Al-Farabi Kazakh National University and Institute of Combustion Problems 2017 International Conference on Functional Materials and Chemical Engineering (ICFMCE 2017) PRODUCTION OF PETROLEUM BITUMEN BY OXIDATION OF HEAVY OIL RESIDUE WITH SULFUR Ye. Tileuberdi, Ye.A. Akkazin, Ye.K. Ongarbayev, Ye.I. Imanbayev, Z.A. Mansurov Dubai, UAE, November 24-26, 2017

Position: Associate professor Al-Farabi Kazakh National University Faculty of chemistry and chemical technology Chair of chemical physics and materials science Position: Associate professor Institute of Combustion Problems Laboratory of oxidation processes of hydrocarbons Position: Senior research fellow Technical University of Berlin Institute of Petroleum Chemistry, Russia China University of Petroleum (Beijing)

Laboratory of oxidation processes of hydrocarbons (Institute of Combustion Problems) 1. Natural bitumen processing and use of oil sands 2. Production of bitumen from heavy oil residues 3. Modification of bitumen by rubber crumb and other 4. Water purification from oil pollution 5. Biological cleaning of soil from oil pollution

OIL PRODUCING SECTOR OF KAZAKHSTAN At present the oil producing sector has a leading position in the structure of national economy of Kazakhstan. The approved extracting stocks of hydrocarbon in RК, including on land stocks are estimated to be 30 billion barrels of oil (4.0 billion ton) and 3.0 trillion m3 of gas. 9th Largest Country by territory 9th Largest Oil Reserves 15th Largest Crude Oil Producer

ACTUALITY OF RESEARCH ACTUALITY THEME At present oil producing sector has a leading position in the structure of national economy of Kazakhstan. Oil bitumen are widely used in many industries, therefore their production is the important economic problem and requires constant perfection. The main problem with road building is the poor quality of bitumen used in asphalt-concrete pavements. Bitumen using in road construction Graphic of bitumen consumption 2

Object of the research The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions.

Scheme and photograph of the unit for oxidation of heavy oil residues 1 - the motor of the mixer; 2 - a branch pipe for a conclusion of gas; 3 - cylindrical reactor; 4 - electric furnace; 5 - agitator; 6 - a branch pipe for a conclusion of products; 7 - the rack; 8 - thermostat; 9 - thermocouple Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours.

Table 1. Physical and mechanical characteristics of the oxidation products of Karazhanbas oil residue with the addition of sulfur at 200 С Amount of sulfur added to oil oxidation, mas. % 5 7 10 Oxidation time, hour 3 3,5 4 The depth of penetration of the needle into the bitumen at 25 °C, 0.1 mm: 295 205 156 206 180 116 27 24 14 Softening point, ° C, not less: 40 42 44 41 45 49 68 78 86 Brittleness temperature, ° C, max: - -21 -23 -25 -14 Penetration index 2,3 0,9 0,4 0,5 1,5 1,1 Standard accordance BND 200/300 BND 130/200 BN 90/130 BN 70/30

Table 2. Physical and mechanical characteristics of the oxidation products of oil residue at the temperature 210 °С with sulfur Amount of sulfur added to oil oxidation, mas. % 10 Oxidation time, hour 2 2,5 3 3,5 4 The depth of penetration of the needle into the bitumen at 25 °C, 0.1 mm: 255 225 155 105 65 9 8 Softening point ring and ball, ° C, not less: 16 23 31 36 41 82 90 98 104 108 Standard accordance - BN 90/10 5 7 276 202 123 86 55 76 56 47 29 24 32 37 40 46 53 44 51 57 62 Brittleness temperature, ° C, max: -18 -12 -10 Penetration index -1,4 -1,9 -1 -0,2 -1,8 1,0 -0,8 0,2 BND 40/60

Figure 1. Dependence of penetration on the oxidation time of products Penetration at 25 °С, 0.1 mm at the 210 °С at the 200 °С Oxidation time, h 1 – without adding sulfur; with sulfur in the amount: 2 – 5 wt. , 3 – 7 wt. , 4 – 10 wt.  With sulfur in the amount: 2 – 5 wt. , 3 – 7 wt. , 4 – 10 wt. 

Figure 2. Dependence of softening point on the oxidation time of products at the 200 °С at the 210 °С Softening temperature, С Oxidation time, h 1 – without adding sulfur; with sulfur in the amount: 2 – 5 wt. , 3 – 7 wt. , 4 – 10 wt.  1 – without adding sulfur; with sulfur in the amount: 2 – 5 wt. , 3 – 7 wt. , 4 – 10 wt. 

The number of carbon atoms The number of carbon atoms Quantity, % Figure 3. Сomponent composition of oxidation products of Karazhanbas oil residue (1) and without sulfur (2) and with 5 % of sulfur at 210 С for 4 hours Quantity, % The number of carbon atoms Сomponent composition of paving bitumen BND 60/90 (1), BND 90/130 (2) and BN 90/10 (3) Figure 4. Сomponent composition of paving bitumen BND 60/90 (1), BND 90/130 (2) and BN 90/10 (3) The number of carbon atoms Сomponent composition of oxidation products of Karazhanbas oil residue (1) and without sulfur (2) and with 5 % of sulfur at 210 С for 4 hours

Chemistry of oil residue oxidation with sulfur Chemistry of the sulfurizing of oil residues and sulfur gas emissions process are: 2RH + SX  R-SX-1-R + H2S R-SX-1-R + [O]  R-SX-1O-R R-SX-1O-R + [O]  R-SX-1O2-R R-SX-1O2-R  R-SX-2-R + SO2 A possible scheme of sulfur interaction with various radicals as below: Ar-CH-CH3 + R-CH2 + S8  Ar-CH(CH3)-S-S6-S-CH2-R And Ar-CH2-R + 2O2  Ar-CH(R)-OO + HO2 Ar-CH(R)-OO + R1H  Ar-CH(R)-OOH + R1 R1 + S2  R1-S-S R1-S-S + R2  R1-S-S-R2 Ar-CH(R)-OOH + R1-S-S-R2  Ar-CH(R)-OH + R1-SO-S-R2.  

CONCLUSION Obtained data allow making the conclusion that the addition of elemental sulfur leads to reduction of time of process of oxidation and mitigation of regimes of process. The results of researches have shown, that oxidation of high-viscous oil residue with the addition of elemental sulfur (5-10 wt. %) at low temperatures (200 and 210 ºC) for short time (3,5-4 hours) can receive bitumen of satisfactory quality. The resulting of oxidation process exhibit elasticity, increased softening point, decreased brittle point, and enhanced strength. These properties allow sulfur bitumen products to be used both as binders for asphalt concretes and as mastics for pavement repair. Also, it allows partially solving the problem of utilization of sulfur which collected in oil extraction regions. Indicators Usually oxidation Oxidation in the presence of sulfur Process temperature, C 250-270 200-210 Process duration, h 5-8 3-4 Air flow, l / min 1 4 Catalyst or sulfur content intoxication, % - 5-7 Bitumen brand BND 200/300, BND 130/200 BND 200/300, BND 130/200, BDD 40/60 Process specificity Temperature is low, time is short Process disadvantage Long oxidation time At high temperatures, sulfur gases are released

Thank You For Your Attention