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This research carries out a critical reappraisal on old work done on wax precipitation and deposition. However, the chief focal point of this work is on pour point. Several researches done on pour point were reviewed. Most of the work done by research workers was on pour point of oil/crude oil and methods of depression. Most of the sedative were successful but this depended on the petroleum oil content at most cases. The linear or depressant chemical construction besides in some instances affected the result of the pour point depression. In some other instances, the molecular weights of the sedatives affected the result of the pour point depression. With mention to concentration, when the concentrations of the sedatives were reduced, an addition in pour point was realized. Conversely, when the concentration was increased, there was an addition in pour point depression.

Chapter 1

Introduction

Wax deposition and control continues to be a challenging job in the oil and gas industry. This is because rough oil contains a mixture of waxes which precipitate out of solution at low temperature and force per unit area conditions. These waxes include normal methane seriess, isomeric methane seriess, alkyl cyclic compounds and alkyl aromatics. However, normal methane series or paraffin waxes are the major types present in petroleum hence, more widely studied. Paraffins with high molecular weight ( C20 to C40 ) are the chief causes of flow confidence jobs in cold environments as respects wax formation and deposition, particularly in subsea grapevines were the temperature could fall below 4A°C. At high adequate temperatures these high molecular weight waxes are dissolved in the petroleum and remain in solution. No formation or precipitation occurs at these temperatures but as the temperature drops below the wax visual aspect temperature ( about 20 degree Celsius ) wax is progressively deposited along the wall of the grapevine and some paraffins dispersed in thecrude. However, if chilling continues, these dispersed paraffins bit by bit accumulate to organize a white odourless, tasteless and waxen solid known as parrafin wax. In the crude oil industry, wax precipitation is unwanted because it may do plugging of grapevines and procedure equipment ( Galeana, 1996 ) . The presence of these waxes thickens the petroleum oil and a uninterrupted physique up of wax could finally choke off the grapevine which could take to a complete loss of production, ensuing in shut down which would intend cost the company allot of money to undertake the job.

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Nowadays, there are many methods of wax extenuation. These include:

Piging ( affecting a hog which automatically scuffs wax from the walls of the grapevines ) .

Chemical dissolver and solvents

Thermal techniques ( which involves keeping the petroleum oil temperature above the wax visual aspect temperature.

Wax inhibitors ( like dispersants, wetting agents, crystal qualifiers and pour point sedatives ) .

Wax precipitation could do operational jobs or finally damage down hole and topside equipment although this occurs more often in subsea equipment as a consequence of really low ambient sea temperature. Because of the long concatenation waxes in rough oil, they are more hard to command compared with those present in condensates. The wax visual aspect temperature could be every bit high as 50 degree Celsius for some oil and depends on the force per unit area, oil composing and the bubble point ( Kelland, 2009 ) . This high temperature as respects composing is normally as a consequence of the length of the paraffin concatenation present. Normally, the longer the concatenation the higher the thaw point and hence, the more hard it is to maintain it in solution. Besides with a high adequate force per unit area, waxes could get down to organize at temperatures every bit high as 50 degree Celsius or over. It is by and large accepted that the conditions for wax formation or deposition are high force per unit area and low temperature. However, this implies that the lower the temperature the more likely it is for waxes to precipitate out of solution, since waxes could still be deposited at well higher temperatures.

There are several methods of wax control for the oil and gas industry, nevertheless, this reappraisal focuses on methods of pour point depression.

Chapter 2

LITERATURE REVIEW

3.1 Microbial intervention of waxen petroleum oils for extenuation of wax precipitation

( Etoumi A, 2007 )

Etoumi, A ( 2007 ) carried out an experiment on microbic intervention of waxen petroleum oils for extenuation of wax precipitation. The stuffs used in the experiment are discussed briefly below.

3.1.1 Sarir petroleum oil

The Sarir petroleum oil was obtained from the Sarir field in eastern Libya. The oil is production is done through a 34-inch grapevine to the Tobrok terminus abd the distance between the field and the seaport is about 513.6A kilometer. The oil from this field has a wax content of 13 wt. % , sulphur content of 0.133 wt. % , API gravitation of 35.9, and Pour point temperature of 24A A°C.

3.1.2 The micro-organism

Microbes were acquired from saltwater deposit contaminated with hydrocarbon. The deposit samples were gotten from different locations of Alharka terminus in eastern Libya.

Enrichments civilization experiments were done in batch experiments utilizing a bioreactor incorporating 1.8A L of Enrichment Salts Medium ( ESM ) . The salt medium was sterilized, and after sterilisation, saltwater deposit and rough oil were added to the sterilized ESM. The bioreactor was kept at a temperature of 37A A°C. The incubation was 7A yearss.

The bacterial civilizations isolated were PRCW E1, E2, B1, B2, A1, and A2. PRCW B1A was identified as PseudomonasA species and PRCW E1A and E2A were identified as filiform type ofA ActinomycesA species through microscopic scrutiny.

Fig 2: A Pure isolated civilizations ( Etoumi A, 2007 )

Fig. 3A Growth curve of isolate PRCW E1. ( Etoumi A, 2007 )

Fig. 4: A Growth curve of isolate PRCW B1. ( Etoum

Table1: Specific growing rate and emulsification activity per centum on kerosine of six isolates. ( Etoumi A, 2007 ) .

Isolates

Growth rate ( ha?’A 1 )

E24A ( % )

PRCW A1

0.0673

36

PRCW A2

0.1365

53

PRCW B1

0.2430

90

PRCW B2

0.0385

50

PRCW E1

0.1926

66

PRCW E2

0.0562

0

The consequence for the emulsification activity showed the isolates were able to emulsify n-hexadecane and Sarir petroleum oil which are non-miscible hydrocarbons. The isolates produced considerable sum of bio-surfactant during growing on 0.5 % ( v/v ) ofA n-hexadecane.A Table 1 shows the specific growing rate and emulsification activity of six isolates with Kerosene. Besides from the tabular array PRCW B1A and PRCW E1A had emulsification activity per centum ( E24 % ) of 90 and 66 % severally. Etoumi A, 2007 compared these consequences with other beings which produce bio-surfactant and suggested PRCW B1A may be a good campaigner to suppress paraffin deposition.

Harmonizing to Lazar et Al. ( 1999 ) , bacteriums control wax deposition by metabolizing bing paraffin already precipitated, so partly digest the paraffin by interrupting bonds between C atoms until the paraffin becomes more nomadic. When this is done, the bacterium attacks other paraffin molecules. This means they do non truly devour the oil.

Bio-surfactants formed by the bacteriums besides contribute to the dislocation of paraffins. Since the bacteriums easy move from one location to another, this contributes to the effectual interruption down of paraffins in rough oil.

Harmonizing to Etoumi A, 2007, gas chromatographic experiment on untreated petroleum oil, 1 and 5 % ( v/v ) petroleum oil with strains PRCW E1A and B1A showed a noticeable fluctuation. The consequences show that the microbic dislocation of paraffinic hydrocarbon at 1 % ( v/v ) was higher than that gotten at 5 % ( v/v ) .

Fig. 5: A Gas chromatograms of Sarir petroleum oil, ( A ) untreated petroleum oil sample, ( B ) 1 % ( v/v ) of treated petroleum oil with strain PRCW E1, ( C ) 5 % ( v/v ) of treated petroleum oil with strain PRCW E1. ( Etoumi A, 2007 ) .

Fig. 6: A Gas chromatograms of Sarir petroleum oil, ( A ) untreated petroleum oil sample, ( B ) 1 % ( v/v ) of treated petroleum oil with strain PRCW B1, ( C ) 5 % ( v/v ) of treated petroleum oil with strain PRCW B1. ( Etoumi A, 2007 ) .

WAT was measured after microbic treatment.A Table 2A shows that the WAT decreased well after intervention with isolate PRCW E1. However, no important alteration in WAT was observed when the petroleum was treated with isolate PRCW B1.

Table 2: A Wax visual aspect temperature of rough oil before and after microbic intervention.

( Etoumi A, 2007 ) .

Variable

Before intervention

Isolate PRCW E1

Isolate PRCW B1

WAT ( A°C )

50.94

38

51

3.2 INFLUENCE OF ALKANE CLASS-TYPES ON CRUDE OIL WAX CRYSTALLIZATION AND INHIBITORS EFFICIENCY

GarcA±I?a M, et Al. ( 2000 )

Garcia M, et Al. carried out a research on the influence of methane series class-types on petroleum oil wax crystallisation and inhibitors efficiency.

Seven samples of paraffinic petroleum oils were obtained from Venezuelan reservoirs. One commercial paraffin inhibitor ( maleic anhydride I±-olefin alkyl ester copolymer crystal qualifier, identified as C-9 ) was used. ( Etoumi A, 2007 ) .

3.2.1 Enrichment ( doping ) of petroleum oils with paraffin dressed ores

One gm of petroleum was heated to 60A°C for 10mins until complete thaw. Recorded measures of C13-C20 and C20-C44 paraffin fractions were so added.

Lighter petroleum fractions ( H2O and & lt ; 200A°C constituents ) were separated by utilizing atmospheric distillment. Asphaltenes were precipitated from the distillment residue withA n-heptane. Maltenes ( 1.5 g ) were deposited at the center of the pre-column. Saturates were eluted in the forward flow manner, after a pre-heating hold of 5 min, usingA n-heptane at 5 ml/min as the nomadic stage. The aromatics were collected utilizing the same dissolver, in the “ back flush ” manner at 10 ml/min. Resins were backflushed from the cyano columns with two consecutive elutions carried out at 10 ml/min with methylene chloride and chloroform/methanol 80:20 ( v/v ) . Solvents from the detached fractions were evaporated in a rotary-evaporator, and the residues were placed in a vacuity oven kept at 60A°C and 20 in. Hg, until changeless weight was achieved.

n-paraffins were removed by inclusion of the saturate fraction in a 5 A molecular screen, utilizing dryA i-octane as dissolver in a 1.5:150 ( wt/v ) ratio. The sample was refluxed for 24 H, so theA i-octane solution was decanted. The screens were refluxed twice utilizing the same dissolver, over two periods of clip of 30 min. TheA i-octane solutions were assorted and the cyclo+isoparaffins were obtained after solvent remotion by distillment. Normal paraffins were recovered after destructing the screens utilizing hydrofluoric acid.

3.2.2 Word picture of the detached fractions

The pureness of the saturates, aromatics, rosins and asphaltenes fractions was verified by Thin Layer Chromatography with Flame Ionization Detection ( TLC/FID. The & gt ; 200A°C residue and theA n- and cyclo+isoparaffin fractions were characterized by High Temperature Simulated Distillation ( HTSD ) .

3.2.3 Enrichment ( doping ) of petroleums with cyclo+isoparaffin dressed ores

Mixtures of rough oil and stray cyclo+isoparaffins were prepared and kept to about 500 milligrams, being placed in 10 milliliter phials. The dopant concentration varied between 27 and 64 wt % of the above mass. Sample homogenisation was carried out.

3.2.4 Crystallization alterations in petroleums and finding of the activity of a commercial paraffin inhibitor

Cloud point finding was used as a method to supervise the alterations induced on the petroleum oils by the add-on of the stray paraffin fractions. The activity of a commercial paraffin qualifier ( C-9 ) was followed utilizing the same cloud point measuring. Comparison was ever referenced to the original petroleum, and the inhibitor activity value ( cloud point depression ) corresponds to the original petroleum oil cloud point minus the additivated petroleum cloud point.

3.2.5 Effectss on the petroleum oils cloud point due to enrichment with light and heavy methane series dressed ores

Previous surveies show that multimodal petroleums, with abundant & lt ; C24 constituents ( Type II ) , were observed to better their belongingss with the usage of crystal.This is non the instance for monomodal petroleum oils, with big concentration of & gt ; C24 methane seriess ( Type I ) , which were found to be insensitive to the action of these inhibitors. To farther support these findings, man-made blends were prepared utilizing these two types of petroleums. Linear furnace lining Type I crudes were enriched with light methane series dressed ores ( C13-C20 ) in an effort to mime the Type II petroleums. Inhibitor sensitive Type II petroleums were enriched with big paraffins ( C20-C44 ) in order to mime Type I crudes. Representative C figure distributions for virgin petroleums can be observed in the chromatograms ( fig. 5 ) .A

Fig. 5: A Gas chromatograms of virgin petroleum oils: ( a ) petroleum M-4 ( Type I ) ; ( B ) petroleum G-8 ( Type II ) . ( GarcA±I?a M, et Al. 2000 )

Table 3: Activity of 2000 ppm of C-9 paraffin inhibitor on man-made waxy petroleums ( values in parenthesis=wt % & gt ; C24 ) . ( GarcA±I?a M, et Al. 2000 ) .

Virgin petroleum

C-9 Activity ( A°C ) a

Original

Man-made blendb

Type Intelligence community

M-4 ( 63 )

0

3 ( 33 )

N-9 ( 52 )

a?’2

1 ( 33 )

N-4 ( 77 )

3

a?’6 ( 33 )

N-6 ( 82 )

1

a?’3 ( 33 )

Type IId

G-8 ( 38 )

13

5 ( 63 )

O-7 ( 39 )

10

a?’1 ( 63 )

N-1 ( 31 )

11

5 ( 63 )

a – Cloud point depression regard to a control sample ( without additive ) .

b – Dopant=paraffins C13-C20 ( for Type I ) and C20-C44 ( for Type II ) .

c – Type I=monomodal crudes rich in & gt ; C24 methane seriess.

d – Type II=multimodal crudes rich in & lt ; C24 methane seriess.

After doping, linear furnace lining Type I crudes did non alter the behaviour to the presence of the C-9 crystal qualifier. At the same clip, doped Type II crudes drastically lost their response to this linear. These experiments support old findings in the sense that important proportions of heavy paraffins are found to be responsible for the inefficiency of crystal inhibitors. However, the add-on of light paraffins to refractory Type I crudes did non better the inhibitor public presentation upon them. This could be improved by increasing the concentration of light paraffins even more, but this is an unpractical and wasteful attack.

3.2.6 Isolation and word picture of methane series dressed ores from M-4 petroleum

The consequence of whole methane series fractions on wax crystallisation was investigated. Whole methane series fractions are normally known as “ saturates ” . In the instance of saturates, there are three class-types: ( I ) the additive or normal methane seriess ; ( II ) the iso or branched methane seriess ; and ( III ) the cyclic methane seriess, known besides with the term naphthenes or cycloparaffins.

Alkane class-type fractions were separated from M-4 petroleum oil with the intent of analyzing their consequence on wax crystallisation after doping the petroleum ( M-4 ) with these fractions.A Table 4 summarizes fraction outputs for each phase during M-4 rough oil separation. Recovery of stray fractions was 88.96 wt % . Losses ( 11.04 wt % ) occurred during the molecular sieving adduction, more specifically, during the devastation of screens andn-alkanes recovery.

Table 4: A Fraction outputs for M-4 petroleum oil separation ( values in parenthesis indicate wt % based on the original petroleum oil ) , ( GarcA±I?a M, et Al. 2000 ) .

Phase

Fraction

Output ( wt % )

Distillation ( 200A°C )

Volatile fraction

28.01 ( 28.01 ) a

Distillation residue

71.99 ( 71.99 )

Residue 200A°C+deasphalation

Asphaltenes

0.26 ( 0.19 ) a

Maltenes

99.60 ( 71.71 )

HPLC of & gt ; 200A°C maltenes

Saturates

77.61 ( 55.64 )

Aromatics

20.53 ( 14.72 ) a

Resins

0.88 ( 0.63 ) a

Saturates inclusion

n-Paraffins

33.28 ( 18.51 ) aA andA B

Cyclo+isoparaffins

48.31 ( 26.89 ) a

Entire

Recovered petroleum

( 88.96 )

a – Isolated fractions.

b – Noticed losingss were observed during this measure ( expected: 28.75 wt % ; found: 18.51 wt % ) .

Table 4A shows the C figure distribution for the whole petroleum, the & gt ; 200A°C distillment residue and its cyclo+isoparaffins. Abundance of & gt ; C24 constituents for the residue was 78 wt % , higher than the value matching to the whole petroleum ( 63 wt % ) . Removal of the light terminal constituents ( C5-C14 ) during distillment can account for this difference. The cyclo+isoparaffins fraction ( 26.89 wt % of the petroleum ) was found to incorporate 84 wt % of C24+ constituents. These findings show that iso+cycloparaffins are, in norm, larger in molecular mass thanA n-alkanes.

Table 5: A Carbon figure distribution of M-4 petroleum oil and its fractions by high temperature gas chromatography. ( GarcA±I?a M, et Al. 2000 ) .

Fraction

Distribution

& gt ; C24 ( wt % )

Whole petroleum

C5-C44

63

Residue & gt ; 200A°C

C14-C70

78

Cyclo+isoparaffins

C16-C60

84

Fig. 6A shows an expanded overlaid of the HTSD chromatograms matching to the saturates fraction from the whole petroleum and the one corresponding to its cyclo+isoparaffin fraction. Two types of signals can be distinguished: crisp extremums, attributed to theA n- and isoparaffins, and an intense bulge caused by the elution of the cyclic paraffins. The right assignment of theA n- and isoparaffins signals can be assessed with a elaborate review of the overlaid chromatograms. It is apparent that there is a keeping clip displacement in the cyclo+isoparaffins fraction. In other words, one or more compounds from these categories are eluted between two intense extremums matching to theA n-paraffins nowadays in the whole saturates fraction. For a more accurate favoritism, high-resolution chromatographic columns and internal criterions ( i.e.A n-paraffins ) are required. Some writers use NMR-DEPT techniques ( Nuclear Magnetic Resonance Distortionless Enhanced by Polarization Transfer ) to clearly separate between CH2A and CH3/CH signals in theA 13C NMR spectrum, which can assist for the confirmation of fractions pureness. However this was beyond the intents of the present survey.

Fig.6: A High temperature gas chromatograms of M-4 petroleum oil saturates and its cyclo+isoparaffins fraction. ( GarcA±I?a M, et Al. 2000 ) .

3.2.7 Consequence of petroleum oil enrichment with cyclo+isoparaffins fraction on the cloud point and wax inhibitor activity

Table 6A shows the cyclo+isoparaffins doses used for the enrichment of the M-4 petroleum oil. Five “ man-made ” petroleums were prepared ( entries 2-6 ) , with a brown waxy solid visual aspect at room temperature, similar to that of the original oil ( entry 1 ) . FromA Fig. 6, it is possible to detect that there is no alteration in the cloud point value below a cyclo+isoparaffins concentration of ca. 40 wt % . The selective add-on of branched and cyclic methane seriess appears to impair the ordination of wax crystals in the present instance. However, one time a critical concentration is surpassed ( ca. 45 wt % ) an addition of the cloud point is observed for the prepared man-made blends.

Table 6: A Enrichment of M-4 petroleum with its stray cyclo+isoparaffins fraction. ( GarcA±I?a M, et Al. 2000 ) .

Entry

Crude aliquot ( milligram )

Cyclo+paraffin

Sum added ( milligram )

Wt %

1

500

0

27

2

462

50

34

3

419

100

41

4

345

150

49

5

407

200

51

6

253

250

64

a – Deliberate concentration for the man-made M-4 blend.

Fig. 6.A Consequence of cyclo+isoparaffins concentration on the cloud point of M-4 petroleum blends. ( GarcA±I?a M, et Al. 2000 ) .

The activity of the commercial crystal modifier C-9 was besides evaluated for the samples presented inA Table 6, and the consequences are presented inA Fig. 7. The inhibitor activity was measured as the cloud point of the oil blend minus the cloud point of the inhibitor treated sample. Negative activity values represent an increase of the cloud point after inhibitor add-on, and the antonym is a better public presentation on the inhibitor activity ( a lessening on the cloud point in the presence of this merchandise ) . The zero point in the activity graduated table represents a void linear consequence. The consequences indicate a little lessening in the inhibitor activity up to 41 wt % of cyclo+isoparaffins, being the less affected the one for 8000 ppm inhibitor concentration. Beyond this point for paraffin concentration, the inhibitor activity starts to better up to a value of four grades. The improved inhibitor activity is likely due to an structural upset introduced in the wax crystals when the concentration of cyclo+isoparaffins is greater than ca. 50 wt % .

Fig. 7.A Activity of the commercial crystal modifier C-9. Experiments carried out with M-4 petroleum blended with its cyclo+isoparaffins fraction. a?- ( Activity determined as rough oil blend cloud point minus linear treated petroleum blend cloud point ) . ( GarcA±I?a M, et Al. 2000 ) .

3.3 Effect of asphaltenes on petroleum oil wax crystallisation.

Pavel Kriz and Simon I. Andersen

Pavel Kriz and Simon I. Andersen carried out research on consequence of asphaltenes on petroleum oil wax crystallisation.

Asphaltene-in-toluene blends were foremost prepared. Then asphaltene-in-toluene mixtures were blended with the oil to achieve the same concentration of asphaltene in all samples ( 0.1 wt % ) . The blending temperature which was found to be really of import was 90 A°C. If temperature was excessively low, the wax web was partially developed and the asphaltenes could non be to the full applied interior.

For each asphaltene-toluene-oil blend, a control sample was prepared to acquire rid of the influence of dissolver in consecutive experiments. This control sample was the rough oil diluted with the methylbenzene. The other set was prepared in a similar manner but the concentration of asphaltene was changed with fixed toluene concentration. The samples were prepared in concentration of 0.01 to 0.5 wt % of asphaltenes with toluene fixed at 28 wt % .

3.3.1 Wax Appearance Temperature ( WAT ) Measurement

WAT was calculated with the usage of polarized light microscopy. The sample was heated to 80 A°C and so cooled at a rate of 1 A°C/min to 0 A°C. This measuring was repeated three different times for each sample.

The experiment showed that the asphaltenes added to samples provided crystal sites for waxes.This occurred when asphaltene concentration was 0.05 wt % or higher. Conversely, at really low concentration ( 0.01 % ) , WAT was out of the blue high at about 10 A°C higher than the WAT for asphaltene-free oil. Pavel Kriz and Simon I. Andersen suggested that this behavior was due to the fact that the asphaltenes were absolutely dispersed or about dissolved and that they were impacting paraffins at the molecular degree. With this, there are a figure of likely crystal sites and they are merely approachable for paraffins because there are few asphaltenes per unit volume with more or less no hazard of spacial intervention. As asphaltene concentration is increased nevertheless, the surface country or figure of possible sites additions. Hence, possibly the WAT is additions besides. This all comes to an terminal when the critical asphaltene concentration in the solution is reached. Here, the highest WAT is rattained and the asphaltene flocculation begins. This decreases the surface country badly.

3.3.2 Interaction of waxes with pour point sedatives

Yin et Al.

Yin et Al. carried out an experiment on the interaction of waxes with pour point sedatives. The influence of pour point sedative on wax precipitation at low temperature was investigated. The sum of precipitated wax from the paraffin solutions with and without pour point sedatives were studied at different temperatures.

3.3.3 Material and Characteristic

Yin et Al. made usage of theoretical account oil which is composed of isooctane ( a crude oil distillation with pureness of 99.9 % ) and wax. The waxes which were supplied by Dallian Petrochemical Corporation were estimated to hold runing points of 57.2 degree celcius and 67 degree Celsius severally.

Fig. 8: composing of waxes as measured by gas chromatography. ( Yin et al. )

The pour point sedatives used in this survey were the derived function of poly long alkyl methacrylate ( CE ) and the alkyl naphthalene copolymer ( T801 ) .

Yin et Al. used two paraffin solutions to mensurate pour point. One of the solutions was made of 10 wt. % of 52.2 degree Celsius wax in isooctane, and the other on was made of 10 wt. % of 67 degree Celsius wax in isooctane. They were both heated to 80 grade Celsius for continuance of 2 hours and so left to chill standing as the pour points of the solutions with and with no pour point sedatives were measured by the Chinese national criterion GB 510-1983 method.

The consequences arrived at by Yin et Al. showed that pour point sedatives do non forestall wax precipitation to the full but merely do precipitation to happen at a lower temperature.

Since the pour point sedatives are effectual in different concentration scope, the concentrations of both sedatives were different for the experiment. Yin et Al. pointed out that for effectivity, the poly long alkyl methacrylate should be no less than 50 ppm and the alkyl naphthalene copolymer should stay in the scope of 0.1 to 1.0 % .

Samples

Composition

0A ppm

500A ppm CE

1 % T801

Solution 1

10 % wax1 in isooctane

12

11

& lt ; a?’5

Solution 2

10 % wax2 in isooctane

22

9

& lt ; a?’5

Table 7: Composition and pour point of the paraffin solutions in degree Celsius. ( Yin et al. )

From the tabular array, CE proved to hold really small or no consequence on solution 1, nevertheless, T801 proved to be really effectual in dejecting the pour point of the solution. In solution 2 incorporating CE, a good degree of pour point depression was noticed although, T801 still proved allot more effectual holding the same degree of depression on solution 1 and 2.

Samples

0

0.2 %

0.5 %

1 %

Pour point

12

& lt ; a?’5

& lt ; a?’5

& lt ; a?’5

Table 8: Pour point ( in grades Celsius ) of solution 1 with different concentrations of T801 PPD. ( Yin et al. )

From the tabular array, T801 proved to hold the same consequence when different concentrations were used. This once more shows that this pour point sedative is really effectual even to concentration every bit small as 0.2 % .

Samples

0

50A ppm

100A ppm

500A ppm

5000A ppm

Pour point

22

16

13

9

8

Table 9: Pour point ( in grade Celsius ) of solution 2 with different concentration of CE pour point sedative. ( Yin et al. )

From the tabular array, with addition in concentration of CE, the effectivity additions. However, the pour point depressions are higher at 50 ppm to 500 ppm. When the concentration of CE is increased to 5000 ppm from 500 ppm, merely a depression of 1 degree Celsius is noticed. This means that this pour point sedative is non effectual in big sums. Besides with the pour points arrived at, CE is still non every bit effectual as T801 sedative.

3.4 Machado et Al.

Machado et Al. carried out an experiment to measure the consequence of vinyl ethanoate content of ethylene-co-vinyl ethanoate ( EVA ) copolymers on viscousness and pour point of Brazilian petroleum oil. They besides attempted to associate the petroleum oil WAT to the cloud point of the EVA every bit good as its public presentation as a pour point sedative.

3.4.1 Materials and Methods

Three samples of rough oil were used in the research. Two of the samples were obtained from Albacora field and the last was obtained from Badejo field in Brazil.

Table 10: A Characterization information for EVA copolymers. ( Machado et al. )

Copolymer

Vinyl ethanoate content ( wt. % )

Molecular weight

MI„w

Palladium

EVA 20

20

10A-104

3

EVA 30

30

14A-104

3

EVA 40

40

10A-104

2

EVA 80

80

63A-104

3

Vinyl ethanoate content was determined by thermo hydrometric analyses ( TGA ) while molecular weight was determined by size exclusion chromatography ( SEC ) .

Table 11: A Crude oil word picture. ( Machado et al. )

Crude oil

Shell paraffin contentaA ( % )

WATbA ( A°C )

Pour point ( A°C )

Albacora 1

2.4

16.9

a?’8.0

Albacora 2

5.4

22.5

6.0

Badejo

7.2

19.5

18.0

The WAT was determined by differential scanning calorimetry ( DSC ) , at 5 A°C/min. The Pour points were determined by warming the petroleum oil which contained EVA.

Cloud points of the EVA solutions were taken to be the temperature, at which the crystals were wholly dissolved. This was done by ocular observation. The solvent media were cyclohexane, isooctane and dodecane.

For Albacora 2 petroleum oil, a decrease in pour point of 26 A°C was attained. This occurred when 50 and 500 ppm of EVA 20 was added to the petroleum oil. However, the sedative lost its competency when the concentration was increased to 1000 and 5000 ppm.

Table 12: A The influence of the EVA copolymers on the pour point of the Albacora 2 petroleum oil. ( Machado et al. )

Linear concentration ( ppm )

Pour point decrease ( A°C )

EVA 20

EVA 30

EVA 40

EVA 80

50

& gt ; 26

22

10

0

500

& gt ; 26

& gt ; 26

& gt ; 26

0

1000

22

5000

0

& gt ; 26

& gt ; 26

0

A EVA 80 did non demo any efficiency as pour point sedative for this rough oil.

3.4.2 Cloud point of the EVA copolymers in organic solutions

Fig. 9: cloud points for copolymer solutions at 0.1 w/v % .

The solubility sequence for the three pure dissolvers was cyclohexane, isooctane, dodecane. The solubility of copolymer increased as the vinyl acetate content increased for cyclohexane and for treble mixture. However, in most of the other solvent media, the solubility of EVA 30 was intermediate between EVA 20 and EVA 40.

Pour point for the systems: rough oil and petroleum oil/polymeric additive

Table shows the pour point consequences for pure petroleum oils and for the petroleum oil incorporating additive ( EVA 20, EVA 30 and EVA 40 ) .

Table 13: A Pour point of the petroleum oils with and without linear

Linear

Pour point of the petroleum oil ( A°C )

Albacora 1

Badejo

a?’8

18

EVA 20

& lt ; a?’28

a?’21

EVA 30

& lt ; a?’28

a?’25

EVA 40

a?’25

a?’17

The sedatives were more effectual in cut downing pour point of petroleum obtained from the Albacora 1 field. However, for the Badejo field, EVA 40 was less than EVA 20 and EVA 20 was less effectual than EVA 30.

It was so concluded that EVA 30 was the most effectual addictive. This goes to demo that the public presentation of EVA copolymers as pour point sedative is mostly dependent on the copolymer composing.

3.5 Synthesis of polymeric additives based on itaconic acid and their rating as pour point sedatives for lube oil in relation to rheological flow belongingss

Sabagh A, et Al. ( 2012 ) carried out an experiment on the synthesis of polymetric additives based on itaconic acid and their rating as pour point sedatives for lube oil in relation to rheological flow belongingss.

Chemicals used include: Itaconic acid, hexadecyl intoxicant, Octadecyl intoxicant. Two additive saturated long concatenation intoxicant blends NAFOL 20+A and NAFOL 1822 B were supplied from Condeu Chemical Company.

Table 14.A Typical analysis of additive long-chain intoxicant blends ( NAFOL ) . ( Sabagh A, et Al. 2012 )

Properties

NAFOL 20+A

NAFOL 1822 B

Composition, wt %

C16OH

0.9

0.2

C18OH

24.3

15.0

C20OH

24.4

14.8

C22OH

38.2

69.8

C24OH

9.9

0.2

C26OH

2.3

Average C figure ( calculated )

CavA =A 20

CavA =A 22

Density g/cm3A at 70A A°C

0.803

0.802

Hardening point, A°C

56-60

63-65

Ester no. milligram KOH/g

9.9

0.16

Acid no. milligram KOH/g

0.05

0.01

Water, wt %

0.06

0.04

Flash point, A°C

208

204

Iodine no. mgL/100A milligram

8.2

0.23

3.5.1 Lube oil composing

The lubrication oil was obtained from Suez Oil Processing Company ( SOPC ) . The oil was used to measure the public presentation of synthesized polymeric additives. TheA normal paraffin content of the lubrication oil is determined by urea adduction. The oil and the n-paraffin fraction were so analysed utilizing gas chromatography to find the mean molecular weight expressed as the mean C figure on the footing of C figure distribution.

Table 15.A Physicochemical belongingss of investigated lube oil. ( Sabagh A, et Al. 2012 )

Trial

Method

Consequence

Density @ 15A A°C Kg/L

ASTM D1298

0.9083

Color

ASTM D1500

5.5

Pour point A°C

ASTM D97

15

Flash point A°C ( PMC )

ASTM D93

203

Kinematic viscousness @ 40 A°C CST

ASTM D445

243.59

Kinematic viscousness @ 100 A°C CST

ASTM D445

18.94

Viscosity index

ASTM D445

87

Saybolt viscousness @ 100 A°F SUS

ASTM D445

96.8

X ray ( S ) wt %

ASTM D4294

1.084

n-paraffins, wt %

GLC

62.27

Iso-paraffin, wt %

GLC

4.12

Entire paraffins content, wt %

Urea adduct

66.39

Average C figure ( n )

GLC

28.56

Table 16: A Characteristization of the synthesized polymeric additives. ( Sabagh A, et Al. 2012 )

Linear appellation

Composition

Molar ratio alkyl itaconate-styrene ( % )

Average side C length ( Cav )

M.wt.

Poly dispersity index

PPD 1

PPD 2

PPD 3

Poly ( hexadecyl itaconate-styrene )

25:75

50:50

75:25

16

40313

45411

38513

1.68

1.70

1.50

PPD 4

PPD 5

PPD 6

Poly ( octadecyl itaconate-styrene )

25:75

50:50

75:25

18

40933

48415

41513

1.70

1.72

1.62

PPD 7

PPD 8

PPD 9

Poly ( NAFOL 20+A itaconate- cinnamene )

25:75

50:50

75:25

20

58298

35026

28858

1.57

1.50

1.31

PPD 10

PPD 11

PPD 12

Poly ( NAFOL 1822 B itaconate cinnamene )

25:75

50:50

75:25

22

60096

37710

30512

1.58

1.55

1.20

3.5.2 Word picture of copolymers

The constructions of the synthesized mono-esters alkyl itaconate and copolymers with cinnamene were established utilizing Infrared ( IR ) spectroscopic analysis. The infrared spectra were calculated by utilizing the theoretical account Genesis series ( USA ) infrared spectro-photometer following KBr technique. The construction of the prepared mono-esters alkyl itaconate and copolymers with cinnamene was found utilizing atomic Magnetic Resonance Spectroscopic analysis. Copolymers of the different alkyl itaconate with cinnamene were so abbreviated as PPD1-PPD3 ( C16 ) , PPD4-PPD6 ( C18 ) , PPD7-PPD9 ( C20 ) , PPD10-PPD12 ( C22 ) . The esterification and copolymerization are shown in fig 10.

fig 10. esterification and copolymerization ( Sabagh A, et Al. 2012 )

3.5.3 Pour point measuring ( ASTM D 97-96 )

The solutions of oil soluble samples PPD1-PPD12 in methylbenzene were prepared utilizing the ASTM, D97-96 method. PPD solutions were introduced into the lubrication oil and examined as pour point sedatives at changing concentrations ( 250, 500,1000,1500,2000 and 3000A ppm ) of. Pour point was set at 2.8A A°C above the existent temperature which the oil solidifies.A

A Influence of pendent concatenation length of the assorted copolymers on their effectivity in footings of pour point depression

The different alkyl ironss were effectual on the pour point depression of lube oil. However, PPD1-3 C16A was more effectual than PPD4-6 C18, PPD4-6 C18A was more effectual than PPD7-9 C20, and PPD7-9 C20 was more effectual thanA PPD10-12 C22. The consequences inA table 16 shows that the depressant efficiency diminutions as the alkyl concatenation length from C16A to C22 is increased. C16A itaconate-styrene attained the best flow humanitarian to the extent of PP2000A ppmA =A a?’15A A°C at molar ratio 50 % :50 % ( PPD2 ) . The consequences show that cut downing the alkyl concatenation length from C22A to C16A improves the interaction between the alkyl concatenation of the copolymer and paraffin in the lubrication oil. This average suppression of wax crystal deposition could be obtained.

Table 16A Consequence of the polymeric additives on the flowability of lube oil. ( Sabagh A, et Al. 2012 ) .

Lube oil

Linear design

Linear concentration, ppm

Nothing

250

500

1000

1500

2000

3000

pp

I”pp

pp

I”pp

pp

I”pp

pp

I”pp

pp

I”pp

pp

I”pp

PPD 1

15

12

3

12

3

0

15

a?’3

18

a?’9

24

a?’12

27

PPD 2

15

12

3

3

12

0

15

a?’9

24

a?’18

33

a?’18

33

PPD 3

15

12

3

12

3

3

12

0

15

a?’6

21

a?’9

24

PPD 4

15

12

3

12

3

0

15

a?’6

21

a?’9

24

a?’12

27

PPD 5

15

12

3

0

15

a?’3

18

a?’9

24

a?’15

30

a?’15

30

PPD 6

15

12

3

12

3

6

9

0

15

a?’6

21

a?’9

24

PPD 7

15

12

3

12

3

6

9

0

15

a?’6

21

a?’9

24

PPD 8

15

12

3

9

6

3

12

a?’3

18

a?’12

27

a?’12

27

PPD 9

15

12

3

9

6

6

9

3

12

0

15

a?’6

21

PPD 10

15

15

0

12

3

3

12

a?’3

18

a?’6

21

a?’9

24

PPD 11

15

15

0

12

3

3

12

a?’3

18

a?’6

21

a?’9

24

PPD 12

15

15

0

12

3

9

6

6

9

0

15

a?’3

18

Influence of the mean molecular weights of the assorted investigated copolymers on their effectivity in footings as pour point depression

The synthesized polymers ( PPD1-PPD12 ) were examined and their mean molecular weights and polydispersity were calculated by GPC analysis. The consequence proved that the molecular weights of the sedatives were different get downing from 28,858 to 60,096 and that the best efficiency is attained at the scope of 40,313 to 48,415 ( PPD1, PPD2, PPD4, PPD5, PPD6 ) . The consequences alsoA show that PPD2 and PPD5, had the highest poly dispersity index and brought about the best pour point depression. The least pour point depressions were attained by PPD9 and PPD12, holding the lowest polydispersity.

When the concentration of the additives was increased, increased action was attained and this had a immense depression on pour point was achieved. It was besides noticed that the pour point continually reduced as the depressant concentration increased to 2000A ppm. Normally, with a lower concentration of depressant side manner growing of the crystal may be slightly hindered and the crystal growing would be slower. This nevertheless does non intend deposition would non still happen. At well high concentrations of sedatives, the side manner growing becomes more hard for the wax crystals.

3.6 Polymethacrylates: Pour point sedatives in Diesel oil

Soldi R, et Al ( 2007 ) carried out an experiment utilizing methyl methacrylate as pour point sedatives in diesel oil.

The methyl methacrylate ( MMA ) used was washed independently times with an aqueous solution of NaOH and washed once more distilled H2O. This was dried with anhydrous Mg sulfate and so distilled.

3.6.1 Synthesis of the methacrylic monomers

In a round-bottom flask connected to a distillment microsystem, octadecyl intoxicant and methyl methacrylate were added ( 1:4 molar ratio ) , every bit good asA p-toluenesulfonic acid ( PTSA ) ( 0.5A mol % ) , and hydroquinone ( 3 % w/w, in relation to MMA ) .

The flask incorporating the reactional medium was heated to 90A A°C, and kept under magnetic stirring by 24A h. The temperature was, so, raised bit by bit until the terminal of the distillment.

The surplus of residuary methyl methacrylate was removed through distillment at a decreased force per unit area and the octadecyl methacrylate ( ODMA ) , was purified in methyl alcohol.

The same experimental conditions were used in the synthesis of tetradecyl methacrylate ( TDMA ) and of hexadecyl methacrylate ( HDMA ) , by utilizing the, severally, fatty intoxicant.

3.6.2 Synthesis of methacrylic copolymers

In a two-necked round-bottomed flask the methyl methacrylate and octadecyl methacrylate were assorted in molar ratio of 50:50. Polymerization was done in a toluene solution. This reaction was carried out at 70A A°C for 17A hours under N ambiance and magnetic stirring. The methylbenzene was so evaporated under low force per unit area.

After the pour point of Diesel oil was established, the influence of measure of dissolver ( methylbenzene ) and the consequence of the fatty monomers on the pour point of the oil was examined. It was seen that the presence of different sums of methylbenzene in the oil had no consequence on its pour point. The measures of monomers used which were higher than the sum of polymeric additive besides had no consequence on the pour point. Hence, there was the demand for a polymeric anchor so as to accomplish the needed consequence of these type of pour point sedative.

To measure public presentation of the different polymeric compounds obtained, a sample of Diesel oil called “ type D ” was used. This oil has a pour point of 0A A°C.

For each of the methacrylic polymer tested in the type D Diesel oil, at two pour point rating were done utilizing linear concentration of 50A ppm.

Table 17: A Consequences of pour point of type D Diesel oil ( pour pointA =A 0A A°C ) treated with 50A ppm of methacrylic copolymers of different composings. ( Soldi R, et al 2007 ) .

Methacrylic additives

Composition in the copolymer

Pour point ( A°C )

Decrease observed ( A°C )

Alkyl methacrylate ( mol % )

Methyl methacrylate ( mol % )

PODMMA73

67

33

a?’22

22

PODMMA55

42

58

a?’18

18

PODMMA37

26

74

a?’10

10

PHDMMA73

66

34

a?’18

18

PHDMMA55

53

47

a?’13

13

PHDMMA37

26

74

a?’7

7

PTDMMA73

67

33

a?’10

10

PTDMMA55

52

48

a?’10

10

PTDMMA37

29

71

a?’10

10

{ Tetradecyl methacrylate copolymers ( PTDMMA ) , poly ( octadecyl methacrylate-co-methyl methacrylate ) ( PODMMA ) , hexadecyl methacrylate copolymers ( PHDMMA ) } .

When analyzing the structure-activity relation in polymeric additives for oil and its merchandises it is common to happen in the literature a given composing beyond which an addition in the proportion of active groups does non impact the public presentation of the linear anymore, to the contrary it could do it worse.

From the tabular array, in the instance of the octadecyl group, for the same size of hydrocarbon group, increasing the sum of these groups improved the public presentation of the linear. This is because the long hydrocarbon paraffins have a inclination to interact with the polymer alkyl groups which act as crystallisation karyon. This means that the larger the Numberss of crystallisation karyon, the less free paraffin to blockade fluidness with the decreasing temperature and as a consequence, pour point will be less. On the other manus, if the measure of long groups is excessively high, they could acquire in the manner of crystallisation on the polymer concatenation.

In the countries where a little concentration of the methacrylic linear synthesized shows low pour point values, there is a chance that much smaller doses could be used for a considerable lessening in the pour point of type D Diesel oil.

3.7 Improving cold flow belongingss of canola-based biodiesel

Chastek T, ( 2011 ) carried out an experiment on bettering the cold flow belongingss of canola based biodiesel.

3.7.1 Materials

The Canola-based biodiesel was acquired from Inland Empire Oilseed LLC ( denoted as Biodiesel A ) . Methyl oleate ( 70 % ) ( denoted as Biodiesel B ) , methyl stearate ( a‰?96 % ) , methyl palmitate ( a‰?96 % ) , dioctyl phthalate ( DOP, 99 % ) , and anisole ( 99.7 ) were obtained from Sigma-Aldrich. Tetrahydrofuran ( THF ) ( 99.5 % ) , butyl alcohol ( 99.9 % ) , and pentane ( & gt ; 99 % ) were obtained from JT Baker. Acetone ( 99.99 % ) was obtained from VWR. Gas chromatography was used to mensurate the chemical composings of Biodiesel A and Biodiesel B.

Table 18.A Composition of biodiesel samples. ( Chastek T, 2011 ) .

Melting point, pure, A°C

% in biodiesel Aa

% in

biodiesel Ba

Methyl eicosanoate

20:0

46.4

0.6

0.0

Methyl stearate

18:0

37.7

1.8

1.0

Methyl palmitate

16:0

28.5

3.8

4.7

Methyl palmitoleate

16:1

a?’3.0

0.2

5.3

Methyl gadoleate

20:1

a?’7.8

1.2

0.0

Methyl oleate

18:1

a?’20.2

65.2

79.7

Methyl linoleate

18:2

a?’35

19.1

9.4

Methyl linolenate

18:3

a?’52

8.0

0.0

% in biodiesel is the weight per centum based on peak country of GC measuring.

Polymers were dispersed in Biodiesel A and B through whirl commixture and warming. For polymers supplied as solutions in methylbenzene, the methylbenzene was removed utilizing vacuity heating anterior to uniting with biodiesel.

Cloud points, pour points, and low temperature filterability points were noticed upon chilling samples ( & lt ; 0.3A A°C/min ) . The samples were straight immersed in the temperature bath. All samples presented inA Table belowA were cooled at the same clip for uniformity so that comparative public presentation of the different dissolvers and additives could be right compared. Besides some samples were assorted ( magnetic splash saloon, 300A RPM ) as they cooled merely about 3A A°C below the cloud point. Additional chilling of the samples was done without stirring.

Table 19: Cold flow belongingss of biodiesel with added polymers. ( Chastek T, 2011 ) .

Weight percenta

Cloud point, A°C biodiesel A

Pour pointb, A°C biodiesel A

Low temperature filterability pointc, A°C biodiesel A

Cloud point, A°C biodiesel B

Pour pointb, A°C biodiesel B

Low temperature filterability pointc, A°C biodiesel B

Biodiesel Ad

a?’12

a?’16

Biodiesel Be

a?’22

a?’24

poly ( octyl methacrylate )

1.0

a?’12

a?’19

a?’17

a?’21

poly ( decyl methacrylate )

1.0

a?’12

a?’19

a?’17

a?’22

poly ( lauryl methacrylate ) degree Fahrenheit

1.0

a?’12

a?’46 ( a?’46 )

a?’27 ( a?’44 )

a?’22

a?’42

a?’42

poly ( lauryl methacrylate ) g

0.14

a?’12

a?’28 ( a?’43 )

a?’27 ( a?’27 )

a?’22

a?’27

a?’24

poly ( lauryl methacrylate ) g

0.50

a?’12

a?’43 ( a?’44 )

a?’28 ( a?’43 )

a?’22

a?’35

a?’24 ( a?’28 )

poly ( lauryl methacrylate ) g

1.0

a?’12

a?’44 ( a?’45 )

a?’27 ( a?’38 )

a?’24

a?’37.5

a?’27 ( a?’32 )

poly ( lauryl methacrylate ) g

2.0

a?’12

a?’41 ( a?’43 )

a?’27 ( a?’43 )

a?’24

a?’35

a?’35

poly ( lauryl methacrylate ) g

3.9

a?’12

a?’43 ( a?’43 )

a?’27 ( a?’43 )

a?’24

a?’33

a?’35

PLMA-b-PMMA

1.0

a?’12

a?’41 ( a?’47 )

a?’27 ( a?’43 )

a?’21

a?’39.5

a?’29.5

PLMA-r-PMMA

1.0

a?’12

a?’23

a?’22

a?’42

a?’29.5

poly ( vinyl laurate )

1.0

a?’12

a?’22

a?’22

a?’25.5

a?’29.5

a?’28.5

poly ( hexadecyl methacrylate )

1.0

a?’12

a?’20

a?’7.5

a?’24

PODMA-b-PMMA 38K

0.97

a?’12

a?’12

a?’3

a?’21

PODMA-b-PMMA 63K

1.0

a?’12

a?’17

a?’3

a?’24

poly ( octadecyl vinyl ether-co-maleic anhydride )

1.0

a?’12

a?’19

a?’1

a?’24

poly ( ethylene-co-vinyl ethanoate ) , 18 % vinyl ethanoate

1.0

a?’12

a?’42h ( a?’27 )

a?’22 ( a?’27 )

5

a?’24

poly ( ethylene-co-vinyl ethanoate ) , 50 % vinyl ethanoate

1.0

a?’13.5

a?’14

a?’22

a?’24

a ) Weight per centum of polymer in methyl oleate.

B ) The pour point values in parentheses correspond to stirred samples.

degree Celsius ) The low temperature filterability point values are merely reported if they are notably lower than the pour point of the unmodified Biodiesel ; the values in parentheses correspond to stirred samples.

vitamin D ) Canola-based biodiesel.

vitamin E ) A commercially available proficient class methyl oleate ( 70 % pureness, Aldrich ) was measured for comparing to canola-based biodiesel.

degree Fahrenheit ) Synthesized via ATRP, 13.5A kg/mol.

g ) Purchased from Scientific Polymer Products, 250A kg/mol.

H ) The syrupy composing of the unstirred sample made assignment of PP ill-defined. Extra measurings were made on poly ( isobutyl methacrylate ) , poly ( benzyl methacrylate ) , poly ( hexyl methacrylate ) , and poly ( cinnamene ) . However, initial consequences showed no lowering of the PP or LTFP temperatures. ( Chastek T, 2011 ) .

Measuring pour point temperature provides a instead clear apprehension of what polymers promote the cold flow belongingss of biodiesel. The basic determination was that the poly ( lauryl methacrylate ) and its copolymers well reduced the pour point of biodiesel. The other polymers showed negligible betterment. The polymers public presentations and efficiencies were linked to chemical construction. For poly ( decyl methacrylate ) and poly ( hexadecyl methacrylate ) , they had minimum impact on pour point in malice of their chemical similarity to poly ( lauryl methacrylate ) .

Besides, the poly ( lauryl methacrylate ) copolymers lowered the pour point temperature, but the consequence was non every bit considerable as the poly ( lauryl methacrylate ) monomer. From these consequences, the chemical construction and belongingss of lauryl methacrylate monomer give it high affinity to the crystallization saturated methyl esters. As a consequence of this affinity, poly ( lauryl methacrylate ) can hold an consequence on the saturated methyl ester crystal size more than any of the other additives would hold.

The impact of poly ( lauryl methacrylate ) ( 250A kg/mol ) concentration was besides examined. At 0.14 % , the poly ( lauryl methacrylate ) had a reduced impact on pour point with regard to higher concentrations. It was noted that a 1 % linear concentration may be excessively much for biodiesel dainty rate as allot of manufacturers of pour point sedatives ( PPDs ) suggest 1000A ppm dainty rates. So it is likely that low concentrations could execute better as PPDs frequently have hapless cold flow belongingss.

3.8 Effect of wax inhibitors on pour point and rheological belongingss of Persian waxy petroleum oil

Taraneh J, et Al. ( 2008 ) carried out an experiment on consequence of wax inhibitors on pour point and rheological belongingss of Iranian waxy petroleum oil.

Five samples were provided from the Persian waxy petroleum oils ( crude-1 to crude-5 ) to measure the public presentation of flow humanitarians. The physical belongingss and rheological behavior of the petroleum oils are provided inA tabular arraies.

Table 20.A Physical features of petroleum oils. ( Taraneh J, et Al. 2008 )

Specification

Crude-1

Crude-2

Crude-3

Crude-4

Crude-5

Methods

Specific gravitation at 15.56/15.56A A°C

0.8503

0.8661

0.8846

0.8944

0.9033

ASTM D-4052

API

34.9

31.9

28.5

26.7

25.1

ASTM D-4053

Kinematic viscousness at 40A A°C C.St.

7.828

10.959

12.525

14.689

15.125

ASTM D-445

Kinematic viscousness at 100A A°C C.St.

2.751

3.852

4.656

6.136

8.698

ASTM D-446

Pour point ( A°C )

26

20

17

14

8

ASTM D-97

Asphaltene content ( wt. % )

0.3

1.5

2.8

4.7

7.8

IP-143

Wax content ( wt. % )

13.1

11.2

9.7

7.4

5.2

BP-237

Table 21.A Viscosity ( mPa s ) of petroleum oils. ( Taraneh J, et Al. 2008 )

Type

Shear rate, sa?’A 1

40A A°C

20A A°C

15A A°C

10A A°C

5A A°C

Crude-1

70

14.0

275

580

920

1680

100

14.0

223

460

750

1189

300

13.8

125

265

365

526

Crude-2

70

14.8

301

615

982

1850

100

14.5

250

505

810

1308

300

14.3

155

303

385

675

Crude-3

70

15.5

352

690

1021

2025

100

15.1

320

580

860

1560

300

15.0

210

398

420

715

Crude-4

70

15.9

401

750

1562

2950

100

16.1

390

640

1050

2010

300

16.8

280

480

490

886

Crude-5

70

16.9

489

910

2130

3852

100

17.0

550

850

1680

2541

300

17.9

405

620

630

985

Four different types of commercial ethylene-vinyl acetate copolymer ( EVA ) were used as flow humanitarians.

Table 22.A Characteristics of polymers used. ( Taraneh J, et Al. 2008 )

Features of polymers

EVA20

EVA40

EVA80

EVA32

MwA ( 104 )

10

10

63

5.5

Composition ( VA content ) ( wt. % )

20

40

80

32

The waxen petroleum oils used have different asphaltene contents. The asphaltene content of petroleum 5 was ( 7.8 % ) more than the asphaltene content of petroleum 1 ( 0.3 % ) . The wax content of these petroleum oils besides varied from 5.2 % to 13.1 % which affected pour point behaviors.

Consequence of molecular weight of flow humanitarian and asphaltene content of rough oil on pour point of the Persian waxy petroleum oil

Table 23.A Viscosity ( mPa s ) of petroleum oils at a shear rate of 100A sa?’A 1A treated with flow humanitarian EVA80 and EVA32 in different concentrations

Type

Concentration ( EVA80 ) , ppm

40A A°C

20A A°C

15A A°C

10A A°C

5A A°C

Concentration ( EVA32 ) , ppm

40A A°C

20A A°C

15A A°C

10A A°C

5A A°C

Crude-1

500

10

39

155

415

760

500

13

44

368

691

992

1000

8

30

120

360

710

1000

10

38

292

612

874

2000

2

25

98

310

680

2000

5

34

221

538

842

Crude-2

500

14

42

180

440

780

500

12

42

352

656

910

1000

12

36

140

380

740

1000

9

36

268

584

855

2000

7

30

110

340

715

2000

4

30

197

502

810

Crude-3

500

16

45

210

492

810

500

11

40

302

602

895

1000

14

40

180

410

780

1000

9

32

210

554

802

2000

9

35

150

385

730

2000

4

24

170

471

780

Crude-4

500

16

47

280

530

865

500

11

38

250

590

820

1000

15

42

225

485

812

1000

9

32

190

510

780

2000

9

38

186

427

785

2000

3

24

150

410

720

Crude-5

500

18

52

352

587

912

500

9

38

170

440

750

1000

16

48

286

512

868

1000

7

32

110

350

710

2000

10

43

227

487

802

2000

1

25

90

310

683

From the consequence on viscousness decrease of the rough oil with different concentration of flow humanitarian dissolved in cyclohexane at a shear rate of 100A sa?’A 1, the high molecular weight EVA80 has a good efficiency for petroleum 1 which has small asphaltene ( 0.3 % ) . On the other manus, lower molecular weight EVA32 is the best flow humanitarian for petroleum 5 with high asphaltene content ( 7.8 % ) .

It was besides noticed that the high molecular weight flow humanitarian shows better effectivity on pour point of rough oil with low asphaltene content. In add-on, the lower molecular weight flow humanitarian shows a better competency for rough oil with higher asphaltene content.

Table 24.A Effect of different flow humanitarians on the pour point of the petroleum oils with different concentrations. ( Taraneh J, et Al. 2008 )

Type

Concentration, ppm

EVA80

EVA20

EVA40

EVA32

Crude-1

500

15

19

21

20

1000

5

13

16

14

2000

a?’A 2

9

13

10

Crude-2

500

14

15

16

16

1000

7

8

10

10

2000

1

4

7

6

Crude-3

500

12

9

12

10

1000

7

3

6

5

2000

2

a?’A 1

3

1

Crude-4

500

9

7

10

7

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