Utilization of α-olefins obtained by pyrolysis of waste high density polyethylene to synthesize α-ol

第37卷第3期燃料化学学报Vol, 37 No. 32009年6月Journal of Fuel Chemistry and TechnologyJun. 2009文章编号: 0253-2409(2009 )03-0302-09Utilization of a-olefins obtained by pyrolysis of waste high densitypolyethylene to synthesize x-olefin-succinic-anhydride based cold flow improversNorbert MISKOLCZI, Richard SAGI, Laszl6 BARTHA, I.via FORCEK( University of Parnonia, Chemical Engineering and Process Engineering Instiute,Department of Hydrocarbon and Coul Processing, Egyetem street 10, Veszprem, H-8200, HUNGARY)Abstract: A new route of utilization of a-olefin rich hydrocarbon fractions ohtained by waste polymer pyrolysis was investigated. aolin-succenic-anhydride intermediate-based pour point depressant additives for diesel fuel were synthesized , in which reactions neededa-ulefins were obtained by pyrolysis o[ waste high-density polyethylene ( HDPE). Fraction of a-olefins was proluced by the de-polymerization of plastie waste in a tube reaclor at 500 C in the absence of catalysts and air. C1, -n range of mixtures of olelfins andparafins were separated for synthesis and then, these hydrocarbons were reacted with maleic-anhydride ( MA) for formation of a-olefin-suceinic-anhydride intermediates. The olefin-rich hydrocarbon fraction contained approximately 60% of olefins, including 90% - 95%a-olefins. Other intermediates were produced in the same way by using commrcial Cx a olein insted of Cr - olefin mixture. Thetwo diferent experimental intermediates with number average molecular weights of 1 850 g/mol and 1 760 g/mol were reacted withdiferent alcohols: 1-butanol, I-hexanol, I-octanol ，i-butanol, and c-hexanol lo produce their ester derivatives. 'The synthesized tenexperimental pour puint depressants were added in diflerent concentrations to conventional diesel fuel, which had no other additivecontent before. 'The structure and eficiency of experimental additives were fllowed by diferent standardized and non-standardizedmethods. Resuls showed that the experimental additives on the busis of the product of waste pyrolysis were able to decrease not only thepour but also the eloud point and cold filter plugging point (CFPP) of diesel fuel, whose efecte could be observed even if theconcentration of additives was low. Furthermore, all aditives had anti-wear and anti friction ffects in diesel fuel.Key words: waste polymer; chemical recyeling; petrochemical utilization; a-olefin-succinic anhydride intermediate based pour pointdepressant; antiwear and antifriction electsCLC number: TF624.8Document code: AFor diesel fuels ( especially in winter) the pourwhich the most prospective is the so called chemicalpoint depressant additive is one of the most importantrecyceling when the long carbon chain of plastics arecomponents of additives or additive packages.cracked into smaller fragments basically because of theCenerally, the pour puint additives are able to decreasethermal effect. Generally, the destruction reactions arethe cloud point and cold filer plugging point too. Thecarried out between 450 C and 1 000 C depending ona-olefin-succinic-anhydrideintermediate-basedthe raw materials and the target products. Namely, theadditives are widely used as pour point depressants information of gases can be observed over 700 C，andthe oil industry'-n.therefore, 450 C ~ 700 C is used when the mainThere are more interests to find alternative waysproducts are liquids (e. g.，gasoline, light oil, etc. ).for their replacement or at least to find other sources ,In thermal cases, the chain broken reactions are donewhich can considerably decrease the prices ofby radical mechanism and liquid products are aliphaticfeedslocks, such as olefins and other petrochemicals.olefins and paraffins in case of polyolefin ( HDPE andIt is also well known and demonstrated in thePP) pyrolysis. To reach the higher yield of a-olefins ,publications that the plastic consumption isthe polyethylenes ( LLDPE, LI)PE, HDPE, etc. ) areconsiderably increasing (by 3. 0% ~4. 0% annually )preferred. In our case it is important because, as it isand it is over 300 Mu nowadays. The problems ofwell known, there are quite big differences among theplastics are twofold: the increasing consumption ofreactivity of dfferent olefins ( vinyl，vinilydene,plastics generates higher prices of their raw materialsvinylene) during reactions of co-polymerization (e. g( especially olefins )，while the utilization of thewith MA). 'The a-olefins have the best property for theenormous waste plastics is a critical but unsolvedmentioned reacsos-223-30)0 .problem. To solve the environmental problems of wasteThe Exxon Research and Engineering Companypolymers ( decrease the mass of waste plastics )synthesized such pour point depressants on the basis ofnumerous recycling ways have been developed, from the reaction of_ maleic-anhydride and olefins with中国煤化工Received date: 208-12-11; Reccived in rerised form: 2009-03-24.YHCNMHGCorresponding author: Ricthard Sopj, E-mail: rspf@ almos. uni-pannon. hu.First author: Norhert Mskolezi( 1978-) , male, PhD, astant polessor, waste polymer relig.本文的英文电子版出Elsevier出版社在ScieneDireat上出版( htp://www. sciencediret. comv/ mience/jumal/18725813)。第3期Norbert MISKOLCZI et al; Uilization of a-olefins obtained by pyrolysis of waste high density polyethyle-..303different carbon length, which were used in lubricatingmethods. Additives on the basis of the product of wasteoils' 121. The copolymers were synthesized at 70 C ~pyrolysis were able to decrease not only the pour but80 C for 18 h in the presence of aromatic peroxidealso the cloud point and CFPP of diesel fuel.catalyst and then， they were purified by dialysis.Furthermore, these effects could be observed even ifPurified copolymers were reacted with different alcoholsthe concentration of additives was low. All additivesin the presence of p-toluene-sulphonic-acid. It washad anti-wear and anti-friction effects in diesel fuel,found that among the used alcohols， the estertoo.derivative of 2-ethyl-hexanol gave the best result in thepour point depressing effect.ExperimentalSimilarly, as it was said before, the Standard Oil1.1 MaterialsDevelopment Company also produced pour point1.1.1 Cracking apparatus and a-olefin rich fractiondepressants by the use of individual a-olefins andFor production of a-olefin-succinic-anhydridemaleic-anhydridel4,t5. In their experiments maleic-intermediate，a-olefin rich fraction obtained byanhydride and C2-18 a-olefins were used in differentpyrolysis of waste high density polyethylene ( HDPE)molar ratios in different solvents as benzene,and commercial maleic-anhydride were used. Thechloroform，and diethyl-ether in the presence ofapplied cracking apparatus is a tube reactor with threebenzoyl peroxide catalyst. The temperature of reactionmain parts: feed unit, reactor, and separation unit.was basically affected by the characteristie of solventsThe pyrolysis temperature inside the tube reactor wasand the solvent impurities were disilled at air pressure500 C and in order to reach higher yields of a-olefinsfrom the copolymer end products at the end of theno catalyst was used. As it is well known, the catalystsreaction. Numerous differences were observed amongcan modify not only the carbon frame of the productsproperties and efficiency in their pour point depressantbut also the position of the double bonds because theyeffcts. It was found that the longer the chain of olefinsare rather shifted to internal position fromthe deeper was the pour point.terminal23-26). It is very important from the point ofThere are some patents which mentioned the waysview of further applications because of the fact that theof the synthesis of pour point depressants by thereactivity of olefins with different structure is notablyreaction products of maleic-anhydride and differentdifferent. Gases, light oil, and heavy oil were formedunsaturated hydrocarbons , especially a-olefins' 1.171.in the decomposition reactions from which the light oilThe aim of our work was to produce a-olefin-was used in our experimental work. Light oil wassuccinic-anhydride intermediate on the basis of poucondensed using a water condenser(20 C ) thenpoint depressants for diesel fuels. a-olefin rich fractioncollected and analyzed， whereas heavy oil waswas obtained by pyrolysis of waste high densitywithdrawn into a closable borosilicate glass samplepolyethylene because we wanted to investigate theholder.possbility of the petrochemica-like utilization of theThe main properties of the used light oil are shownproducts of pyrolysis. The fuel-like or energeticin Table 1.application of the products of waste plastic treatment iswidely demonstrated in the publications but theirTable 1 Main properties of the c-olefIn rich fractionobtained by pyrolysis of waste HDPEpetrochemical utilization is a new but perhaps moreprospective route in case of selectively collected purStandardPropertiesLigh oildeviationpolyolefins. In the first five cases, a-olefin-succinic-anhydride intermediate was synthesized by usingCarbon numberC1-nmaleic-anhydride and a-olefin rich fraction of pyrolysisOlefins /%VinyI /%4and it was reacted with different alcohols: 1-butanol,Vinylidene /%31-hexanol，1-octanol， i-butanol， and c-hexanol lVinylene /%produce their ester derivales. Other five experimentalParafins /%4:additives were produced in the above mentioned waOthers /%using commercial C20 a-olefin instead of CI, -n olefinDensilv p/.cm-)(at 20 C )0.8220.002mixtures. Then， the ten experimental pour pointPoul中国煤化工8depressants were added in different concentrationsRef iYHCNMH G207.4490 0. 0005(0.01%, 0. 05%, 0. 1% and 0. 2% ) to conventionalAol5diesel fuel， which had no other additive contentKin.viscosity at 40 C /mm'.s~3.840.04before. The structure of experimental additives wasSulphur content /mg*(kg) -'nofollowed by different standardized and non-standardizedImpurities304燃料化学学报第37卷Its carbon number distribution was between C17-22instrument. The anti-wear property, namely, the wearand contained olefins，paraffins, and other compoundsscar diameter ( WSI) )，which was characterized( napthenes and aromatics ). According to FT-IRaccording to ASTM D-2783 88 slandard. For theanalysis，the vinyl position olefins meant the dominantdetermination of the anti-riction eficiency, a Pt-100part inside olefins was more than 90% related to alltype thermometer was connected to the test equipmentolefins, which should have been enough for additiveand through an A/D converter to a PC. The dala weresynthesis with acceptable reaction rale and conversion.recorded and figured in a PC. The principle of ourOther properties seemed like a commercial diesel fuel.method is on the basis of the relation that the higherSulphur and other impurities were not measured, whichthe friction between the two surfaces, the higher theis quite a big advanlage not only in case of energyfinal temperature.utilizalion of hydrocarbons but also in their utilization1.3 Pour point depressantsfor additive synthesis. Namely， impurities can1.3.1 ExperimentaladditivesFirst，theconsiderably decrease the reaction rale of botlinternediates of experimentaladditives wercopolymerization and esterification.synthesized by reaction of commercial maleic-anhydride1.1.2Reference olefin and alcoholsTo compareand light oil or C2o a-olefin in organic solvent at 100 Cthe properties of experimental additives on the basis of~ 150 C. The process was initiated by peroxidea-olefins obtained by waste HI)PE; pyrolysis referenceradicals and molar ratio of 1: 1 was used. The olefin-additives were produced applying same conditions butsuccinic-anhydride reaction products were eslerified byin these experiments, a commercial C20 c-olefin -1-octanol，1-hexanol， l-butanol， c-hexanol， andobtained by Sigma-Aldrich - was used instead of thei-butanol in solvent under nitrogen atmosphere by theC1-22 light oil.use of catalyst. The reaction temperature was betweenTo reach the predicted structure of pour point110 C ~ 170 C depending on the boiling point of thedepressant additives the a-olefin-succinic-anhydridealcohols. At the end of the reaction procedure, theintermediates were reacted with different alcohols :ester products were purified by evaporation of the1-octanol，1-hexanol， 1-butanol， c-hexanol， andvolatile components and filtration. Table 2 gives morei-butanol, which were also commercial reagents frominformation about the composition of experimentalSigma-Aldrich.additives. From DP-6 to DP-10， additives contained1.2MethodsStandard and non-tandardizedonly synthetie and pure commercial reagents， whilemethods for flow and other properties of additives wereintermediate of additives from DP-1 to DP-5 was formedused. Standard lests were the determination o[ acidby using light oil from wasle HDPE pyrolysis.number, maleic-anhydride conlent, cloud point, pourTherefore, the first five aditives contained paraffinspoint, and cold filer plugging point.from raw materials.The structure of experimental additives wasTable 2 Raw materials of additive synthesesdelermined by infrared technique with a SHIMADZUIR-470 type spectrometer ( resolution: 2. 7 cm”,Additivea-olefin rich fraction + alcoholilumination: Globar light ，monochromator: LittrowDP-1Light oil from pyrolysis + n-octanolprism, detector: KRS 5 type detector with a pyromelerDP-2Light oil from pyrolysis + n-hexanolin crystal window vacuum cell) in the 400 cm~' ~DP-3Light oil from pyrolysis + c-hexanol4 000 cm~' wavenumber range.DP4Lighu oil from pyrolysis + n-bulanolThe average molecular weight and its distributionDP-5Light oil from pyrolysis + ibutanolwere measured by size exclusion chromalography. TheDP-6eicosene + n-octanolgel chromalograph syslem consisted of a Waters 1515DP-7eicosene + n-hexanollype pump, Waters 717 plus Aulosampler unit, andeicosene + c-hexanolWalers 2414 differential refractometer. Samples wereDP-9eicosene + n-butanoldissolved in tetrahydrofurane and then, filered on aDP-10 ".eicosene + i-butanol0.2 μm Millipore ( Millex filter) membrane. Dissolvedcompounds were separaled by three Ultraslyragel1.3.2 Acid number and maleic-anhydride content ofcolumns (7. 8 mm x 300 mm). The system wasaddit中国煤化工maleic-anhydnidecalibrated by using polystyrene standards and theconte: and 2. The acidcalibration curve was described by a 3" ordennumtYHCN M H Gde contetgavepolynomial.information about the degree of conversion of theThe anti-wear and anti-friction properties wereassumed reactions. These properties were measuredlested by a modified Stanhope-Seta four ballboth in case of the copolymer intermediates and第3期Norbert MISKOLCZI el al: Utilization of a-olefins obtained by pyrolysis of waste high density polyethylene...305_additives. The grealer was the decrease of the acidlight oil because paraffins were not able to react withnumber between copolymer intermediates and final .maleic-anhydride. The low amount of maleic-anhydridestructure of experimental aditives, the higher was thecontents showed that presumably homopolymerizationreaction conversion of esterification.could be done in addition to copolynerization but onlywith very low reaction rate.12eicosene1.3.3 Fourier transformed infrared analysis，100light oilExperimental additives were also investigated byinfrared technique. The infrared spectra of pour point80-depressants within the wave number range of4 000cm~' and 400 cm-' are shown in Figures 3 and茗60一4.40-_NC1C4_bAlcoholsFigure 1 Acid number of additives ( Slandard deviation was3 mgK0H/g) ( Acid numbers were 212 mgK0H/g and198 mgK0H/g in case of eicosene and light oil baseda-olefin-succinic-anhydride intermediates , respectively )_The acid numbers of eicosene and light oil-baseda-olefin-succinic-anhydrideintermediateswere212 mgK0H/g and 198 mgKOH/g, respectively , while4000 3500 3000250020001500 1000their maleic-anhydride contents were 1.5 mg/g andWavenumber σ /cm'1.7 mg/g, respectively.Figure 3 Infrared spectra of aditives (4000 cm~'400 cm~').a: DP-I; b: DP-2; c: DP-3; d: DP4; e: DP-5cicosene |Iight oil |ag 0.3b言02乏h0.0 Li-C4Figure 2 Maleic-anhydrid content of additives ( Standard2500 2000 1500 1000deviation was 0. I mg/g)( MA contents were 1.5 mg/g andWavenumber σ /em'1.7 mg/g in case of eicosene and light oil basedFigure 4 Infrared spectra of aditives (4000 cm-' 400 cm*)a-olefin suecinic-anhydride intermnediates , respectively)a: DP-6; b: DP-7; c; DP-8; d; DP9; e: DP-10Data well presented that the acid numbers andIn spectra of each sample typical vibrations of a-maleic-anhydride contents of theretically solvent andolefin-succinic-anhydride -ester polymers were detectedmaleic-anhydride free additives closely approachedwith some disparities of products from two differenttheir theoretical values， which predicted the highintermediateg ( hv the 11e nf commercial pure eicoseneconversion of copolymerization and esterification inand a-中国煤化工cracking of waslecase of each additives. It could also be concluded thatHDPEYHCNM H G$were observedthe degree of esterifcation was lower in case of lightbetween , wucm ana 。oU cm 1 because of theoil-based copolymer, than by the other intermediate.alkyl chains from olefins and paraffins， both whichThe lower rates of conversions were caused by thewere built and not built in the polymer structure.saturated hydrocarbon content ( approximately 40%) of306燃料化学学报第37卷Otherwise, this range is the range of C- -H stretchingadditives synthesized withvibration of - -CH2- and - -CH; groups: asymmetric1-octanol ( DP-1 and DP-6 ). Some differences(u。CH2 ) and symmetric ( v,CH2 ) stretchingwere observed in the wave number range of 800 cm-vibrations of the- -CH2- groups resulted in absorption~ 1 000 cm~'，where C-H stretching vibrationsbands at wave numbers of 2926 cm -1 and 2 836 cm ~',caused infrared bands. The infrared band at 720 cm~respectively，while those of 一 -CH， groups atwas caused by the mowing vibration ( β。CH2) of2962 cm~' and 2 872 cm -1 , respectively.一CH2一groups. The intensity of this band wasOn the FT-IR spectra of intermediates, the threeproportional to the length of carbon chains.characteristic bands of five membered succinic-1.3.4 Results of size exclusion chromatography Theanhydride rings， which were built in the copolymerstructure of the additives was measured by sizestructure, were well visible from the symmetric andexclusion chromatography ( SEC) too, and Table 3asymmetric stretching vibrations of C= 0 that was theshows the results of this analysis. On the basis of datamore intensive, which was found at lower wave numberavailable considerable differences were observed among(1 700 cm~'). This band is referred to the ring likefinal structure of polymers that were synthesized bystructure. In the wave number range of 1 140 cmusing commercial , pure eicosene, and light oil, which1 000 cm，the asymmetric stretching vibration cwas obtained by pyrolysis of waste HDPE. The averageC-0-C gave an intensive band. In some cases, FTnumber of molecular weights of eicosene on the basis ofIR activity was found in the range of aromatic anda-olefin-succinic-anhydride intermediate and light oilolefinic materials, which is referred to the unreactedthebasisof a-olefin-succinic anhydrideolefins and aromatics from solvent that could not beintermediate were 1 850 g/ mol ( polydispersily (a) oftotally removed from the intermediates and additives.1.40) and 1 760 g/mol ( polydispersity of2.15) onAfter the esterification some C = 0 bands werethe basis of polystyrene standard, respectively. Nofound mainly from esters. These were separated fromsignificant difference was observed between the twoC= 0 bands of copolymers ( intermnediates ) becausedifferent intermediates ，which means that presumablythese could be seen in lower wave band ranges. Thesimilar structure could be synthesized. Otherwise, thecarboxylic-acid refer bands were more intensive in casesimilarity of the intermediates could be predictable fromof alcohols with lower carbon atoms (e. g. DP4,he FT-IR spectra of experimental additives (see inDP-5, DP-9 or DP-10) , than in other case , while thesection 1.3.3.).intensity of two bands were nearly equal in case ofTable 3 Average molecular weights of additives ( Standard deviation was 50 g mol)Light oil bused alen-succinic-anhydrideEicosene based a oelen-succenic-anhydridePropertiesintemediateinternediateAdditiveDP-1DP-2DP-3DP4 DP-5DP-6DP-7DP8DP9_ DP-10AlcoholCxCc-C6C。i-Csc-C。i-C,M./g.mol -1247022502020198021102300 2 3602100 2130 2 260M./g.mol”' 50604880 4280 4850 4 8703 88043303440 3 8503 730M,/g'mol -8 9008780 7 100 6750 6 9908330 8 2406710 6490 6 550Mp/g*mol-'3 0003 1302450 2 4602 21035203 1902 5203300 2 8002. 052.172.12 2. 452. 311.691.831. 641.811.65The weight average molecular weight (M.) ofadditives，perhaps the saturated hydrocarbon contentadditives was between 2 360 g mol and 2100 g/mol incould be blamed, which was not suitable for reactingcase of the last five additives, while that of the firstwith maleic-anhydride and producing the expectedive additives was between 2 470 g/mol andstructure. In contrast, the more variation of the olefin1 980 g/mol on the basis of polystyrene standards. Itstructure in light oil could support the formation ofmeans that the structure variance of polymers that weredifferent polymer structure as data of polydispersitiesproduced by the use of light oil was greater than that of3how中国煤化工in the last five cases when commercial pure eicoseneanalyses and gelwas used. The polydispersity in the last five cases waspernYHC N M H Gollowing scheme ofnearly 1.64~1.83, while in the first five cases it wasreaction was supposed ( Figure 5)，where m is thebetween 2. 05 ~ 2.45. In one hand, for the lowernumber of monomers of intermediate, n + 3 is theaverage molecular weight in case of the first fivcarbon atom number of a-olefins, and h + 1 is the第3期.Norbert MISKOLCZI et al; Utilization of a-olefins oblained by pyrolysis of waste high density polyethle..307carbon atom number of alcohols, which were used inesterification.ax-olefin(m+1CHfCHCHjJCH=CHsolventinitiator(m+1) o=maleic-anhydridea-olefin-succinic anhydride intermediate+2(m+1)CH(CHXOHCH o=+(m+1)HO。CH, ImCH,'Ch CHa-olein-succinic anhydride iniermediate cster derivatewhere k=3, 5or 7;m-0-6;n=7-10Figure 5 Possible reaction scheme2 Results and discussionmaterial obtained by HDPE pyrolysis could be theCloud point， pour point and CFPPreason in case of C17-n a-olefins-suceinic-anhydridedecreasing effects The experimental pour pointintermediate on the basis of experimental additives. .depressant additives were blended in concentrationlevels of 0. 01%，0. 05%，0. 10%，and 0. 20% to75F! 001%■0059conventional diesel fuel produced by MOL Plc. ，0.10%口0.20%Danube Refinery. Then, the most important so calledcold side properties ( pour point, cloud point, coldfiter plugging point ( CFPP )) were measuredaccording to relating standards. The diesel fuel had a .density of 0. 859 g/cm' , sulphur content of 32 mg/kg,豆25-cloud point of -2 C, pour pointof - 12 C, CFPP of-5 C，viscosity of 3. 80 mm'/s (at 40 C)，andflash point of95 C. Figures 6~ 11 show the changesof cloud point, pour point, and CFPP of diesel fuelDP-1DP-2DP-3DP-4DP-5containing diferent concentrations of experimental .Figure 6 Relative pour point decreasing efeet of additives onadditives.the basis of light oil product of pyrolysisAs the Figures 6 and 7 show, the most significant(Pour point of diesel fuel was -12心)difference between the two different type of25 F0.01% 0.05%experimental additives was the tendency of relative1.10%口0.20%pour point decreasing efect. In case of additives on the100 tbasis of C2 a-olefin-succinic-anhydride intermediate ,increasing tendency was found in relative pour point75decreasing efficiency, that is to say higher efciency ofadditives could be observed with their increasingconcentration ( Figure 7 ). On the contrary， theefficiency of additives produced from C17-2 a-olefins-25 tsuccinic-anhydride intermediate decreased with theirincreasing concentration ( Figure 6). It was also statedDP-9 DP.10that the eficiency of DP-1- _DP-5 was similar to the中国煤化工esterified products of C20 a-olefin on the basis ofintermediate in their lower concentration range ( belowFigure.MYTHC N M H Geffet of adtives onthe basis of eicosene ( Pour point of diesel fuel was -12 C)0.1%).For the unfavourable tendencies on Figure 7，As it was mentioned before the olefin rich light oilpresumably the saturated content of light oil raw308燃料化学学报第37卷contained also approximately 40% of saturatedThe decreasing tendency of eficiency on Figure 8compounds besides 60% of olefins ( intemnal andshould also be the consequence of the saluratedterminal). If the temperature and vacuum pressureimpurities of additives. In each case, the best resultwere not adequate for the separation via their boiling,was found when n-octanol had been used forthey could quite easily be stayed at the mixtures ofesterification in the second reaction. Change of cloudreaction end-products. The paraffin is unfavourablepoints could be seen only relating to nonbranchedcompound during the decrease of pour point decreasealiphatic alcohols. The cloud point decreasing effectbecause actually paraffins can cause higher values ofwas better at approximalely 300% when DP-1 andpour point via their crystallization ( both initiation anDP-2 was used in 0.01%, whereas it was only 250%nucleus growth). The higher was the concentration of of DP6 and DP-7. Increasing their concentration tothe experimental additives conlaining also accumulaled0. 20% , the values were dropped to 200% in case ofparaffins， the worse was the pour point decreasingDP-1 and DP-2, while that increased to 400% of DP-6efficiency.and DP-7.In relation to alcohols from same structure budifferent carbon atom number, the best pour point400 F- 0.01% .0.05%decreasing efeet of experimental additives was found in0.10%口0.20%case of reaction product of intermediates and 1 -octanol ,，300where the relative efficiency was approximately 75%and 70% in case of light-oil-based and eicosene-based-additives ( using 0. 01% of additive) , respectively. If; 200their concentration reached the 0. 20% the efficiency( with contrary tendency) could be modified to 50%100and 125% of light-oil-based and eicosene-basedadditive, respectively. If the structure of alcohols waschanged no considerable difference was found in lowerDP-6DP-7DP-8DP-9 DP-10concentration range， but the DP-10 had a bitFigure 9 Relative cloud point decreasing eflet of additivesfavourable property than DP-9 using 0. 10 and 0. 20%based on eicosene( Cloud point of diesel fuel was -2 C)concentration. It means that the branched structure ofalcohol was more advantageous in pour point depressingThe cold filter plugging points of diesel fuels canthan linear alcohol relating same carbon number. Thebe found in Figures 10 and 11 ，which partly showedsame result was found in the experimental work ofdifferent result as it was mentioned. Because aditivesothers, which was declared in lots of patents andfrom DP-6 to DP-10 gave betler results than DP-1-DP-scientifie papersl12-15.5, but, in interesting way， the cold filter pluggingSimilar results were found on Figures 8 and 9,point was the lowest using n-butanol instead of n-which represent the change of cloud points of fuels withoclanol. It means that the lowest was the carbonthe concentration of additives.number of alcohol and the best was the CFPP. Thistendency was opposite to that mentioned above.300- 0.01%口005%o 0.10%口0.20%125! 0.01%二005%! 0.10%口0.20%e 20075t 100三50DP-1DP-DP-3DP-4DP-5中国煤化工Figure 8 Relative cloud point decreasing efet of additivesJH.CNMH Gbased on light oil produet of pyrolysisFigure IU" Kelative CF PP deereasing efiet of additives based(Cloud point of diesel fuel was -2 C)on light oil product o[ pyrolyis( CFPPof diesel fuel was -5 C)第3期Norhert MISKOLCZA et al: Utilization of a-olefins obtained by pyrolysis of wasle high density polyethylene.. 309Other important property was the anti-friction175effect，which could be followed via the temperature1500.10% 口0.20%increase during operation. This property was also tested足125by four ball equipment, using 300 N load also. Thetemperatures of four samples were registered till1003 600s. Results are shown in Figure 13.751Generally, the anti-friction efficiency is better if250|the frictional heat is lower, i. e.，the temperalure islower. According to curves of lemperatures of diesel25fuels containing additives in the above mentionedamounts some differences could be seen among them.DP-6DP-7DP-8DP-9DP-10The lowest temperature could be registered in dieselFigure 11 Relative CFPP decreasing efet of additives basedfuel containing commercial additive package 0on eicosene( CFPP of diesel fuel was -5 C)0.05% , bul the other two experimental additives werealso able to decrease the friction between the surfaces2.2Anti-wear and anti-friction effects Tof steel balls during the whole test because theyinvestigate the anti-wear or anti-friction properties, thedecreased the temperature of test fuels with 0. 05%additives were tested by so called four ball tests, as itwas mentioned before. In this test， the anti-wearadditive content.property of additives were followed via the wear scar7:diameter ( WSD) of stainless steel balls. Results areshown in Figure 12. In this experiment, the additives)Fwere blended to diesel fuel and results were compared5(with those found by the use of commercial additivepackage. The used experimental additive content was. DF+DF-60. 05% and the sulphur content of the test diesel fuelDF+DF-1(DF) was 14 mg/kg. The applied load was 300 N and- DF+packagein case of commercial reference additive package also0. 05% was usedAs Figure 12 shows， the0 500 1000 1500 2000 2500 3000 3500 4000experimental additives could decrease the wear scarTime 1/sdiameler on the stainless steel testing ball related to thetest diesel fuel. 'The decreasing ratio of WSD was theFigure 13 Change of the temperature of diesel fuels duringhighest (25. 4%) when additive package was used,the tests ( Standard deviation was2 C)but this value was 22. 5% and 23. 8% in case of DP-13 Conclusionsand DP-6 additives, respectively. Both experimentaladditives were synthetized by using of Cg a-alcohol andThe decreasing of the pour point, cloud point,only the inlermediales were diferent, as Table 1and cold filter plugging point was found by the use ofexperimental additives， but significant differenceshows.between the two different groups of the experimental1.2 Fadditives was found. In case of additives on the basisof C2n a-olefin-succinic anhydride intermediate,0上increasing tendency of relative cloud, pour point, andCFPP decreasing effects was found， while that a.8 tadditives produced from C17-22 a-olefins-succinic-anhydride intermediate was decreased with theirconcentration. The reason behind the phenomenon was0.4 the saturated hydrocarbon content of light oil raUn心matelis in case ofC17-22a-ole中国煤化工ermnediatebasedexper:YHC N M H Gre, additives hacDDF+package DF+DP-1DF+DP-6anti-wear and anti-friction properties in diesel fuel atFigure 12 Change of the wear scar diameter on test balls0.05% concentration level.( Standard deviation was 0. 05 mm)310燃料化学学报第37卷References[1」 COUTINIOJ A P, MIRANTE F, RIBEIROJ C, SANSOT J M, DARIDON」L. Cloud and pour points in fuel bleds[J]. Fuel, 2002, 81(7):963-967.2] ht:///w./ chevron. com/ po/vst/0tfeu/s/ou/durue/Dieserer F'uel. _Tech. _Reriew. pdr (acesed 2009).[3] WANC s L, FLAMBERG A, KIKABHAI T. Select the optimum pour point depressant: Feedsocks and products[J]. Hydrocabon Process,1999，(78) 59-62.4] MACHADO A L C, LUCAS E, CONZaLEZ C. Poly( ethylene cninil-aretate) ( EVA) as wax inhibior of a Brailian crude oil: 0il vscosit,pour point and phase behaviour of ongaie solutions[J]. 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