44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

EVALUATION OF FEASIBLE WAYS FOR REFINERY NAPHTHA STREAMS PROCESSING

Dicho Stratiev1, Todor Tzingov, Ivelina Shishkova, Antoaneta Pavlova, Pavlina Ivanova
1

Lukoil Neftochim Bourgas- R&D Department, 8104 Bourgas, Bulgaria, e-mail: stratiev.dicho@neftochim.bg

KEY WORDS: naphtha ,catalytic reformer, isomerization ABSTRACT

Naphtha streams from crude distillation of Ural crude, middle distillate hydrotreaters, vacuum gas oil hydrotreater and visbreaker have been characterized with the aim to evaluate the most appropriate way for their processing in the refinery. It was found that their octane ratings (RON) varied between 42 and 72. Their sulphur content varied between 370 and 3300 ppm. The middle distillate hydrotreater naphthas contained the highest level of sulphur and the relative part of H2S from their total sulphur varied in the range 33 100%. The content of aromatics in the investigated naphtha streams varied between 4.5 and 17.6 vol. %. It was found that the mixed heavy wild naphtha fraction had higher characteristic index 2+N = 68.2 than the straight run heavy naphtha (fraction 100 1800C) 2+N =54.9. This is an indicator that the naphtha streams from the middle distillate hydrotreaters and the vacuum gas oil hydrotreater are more suitable as a feedstock for catalytic reforming than the straight run heavy naphtha from Ural crude. However, the mixed light wild naphtha fraction contained less C5 and C6 hydrocarbons (17.2%) than the straight run light naphtha, fraction 40 1000C, (47.7%). Therefore, the straight run light naphtha from Ural crude is more suitable as a feedstock for C5C6 isomerization. The addition of visbreaker naphtha to the mixed heavy wild naphtha fraction has led to a reduction of the characteristic index 2+N from 68.2 to 64.1 and an increase of olefins content from 0.5 to 7.7 wt.%. The analysis of metal content in the investigated naphtha streams showed a higher content of lead (27 ppb) in the secondary naphtha streams than the straight run naphtha streams (< 1 ppb). The higher content of lead in the secondary naphtha streams could prohibit their use as a feedstock for catalytic reformer because the typical limit of lead content for catalytic reformer feed is 5 ppb.

INTRODUCTION Low octane naphtha fractions are produced except by crude oil straight run distillation also by secondary processes as middle distillate fractions and heavy vacuum gas oils hydrotreatment and heavy residues conversion processes like Visbreaker unit. It is well known that two processes of low octane number naphtha upgrading exist. These are low octane number naphtha (C5C6) isomerization and heavy low octane number naphtha (fraction C7- C11) catalytic reforming. It is not desirable low octane naphtha fractions with initial boiling point below 80.6 oC according TBP to be subject to catalytic reforming by reason of standard motor naphtha benzene content limitation not more than 1.0 % v/v. That is why, low octane naphtha fractions of typical boiling range of 30 180 oC have to be fractionated to light naphtha fraction of the range 30 81 oC and heavy naphtha fraction of the range 81 180 oC as

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

the light naphtha has to be turn to isomerization and the heavy one to catalytic reforming. The present work furnishes one study on the properties of primary and secondary low octane naphtha streams at LNB refinery and evaluation of the optional trends for their further processing. RESULTS Physical and chemical properties of straight run naphtha fractions (light and heavy low octane naphtha) produced by Ural crude oil atmospheric distillation are presented at Table I. Physical-chemical properties of secondary low octane naphtha fractions produced at middle distillate fractions and heavy vacuum gas oil hydrotreatment units and vacuum residue Visbreaker unit are presented in Table II. Physical-chemical properties of feeds and stable hydrogenates produced of them at LNB middle distillate hydrotreatment units are presented in Table III. The PIONA analyses of primary and secondary naphtha produced at LNB refinery are presented in Table IV. In Table V are shown compositions of mixed naphtha samples which PIONA analyses are shown in Table IV. In Table VI are included physical-chemical properties of Visbreaker unit naphtha with different end boiling points. The Visbreaker unit naphtha with different end boiling points PIONA analysis is presented in Table VII. In Table VIII is shown PIONA analysis of LNB hydrotreatment units mixed wild naphtha, Visbreaker unit naphtha, 50 % mixed wild naphtha / 50 % Visbreaker unit naphtha before and after hydrotreatment. Hydrocarbon composition is shown in Table IX and sulfur compounds composition of C5 fraction produced at LNB Gas Fractionation Unit are indicated in Table X. RESULTS DISCUSSION Data in Tables I and IV shows that light straight run low octane naphtha (LON) is fraction boiling in the range of 37 91oC and consists mainly of C5C8 hydrocarbons and contains minimum quantities of C4 and C9 hydrocarbons. Heavy straight run LON is fraction boiling in the range of 103 179 oC and consists mainly of C7 C11 hydrocarbons and contains minimum quantities of C6 hydrocarbons. It may be noted from this data that Ural petroleum straight run LON produced at crude oil atmospheric distillation units is not adequately accurate fractionated and the effectiveness of benzene precursors (mainly C6 naphthenes) separation from heavy LON is not sufficiently high and may be this is due to the fact that the fractionator separating naphtha to light and heavy fractions has not been design to achieve high separation accuracy. Thus, this data allows also to make a conclusion that distillation characteristics of both naphtha fractions could not be used as reference whether heavy LON contains or not any benzene precursors (C6 hydrocarbons), which shall be converted to benzene at Catalytic Reforming Unit. Table II data shows that secondary LON are unstable and contain C2 C4 hydrocarbons and considerable quantity hydrogen sulfide. The total sulfur content of the different secondary LON varies between 370 and 8800 ppm and hydrogen sulfide percentage is between 19 and 100 %. 92 % of total sulfur content is hydrogen sulfide in wild naphtha sample obtained as result of hydrotreatment units wild naphtha mixing in ratio indicated in Table V and it is removed by sample stripping with nitrogen (Table IV). Arenes content according to FIA method in hydrotreatment units wild naphtha varies between

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

4.5 and 17.6 % v/v as the HT-4 wild naphtha has the highest arenes content because in it FCC light catalytic gas oil is processed. That is why HT-4 feed has the highest arenes content (Table III) as compared to all other LNB middle distillate fraction hydrotreatment units. It is obvious from the presented data that arenes content in the wild naphtha of the different middle distillate fraction hydrotreatment units (HT-1 HT-4) not always correlates to arenes content in these units feed. Thus, for example feeds for HT-2 and HT-3 units contain between 27.5 and 30 % arenes but arenes content of these units wild naphtha is about 4.5 % while HT-1 unit feed arenes content is 21 % but this unit wild naphtha contains 5.7 % v/v arenes. Similarly, feed for heavy vacuum gas oil (HVGO) hydrotreatment contains about 40 % arenes but this unit wild naphtha contains 8.3 % v/v arenes which are less than HT-4 wild naphtha arenes content which feed contains 38.4 % arenes. Table I Physical-chemical properties of light and heavy low octane naphtha (LON) produced at Ural crude oil atmospheric distillation unit

Properties Density, d420 Total sulfur content, % Distillation, ASTM D-86 IBP., 0 5% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % EBP, 0

Light LON 0.6733 0.0910 37 47 49 54 58 61 65 68 71 78 81 91

Heavy LON 0.753 0.0748 103 112 115 118 123 127 132 137 143 150 159 179

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Table II Physical - chemical properties of secondary low octane naphtha produced at LNB.
Properties Density at 15 oC, g/cm3 Sulfur Total Mercaptans Hydrogen sulfide Others Group hydrocarbon composition (ASTM D1319 FIA method), % v/v Saturates Olefins Arenes (Aromatics) Distillation, oC IBP 5% v/v 10% v/v 20% v/v 30% v/v 40% v/v 50% v/v 60% v/v 70% v/v 80% v/v 90% v/v EBP/Recovery, % v/v HT-1 0.7350 % of m total S 930 460 470 49.46 50.54 HT-2 0.7195 % of m total S 3300 1100 2200 33.33 66.67 HT-3 0.7142 % of m total S 2100 1500 600 71.43 28.57 HT-3* 0.6961 HT-4 0.7740 % of m total S 370 0 370 100 FCC Hydrotreater (FCC HT) 0.7418 % of m total S 2500 2500 100 Thermal Cracking (TC) 0.7201 % of m total S 8800 3200 37 1700 19 3900 44 Catalytic Reforming (CR1) 0.6700 % of m total S 1300 270 1030 20.8 79.2

92.87 1.40 5.73 39 96 103 108 110 112 114 117 120 123 130 143

94.25 1.00 4.75 33 64 72 82 89 94 99 103 107.5 113 121 139/96

94.55 0.92 4.53 32.5 59 67 78 85 90 95 99 103 108.5 117.5 123/95

97.00 0.90 2.10 32.5 55.0 62.0 71.0 77.5 82.0 85.0 88.0 91.5 94.0 97.5 109.5/97.5

81.36 1.04 17.60 72 98 115 128 139 150 159 169 176 185 197 219

91.68 8.32 48 78 86 93 97 102 106 110 114 120 127 141/97

53.37 37.94 8.69 32 52 60 74 83 92 100 107 114 123 162 293/95 29 47 53 59 63 65 67 69 71 75 84 104

*Diesel fraction and Visbreaker unit naphtha fraction have been processed at HT-3.

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Table III Characteristics of the diesel fraction hydrotreatment unit feeds and stable hydrogenates at LNB

Properties Feed Density at 15 0, ISO 3675 Distillation, 0C, ASTM D 86 IBP 5% 10% 50% 90% 95% EBP Sulfur, % mass, ASTM D 2622 Nitrogen content, wt ppm, ASTM D 4629 Bromine number, g Br2/100 g, ASTM D 1159 Arenes, % mass, EN 12916 including Mononuclei Polynuclei Cetane index ASTM D-4737 0.801

HT-1 Hydrogenate 0.796

Feed 0.840

HT-2 Hydrogenate 0.833

Feed 0.858

HT-3 Hydrogenate 0.847

Feed 0.840

HT-4 Hydrogenate 0.836

176 197 199 210 231 235 247 0.25 2 1.1 21.0

180 196 200 208 230 233 246 0.0015

191 215 225 260 315 335 353 0.8

202 213 225 257 314 333 349 0.0031

194 250 270 308 348 358 369 1.1 228

210 247 262 301 344 352 366 0.0048

179 198 210 243 272 281 296 0.47 135 5

182 200 209 240 269 278 294 0.001

7-9 27.5 27.5

3 30.0 30.0

38.4

38.4

15.0 6.0 50.1 51.9

18.2 9.3 50.2

21.9 5.6 52.5

19.5 10.5 55.5

23.7 6.3 58.4

23.2 15.2 43.8

29.8 8.6 44.6

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Table IV PIONA analysis of primary and secondary naphtha produced at LNB

Mixture 1 (Wild naphtha from HT 1,2,3,4, CR1, FCC HT) Mixture 2 (Wild naphtha from HT-1,2,3,4, CR1, FCC HT, TC), 0.04 0.68 1.8 2.96 5.28 5.67 4.87 0.82 0.46 0.36 0.12 0.06 0.05 0.04 23.21 0.49 1.8 6.02 4.48 5.36 2.83 0.56 0.35 0.14 0.05 0.07 22.15 0.61 0.99 1.92 1.99 1.23 0.97 7.71 1.04 6.8 12 13.18 1.73 0.35 35.1

Composition, wt%

LON, LON IBP-100 oC 100-180 oC

n-Paraffins n-C2 0.04 n-C3 0.6 n-C4 1.65 n-C5 2.91 n-C6 5.82 n-C7 5.31 n-C8 4.67 n-C9 0.97 n-C10 0.6 n-C11 0.47 n-C12 0.15 n-C13 0.06 n-C14 0.02 n-C15 Total n-Paraffins 23.27 iso-Paraffins i-C4 0.55 i-C5 1.85 i-C6 6.61 i-C7 3.22 i-C8 6.28 i-C9 3.53 i-C10 0.66 i-C11 0.51 i-C12 0.08 i-C13 0.14 i-C14 Total iso-Paraffins 23.43 Olefins O4 O5 0.1 O6 O7 O8 0.15 O9 0.21 Total n-Olefins 0.46 Naphthenes N5 0.68 N6 8.46 N7 13.82 N8 12.13 N9 1.8 N10 0.49 N11 Total naphthenes 37.38

0.27 14.62 11.93 7.17 1.35 0.02

0.41 4.67 7.74 6.24 2.78 0.19

35.36 0.01 7.56 13.63 8.48 6.72 0.13

22.03

0.08 3.10 7.76 6.62 6.62 0.41

36.53

24.59

0 1.4 10.53 10.27 3.41 0.14 25.75

0.55 0.55

1.15 8.75 13.59 5.79 1.85 31.13

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Composition, wt% Aromatics 6 A7 A8 A9 A10 A11 12 A13 Total aromatics 2A+N Unknowns Total nP (C7+) iP(C7+) O(C7+) N7+ A7+ 2A+N Pb, ppb As, ppb Cu, ppm Na, ppm S, % S, % (after nitrogen purge) % H2 S vs total Sulfur RON MON

Mixture 1

Mixture 2

LON, LON IBP-100 oC 100-180 oC 0.87 0.85 0.33 0.08 1.58 6.22 3.99

0.99 3.64 2.6 0.97 1.82 0.52 0.14 10.68 58.74 4.78 100 17.5 20.6 0.5 40.4 13.9 68.2 23 < 1.3 0.3 1.4 0.086 0.007 91.9 53.7

1.1 3.11 2.44 0.76 1.2 0.6 0.15 0.04 9.4 53.9 2.43 100 18.2 20.2 6.1 39.8 12.1 64.1 24 49 0.4 1.1 0.36 0.22 38.9 54.2

2.05 29.85

11.87 54.87

< 0.1

< 0.1 45.8 1.3

63.2 60.6

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The different hydrotreatment units wild naphtha fractions has been mixed in ratio that they are produced at the refinery (Table V) and Visbreaker unit naphtha has been added to them in ratio shown n Table V. The obtained mixtures analysis is shown in Table IV. Table IV data shows that wild naphtha fractions contain more naphthenes and almost equal arenes content as straight run V/V. Characteristic index 2A + N determining the quality of a given naphtha fraction as Catalytic Reforming fraction feed for 7+ fraction of wild naphtha fractions and their mixture with Visbreaker unit naphtha is higher (68.2 and 64.1) than that of straight run heavy LON (54.9) and consequently wild naphtha fractions are higher quality feed for Catalytic Reforming unit than straight run heavy LON. Unlike straight run naphtha fractions wild naphtha fractions contain lead 23 ppb but do not contain arsenic while straight run naphtha and wild naphtha fractions and Visbreaker unit naphtha (28.5 % Visbreaker unit naphtha) mixture contains between 45.8 and 49 ppb. It is well known that these metals are catalysts poison and it should be provide guard layer at Catalytic Reforming feed hydrotreatment unit when such type feeds are processed. In view of the fact that in wild naphtha fractions and Visbreaker unit naphtha mixture the Visbreaker unit naphtha percentage is 28.5 % (Table

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

V) and that wild naphtha fractions do not contain arsenic hence 100 % Visbreaker unit naphtha should contain 172 ppb arsenic. Table V Compositions of the investigated secondary low octane naphtha fraction mixtures, shown in Table IV
Mixture 1 % 8.9 15.1 19.9 13.3 13.3 29.5 100 Mixture 2 % 6.4 10.8 14.2 9.5 9.5 21.1 28.5 100

HT-1 HT-2 HT-3 HT-4 CR1 FCC HT

HT-1 HT-2 HT-3 HT-4 CR1 FCC HT TC

Table VI data shows that as the Visbreaker unit naphtha end boiling point increases its density and arenes content also increase and olefins content decreases. Table VI Physical-chemical properties of Visbreaker unit naphtha fraction with different end boiling point
Properties Density, d420 Distillation, ASTM D-86 IBP, 5% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % EBP, Recovery Group hydrocarbon composition (ASTM D-1319 FIA method), v/v% Saturates Olefins Arenes (Aromatics) Visbreaker unit naphtha with EBP = 215 0 Visbreaker unit naphtha with EBP = 1430 0.6933 36.0 52.5 60.0 74.0 83.0 90.0 98.0 104.0 111.0 119.0 129.0 143.0 97 Visbreaker unit naphtha with EBP = 125 0 0.6969 35.0 55.5 61.0 69.0 75.0 80.0 85.0 89.0 93.0 99.0 106.0 125.0 95.5

40

215

50.1 36.9 13.0

52.2 44.7 3.2

47.6 49.1 3.3

Table VII data indicates that as the end boiling point decreases the normal paraffins content increases, iso-parrafins content decreases, olefins

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

content increases, naphthene content does not materially change and that of arenes decrease. Table VII PIONA analysis of Visbreaker unit naphtha with different end boiling points
Composition, wt% Visbreaker unit naphtha with EBP =215 0 0.02 0.56 1.42 2.6 3.08 3.77 3.36 2.72 2.4 1.58 0.13 21.64 0.19 1.02 2.16 2.1 3.64 3.46 3.53 1.35 0.47 0.03 17.95 1.25 3.29 5.5 6.62 6.51 3.87 1.61 0.8 0.85 30.3 0.3 1.26 1.58 2.18 2.58 2.55 0.44 10.89 0.6 Visbreaker unit naphtha with EBP = 143 0 0.03 0.05 0.61 4.99 9.61 12.8 0.12 Visbreaker unit naphtha with EBP = 125 0 0.06 0.87 2.19 5.03 7.54 10.41 0.65 0.01

n-C2 n-C3 n-C4 n-C5 n-C6 n-C7 n-C8 n-C9 n-C10 n-C11 n-C12 Total n-Paraffins i-C4 i-C5 i-C6 i-C7 i-C8 i-C9 i-C10 i-C11 i-C12 i-C13 Total iso-Paraffins O4 O5 O6 O7 O8 O9 O10 O11 O12 Total n-Olefins N5 N6 N7 N8 N9 N10 N11 Total naphthenes 6 A7

28.21 0.26 1.74 6.61 7.83 0.65

26.76 0.29 1.83 4.99 5.94 2.32

17.09 0.2 5.01 14.76 18.25 0.91

15.37 1.9 6.33 12.92 17.03 3.72

39.13 0.66 5.02 5.12 1.34

41.9 0.64 2.8 4.06 1.7 0.03

12.14 1.19

9.23 1.48

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A8 A9 A10 A11 12 A13 Total aromatics Unknowns Total

2.3 2.6 3.38 0.28

0.03

9.16 10.06 100

1.19 2.24 100

1.51 5.23 100

It is presented (in Table VIII) PIONA analysis of mixture - mixed wild naphtha of all LNB hydrotreatment units 50 % and Visbreaker unit naphtha fraction 50 % before and after hydrotreatment in order to compare wild naphtha- Visbreaker unit naphtha mixture quality as feed for Catalytic Reforming unit. These data shows that after hydrotreatment of mixture wild naphtha - Visbreaker unit naphtha C7+ fraction characteristic index 2A + N is 54.4 that is closed to that of the straight run heavy LON (54.9) and after fractionation of naphtha fraction to light and heavy ones the last may be successfully used as Catalytic Reforming feed. Here, it should be noted higher lead and arsenic content of the feed containing Visbreaker unit naphtha fraction. Table VIII PIONA analysis of mixed wild naphtha from LNB hydrotreatment units, Visbreaker unit naphtha, 50 % mixed wild naphtha / 50 % Visbreaker unit naphtha before and after hydrotreatment
Composition, wt% Mixture 1 0.04 0.6 1.65 2.91 5.82 5.31 4.67 0.97 0.6 0.47 0.15 0.06 0.02 23.27 0.55 1.85 6.61 3.22 6.28 3.53 0.66 VBN 0.02 0.56 1.42 2.6 3.08 3.77 3.36 2.72 2.4 1.58 0.13 After Hydrotreatment 50 HTN / 50 50 HTN / 50 VBN VBN 0.03 0.04 0.58 0.73 1.535 1.94 2.755 3.48 4.45 5.62 4.54 5.73 4.015 5.07 1.845 2.33 1.5 1.89 1.025 1.29 0.14 0.18 0.03 0.04 0.01 0.01 22.5 28.4 0.37 0.48 1.435 1.85 4.385 5.67 2.66 3.44 4.96 6.41 3.495 4.52 2.095 2.71

n-C2 n-C3 n-C4 n-C5 n-C6 n-C7 n-C8 n-C9 n-C10 n-C11 n-C12 n-C13 n-C14 Total n-Paraffins i-C4 i-C5 i-C6 i-C7 i-C8 i-C9 i-C10

21.64 0.19 1.02 2.16 2.1 3.64 3.46 3.53

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i-C11 i-C12 i-C13 i-C14 Total iso-Paraffins O4 O5 O6 O7 O8 O9 O10 O11 O12 Total n-Olefins N5 N6 N7 N8 N9 N10 N11 Total naphthenes 6 A7 A8 A9 A10 A11 12 Total aromatics 2A+N Unknowns Total nP (C7+) iP(C7+) O(C7+) N7+ A7+ 2A+N Pb, ppb As, ppb Cu, ppm Na, ppm S, % S, % (after nitrogen purge) % H2S vs total Sulfur RON

0.51 0.08 0.14 23.43 0.1

1.35 0.47 0.03 17.95 1.25 3.29 5.5 6.62 6.51 3.87 1.61 0.8 0.85 30.3 0.3 1.26 1.58 2.18 2.58 2.55 0.44 10.89 0.6 2.3 2.6 3.38 0.28 9.16 29.21 2.43 100 18.0 18.8 26.2 11.5 11.8 35.2 24 49 0.4 1.1 0.36 0.22 38.9 72.6

0.93 0.275 0.085 20.7 0.625 1.695 2.75 3.31 3.33 2.04 0.805 0.4 0.425 15.4 0.49 4.86 7.7 7.155 2.19 1.52 0.22 24.1 0.495 2.12 2.45 1.785 2.6 0.4 0.07 9.9 44.0 7.4 100 16.7 18.4 13.1 23.6 12.0 47.6

1.20 0.36 0.11 26.7

0.15 0.21

0.46 0.68 8.46 13.82 12.13 1.8 0.49 37.38 0.99 3.64 2.6 0.97 1.82 0.52 0.14 10.68 58.74 4.78 100 17.5 20.6 0.5 40.4 13.9 68.2 23 < 1.3 0.3 1.4 0.086 0.007 91.9 53.7

0 0.56 5.54 8.78 8.16 2.50 1.73 0.25 27.5 0.5 2.1 2.5 1.8 2.6 0.4 0.1 9.9 47.4 7.5 100 22.5 25.5 0.0 28.8 12.8 54.4

Wild naphtha fractions octane number is 53.7 (RON) while that of Visbreaker unit naphtha is 72.6. Nevertheless of the higher Visbreaker unit naphtha octane number its addition in quantity of 28.5 % to hydrotreatment

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units wild naphtha fraction results to negligible increase of mixture octane number (RON = 54.2). On the base of these data it may be calculated that the Visbreaker unit naphtha mixed octane number is 55.5. The following mixtures have been additionally prepared and their octane numbers has been determined:
No sample 1 18 % TC naphtha - 08.06.09 + 82% IBP 100 oC fraction o 2 50% GFU C5 fraction + 50 % IBP 100 C fraction RON 63.2 76.5 MON 60.6 68

The light straight run LON RON is equal to 64.9 when determined Visbreaker unit naphtha mixed RON is 55.5. The mixed C5 RON is equal to 88.1 when IBP 100 oC fraction RON is 64.9. The C5 fraction, produced at LNB refinery GFU, hydrocarbon composition is included in Table IX. Table IX Hydrocarbon composition of C5 fraction from Gas Fractionation Unit (GFU)
Hydrocarbon Iso-butane n-Butane 2,2-DMPropane Butenes Iso-Pentane n- Pentane Cyclopentane Olefins 5 Isomers 6 Naphthenes 6 n-Hexane Olefins 6 Benzene Isomers 7 Naphthenes 7 % wt. 0.01 4.21 0.14 1.18 39.16 24.95 2.09 0.27 10.15 2.46 3.55 0.06 1.35 2.79 1.23 Hydrocarbon n- Heptane Olefins 7 Toluene Isomers 8 Naphthenes 8 n-Octane Olefins 8 Aromatics 8 Isomers 9 Naphthenes 9 n-Nonane Aromatics 9 Hydrocarbons 10 Aromatics 10 Hydrocarbons 11+higher % wt. 0.74 0.03 1.60 1.40 0.31 0.14 0.001 1.33 0.09 0.04 0.03 0.57 0.03 0.09 0.002

As it is mentioned above mixed research octane number of this fraction is 88.1 and it may be used at motor gasoline production but after hydrotreatment as it contains 500 ppm sulfur. The C5 fraction Reid vapor pressure (RVP) is 95 kPa and its addition to motor gasoline may be limited because of the motor gasoline standard requirement of 60 kPa RVP as per EN 228. In order to evaluate the effect of C5 content in motor gasoline on their RVP we have prepared several mixtures of basic gasoline with 49.1 kPa RVP and C5 fraction and have determined mixtures RVP. This study results are shown on Figure 1.

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Table X Sulfur compounds content of C5 fraction produced at Gas Fractionation Unit

Fraction C5 Components Sulfur, ppm
Sulfur compounds, ppm

1. Mercaptans: Ethylmercaptan n-Propylmercaptan Isopropylmercaptan Tertiary butylmercaptan Secondary-butylmercaptan 2. Sulfides: Dimethylsulfide Methylethylsulfide 3. Disulfides: DMDS MEDS DEDS
Unknowns

4. Hydrogen sulfide Others

399 293 8 83 4 11 58 40 18 46 0 0 13 33 3 506

827 568 19 198 11 31 120 77 43 98

25 73 4 1048

Fig.1 Motor gasoline RVP (Reid vapor pressure) relationship of C5 fraction content in it
80 75 70 65 RVP 60 55 50 45 40

RVP = 1.3527xC5(%) + 49.1 R2 = 0.9969

10

15

20

25

C5 fraction content in gasoline mixture, % C5 ,%

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

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Data on Figure 1 show that gasoline Reid vapor pressure increases lineally as C5 fraction content increases. When gasoline Reid vapor pressure prior mixing with C5 fraction is 49.1kPa required standard limitation of 60 kPa is reached as C5 fraction content in the mixture is 8 %. At higher Reid vapor pressure of the basic gasoline the quantity of C5 fraction that may be added shall be less. CONCLUSIONS The analyses of wild naphtha fractions produced at LNB hydrotreatment units show that after stabilization they are better feed for Catalytic Reforming unit than straight run heavy LON of Ural crude oil. The Visbreaker unit naphtha after hydrotreatment is more suitable for pyrolysis because of higher paraffins content and low naphthenes content. The Visbreaker unit naphtha end boiling point decrease upgrades the Visbreaker unit naphtha quality as potential feed for pyrolysis and worsens its quality as potential feed for reforming after the light fraction (up to C6 hydrocarbons) removal. The mixture of 50 % wild naphtha 50 % hydrotreated Visbreaker unit naphtha after stabilization is suitable feed for catalytic reforming as its characteristic index 2A+N is identical to that of straight run heavy LON of Ural crude oil.