere nomore aggregate yetwhilethe particle diametersweresmallerthanthatbeforeaddingNP.Itindicated that waxy crude oil crystallization character was changed by addingNP. DynamiccoolingXraydiffraction tests ofDaqingcrude oil before andafter adding NP results were shown in Figure 35.

FromFigure 35Aand 35B, we foundthat 2 of Daqing crude oil and Daqing crude oil with NP showed a small crystallizationpeakat21.3under48and45 ,respectively , indicatingthat thewaxprecipitationpointofDaqing crude oil was decreased 3 . We conclude thatNPcan not only change waxy crude oil crystallization character, but also the inhibit paraffincrystallization.

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Fig35A VariabletemperaturescanningXRay DiffractionofDaqingcrude oil 4.CONCLUSIONS 1NP can improve lowtemperature fluidity of Daqing crude oil . Further, with a certain amount of NP added, the pour point and viscosity can be decreased by more than 15and 94%, respectively. Daqing crude oil pipeline can restartsuccessfullyat20after99hourshutdown. 2NP is related to the distribution of paraffin carbon number.Thenalkanesin which n is less than 28 are allergic to NP,andNP whose crystal temperature range covers thatof crude oil paraffin can change waxy crude oil crystallization character. 3NP can inhibit paraffin crystallization, and the wax precipitationpointofDaqingcrudeoildecreasedabout3by addingNP. REFERENCES [1] Zhang Dongmin, Zhang Lixin, Yang Mingshu, etc.

Fig35BVariabletemperaturescanningXRay Diffractionof Daqingcrudeoil withNP Research on Thixotropy and Viscoelasticity of Nanomaterialcontained Waxy Crude with Modification TreatmentThe10thNationalRheologyConferenceThesis Collection,2010197200 [2] Pang Wanzhong, Wang Biao, Chen Lidian. Sensitivity of DaqingWaxyCrudetoPour Point Depressant and the influence of non hydrocarbon componentsofDaqingWaxyCrudeonEffectofPourPoint Depression[J].PetroleumJournal,1995,16(2):125133 [3] Guan Zhongyuan, Wu Lijuan, Guo Shufeng. Research on Compounded Experiment for Pour Point Depressant of DaqingCrudeOil.Oil&Gas Transportation and Storage. 20082793741 [4] ZhangDongmin,JiangBaoliang,ZhangLixin,etc. Influence of Compounded Nanomaterial on Wax Crystallization Characteristics of Waxy Crude. Oil & Gas Transportation andStorage..2011304249254

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[5] Filatov SK and Kotelnikova EN.LIMITS OF ISOMORPHOUS SUBSTITUTION OF MOLECULES IN NORMALPARAFFINS AS A FUNCTION OF TEMPERATURE. Journal of Structural Chemistry 1993 34(4):593601. [6] Zhang Lihui,Sheng Kuilong, Pan Jinliang. Production and Further Processing of Petroleum Wax [M]. Beijing: ChemicalIndustryPublishingCompany,2008,3:1736

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