According to different estimates, geological heavy oil and natural bitumens resources at the Tatarstan deposits make 1,5-
7 billion tons. On the territory of Tatarstan across all bituminous horizons about 450 deposits of natural bitumens have
been found. One third of deposits of this raw materials existing in Russia fall on the share of Tatarstan. Natural bitumens
are valuable material for production of fine chemicals that are used in different spheres of life activities

Gajnullin Vasil Ilyasovich

Kemalov Alim Fejzrahmanovich

Kemalov Ruslan Alimovich

Valiev Dinar Zinnurovich

Indian Journal of Science and Technology

According to different estimates, geological heavy oil and natural bitumens resources at the Tatarstan deposits make 1,5- 7 billion tons. On the territory of Tatarstan across all bituminous horizons about 450 deposits of natural bitumens have been found. One third of deposits of this raw materials existing in Russia fall on the share of Tatarstan. Natural bitumens are valuable material for production of fine chemicals that are used in different spheres of life activities. Natural bitumen is to a different extent oxidized high-viscosity oils of liquid, semi-liquid and hard texture with high content of sulfur, resins and asphaltenes. In contrast to oil, they are characterized by increased content of vanadium, nickel, molybdenum and significantly smaller content of gasoline and diesel fractions. Nevertheless, despite the works performed, no significant success has been achieved in production and processing of bitumens yet. This is mainly because of absence of the relevant equipment. It is necessary to accelerate development of bituminous deposits, creation of complexes with the use of high performance technologies and technical means for most complete extraction of this raw material from the earth and treatment thereof. Implementation thereof will create pre-requisites for commercial exploitation of natural bitumens deposits not only in Tatarstan but in other regions of the Russian Federation as well. To estimate the potential capability of natural bitumens and high viscosity oils it is necessary to perform detailed analysis aimed at determining the graphical charts of the true temperature curve, density, low-temperature, viscosity properties, fraction and hydrocarbon composition

Kemalov A.

Kemalov R.

Valiyev D.

Gaynullin V.

Kazan Federal University Digital Repository

Indian Journal of Science and Technology 2016 vol.9 N18Estimation of potential capability of natural bitumensand high viscosity oils for refining according to fuel-bitumen schemeKemalov A., Kemalov R., Valiyev D., Gaynullin V.Kazan Federal University, 420008, Kremlevskaya 18, Kazan, RussiaAbstractAccording to different estimates, geological heavy oil and natural bitumens resources at theTatarstan deposits make 1,5- 7 billion tons. On the territory of Tatarstan across all bituminoushorizons about 450 deposits of natural bitumens have been found. One third of deposits of thisraw materials existing in Russia fall on the share of Tatarstan. Natural bitumens are valuablematerial for production of fine chemicals that are used in different spheres of life activities.Natural bitumen is to a different extent oxidized high-viscosity oils of liquid, semi-liquid and hardtexture  with  high  content  of  sulfur,  resins  and  asphaltenes.  In  contrast  to  oil,  they  arecharacterized by increased content of vanadium, nickel, molybdenum and significantly smallercontent  of  gasoline  and  diesel  fractions.  Nevertheless,  despite  the  works  performed,  nosignificant success has been achieved in production and processing of bitumens yet. This ismainly  because  of  absence  of  the  relevant  equipment.  It  is  necessary  to  acceleratedevelopment of bituminous deposits, creation of complexes with the use of high performancetechnologies and technical means for most complete extraction of this raw material from theearth and treatment thereof. Implementation thereof will create pre-requisites for commercialexploitation of natural  bitumens deposits not only in Tatarstan but in other regions of theRussian Federation as well. To estimate the potential capability of natural bitumens and highviscosity oils it is necessary to perform detailed analysis aimed at determining the graphicalcharts of the true temperature curve, density, low-temperature, viscosity properties, fractionand hydrocarbon composition.http://dx.doi.org/10.17485/ijst/2016/v9i18/93742KeywordsAdditives, Bitumens, Bituminous materials, Fuels, High viscosity oils, Natural bitumens,Processing, Refining, True temperature distillation curve

Estimation of potential capability of natural bitumens and high viscosity oils for refining according to fuel-bitumen scheme

Indian Journal of Science and Technology, Vol 9(18), DOI: 10.17485/ijst/2016/v9i18/93742, May 2016ISSN (Print) : 0974-6846ISSN (Online) : 0974-5645* Author for correspondence1.  IntroductionAt the current stage the strategic trend of development of the oil and gas industry is increase in the oil conversation depth with the use of relatively new approaches and methods of mining, treatment, transporting and processing of different kinds of Hydrocarbons (HC)1,2.2.  Materials and MethodsThe provided sample of natural bitumen from the Nagornoye deposit contained 30% of water. After dehydration the sample was subjected to analysis aimed at integral determination of the main physico-chemical properties and component composition1. The results of analysis of the natural bitumen from the Nagornoye deposit are presented in the Table 1.As it follows from the Table 1, by content of asphalt-resinous matters (39,8% wt.) the natural bitumen under investigation is referred to the ‘maltha’ class (35-60% wt.). Upon high content of resinous-asphalt-new substances natural bitumen features small paraffin content (0,5% wt.). High sulfur content is also peculiar to this natural bitumen (3,4% wt.).AbstractAccording to different estimates, geological heavy oil and natural bitumens resources at the Tatarstan deposits make 1,5-7 billion tons. On the territory of Tatarstan across all bituminous horizons about 450 deposits of natural bitumens have been found. One third of deposits of this raw materials existing in Russia fall on the share of Tatarstan. Natural bitumens are valuable material for production of fine chemicals that are used in different spheres of life activities. Natural bitumen is to a different extent oxidized high-viscosity oils of liquid, semi-liquid and hard texture with high content of sulfur, resins and asphaltenes. In contrast to oil, they are characterized by increased content of vanadium, nickel, molybdenum and significantly smaller content of gasoline and diesel fractions. Nevertheless, despite the works performed, no significant success has been achieved in production and processing of bitumens yet. This is mainly because of absence of the relevant equipment. It is necessary to accelerate development of bituminous deposits, creation of complexes with the use of high performance technologies and technical means for most complete extraction of this raw material from the earth and treatment thereof. Implementation thereof will create pre-requisites for commercial exploitation of natural bitumens deposits not only in Tatarstan but in other regions of the Russian Federation as well. To estimate the potential capability of natural bitumens and high viscosity oils it is necessary to perform detailed analysis aimed at determining the graphical charts of the true temperature curve, density, low-temperature, viscosity properties, fraction and hydrocarbon composition.Keywords: Bitumens, Bituminous Materials, Fuels, Additives, High Viscosity Oils, Natural Bitumens, Processing, Refin-ing, True Temperature Distillation CurveEstimation of Potential Capability of Natural Bitumens and High Viscosity Oils for Refining According to Fuel-Bitumen SchemeAlim Feyzrakhnamovich Kemalov* , Ruslan Alimovich Kemalov, Dinar Zinnurovich Valiyev and Vasil Ilyasovich GaynullinKazan Federal University, Kremlyovskaya St. 18, Kazan - 420008, Russian Federation; Alim.Feyzrakhnamovich.K@gmail.com, Ruslan.Alimovich.Kemalov@gmail.com, DZinnurovich.Valiyev@gmail.com, Vasilig12@gmail.comVol 9 (18) | May 2016 | www.indjst.org Indian Journal of Science and Technology2Estimation of Potential Capability of Natural Bitumens and High Viscosity Oils for Refining According to Fuel-Bitumen Scheme Table 1.    Indicators of the natural bitumen of the Nagornoye depositIndicators ValuesRelative density, р420 1,02Content, % wt.Sulfur 3,4Asphaltenes 21,8Silica gel resins 18,0Paraffin 0,5Carben carboidesMechanical impurities -Bubble point, °С 106Fraction content, % wt.НК-200°С 0,9200-250°С 3,2250-300°С 9,84300-350°С 8,8350-400°С 10,8400-440°С 7,3Above 440°С 59,16Figures of stripping to specified temperatures are presented in the Table 2; according to the data obtained the TTC of stripping to specified temperatures was designed and shown in Figure 1.Table 2.    Values of stripping to specified temperaturesOil fraction boiling range, °C Stripping % 200 0,9250 4,1300 13,94350 22,74400 33,54440 40,84above 440°С 59,16Figure 1.    TTC of the natural bitumen from the Nagornoye deposit.3.  ResultsAs it follows from the above-specified results, the natural bitumen sample is characterized by insignificant distillate of gasoline and diesel fractions: 0,9 and 21,84% wt., respectively. The total yield of fractions distillated at above 300°С for natural bitumen makes 81,06 % wt. whereas for Devonian oil - 30-35% on the average and for carbonic oil - 39-42% wt. Such high yield of these fractions from the natural bitumen is achieved primarily due to the fractions distillated at above 400°С (66,46% wt.). These fractions are the main raw material for catalytic cracking plant and, therefore, by processing natural bitumen with the use of this plant much more of this fraction may be refined and is shown in Table 3. If we consider natural bitumen as raw material for production of bituminous pavements, then according to the classification presented in the Table 3 it is referred to the group of ‘most suitable’ for this purpose (А=21,8; R=18; P=0,5; 21,8+18-2,5*0,5=38,55, i.е. >8).Table 3.    Classification of oils by their fitness for production of bituminous Group Dependence between content of asphaltenes, resins and paraffin in oil (in % wt.)Oil fitness for production of bituminous pavements I А + R – 2,5 P > 8 Most fit  II А + R – 2,5 P from 0 to 8 At А + R > 6Fit III А + R – 2,5 P < 0 as well as А + R – 2,5 P > 0, But at А + R < 6UnfitThe use of natural bitumens for production of bituminous pavements and different bituminous products proves that recovery thereof may be economically viable since extraction, transportation and processing of natural bitumens according to the traditional procedure makes them non-competitive as compared to ‘ordinary’ oils2-5.Since gasoline fraction is present in a slight amount (0,9% wt.) the analysis was started from the diesel fraction.Two fractions were tested for pour point:Sample No. 1: diesel fraction with distillate temperature up to 300°C.Sample No. 2: diesel fraction with distillate temperature up to 350°C.The provided samples correspond to the summer diesel fuels type by the pour-point temperature. As could be expected, with increase in the distillation degree the pour-point temperature increases: for the sample no. 1 – Alim Feyzrakhnamovich Kemalov, Ruslan Alimovich Kemalov, Dinar Zinnurovich Valiyev and Vasil Ilyasovich Gaynullin Vol 9 (18) | May 2016 | www.indjst.org Indian Journal of Science and Technology 3pour-point temperature (tpour-point) makes minus 24оС; for the sample 2 – tpour-point. = minus 19оС.In order to reduce the pour-point temperature in the sample No. 2 (with higher pour-point) synthetic depressor additive6, 7 was introduced in the amount 0,1% wt. the pour-point decreased to 35оС, i.e. the depressor effect made 16оС.Thus, with the use of depressor additive8 the summer diesel fuel was adjusted to the requirements to winter fuel is shown in Table 4.Indicators of the diesel fraction distilled to 350оС modified through a depressor additive are presented in Table 4.Table 4.    Physico-chemical characteristics of modified diesel fraction distilled up to 350оС Indicators For our productGOST 305 for winter fuelTest methodsFraction composition is distilled over at the t, оС:50%96%310350not >250not >340 GOST 2177-66Kinematic viscosity at 20°C, cSt4,9 1,8- 5,0 GOST 33-82Density at 20оС, kg/m3 826 not >840 GOST 3900-85Copper plate test With-standsWithstandsFlash point (closed cup), оСnot < 35Cloud point, оС -25 not > (-25)Pour-point temperature, оС-35 not > (-35)Total sulfur content, % wt.not >0,5As it follows from the Table 4, modified diesel fuel distilled up to 350оС meets the requirements of the standard for winter diesel fuel. Introduction of additive in the diesel fuel distilled to 300оС results in further decrease in the pour-point temperature: from minus 24оС to minus 43оС.Vacuum distilled fractions (>350°С; >400°С and > 440°С) were tested for compliance with the properties imposed on bitumens. Their characteristics are presented in the Table 5. As follows from the comparison of the Table 5 and Table 6, fraction, etc. Thereafter the studies consisting in modifying the properties of gasoil cuts, namely production of bitumen-polymer compositions were performed.Table 5.    Fraction characteristics: >350°С, >400°С and  > 440°С.Physico-chemical characteristics Oil fraction boiling range, °C>350°С >400°С >440°СRing-and-ball softening point, °С 40 50 58Stretching property, cm 44 18 8,5Depth of needle penetration, 0,1 mm, at 25°С66 20 10The fraction > 350оС features the best indicators in terms of production of a bitumen-polymer composition. The impact of polymer bitumen component directly depends on oil fraction content in the latter. In this light it makes sense to use bitumens with lower softening point for mastic production. Besides, with increase in the softening point bitumen becomes hard and fragile as the asphaltenes content increases and the disperse medium become less elastic and frost-resistant. Addition of oil fractions results in improvement of low-temperature properties of the compound.In order to estimate the possibility of use of heavy oil residue for production of bitumen-polymer compound this fraction > 350о С was modified using the sample of Low-molecular Polyolefin (LPO) - wax-like, semitransparent, hydrophobic substance of white color featuring high adhesion to different materials. The product consists of the mixture of saturated hydrocarbons primarily normal ones. The properties are presented in the Table 6.Table 6.    Physico-chemical characteristics of low-molecular polyolefin NPOPhysico-chemical characteristics Values Melting point, оС 90Dropping point, оС 80Flash-point (open cup), оС 263Molecular weight 1500Initial boiling point,  оС: 3305% boils off at the temperature, оС: 405Main performance characteristics of the bituminous composition obtained: Vol 9 (18) | May 2016 | www.indjst.org Indian Journal of Science and Technology4Estimation of Potential Capability of Natural Bitumens and High Viscosity Oils for Refining According to Fuel-Bitumen Scheme •	 Ring-and-ball softening point - 66 °С;•	 Stretching property - 29 cm;•	 Depth of needle penetration at 25°С - 95 mm ×0,1.Table 7.    Properties of cements MBR (bituminous-rubber cement) according to GOST 15836Physico-chemical characteristicsMastic grade MBR-65MBR-75MBR-90MBR-100Ring- and-ball softening point, ºС 65 75 90 100Depth of needle penetration at 25°С, mm×0,1, not < 40 30 20 1,5Stretching property, cm, not < 4 4 3 2Water saturation during 24 hours, %, not > 0,2 0,2 0,2 0,2Comparative analysis of properties of produced bituminous compound with the GOST 15836 requirements for insulating rubber mastics are shown in Table 7 as well as with properties of asphalt, construction and roofing bitumens8-11 demonstrates that produced bituminous-polymer compound meets the requirements for mastic of the MBR-65.The next stage of work was performance of studies aimed at reduction of viscosity of natural bitumen. Taking into account literature data about the positive effect of different kinds of exposure (ultrasonic, rotary-pulsed and other) on viscosity properties, natural bitumen was subjected to ultrasonic exposure at the plant UZDN-2Т generating ultrasound with the frequency 22 kHz and processing on a Rotary-Pulsed-Acoustic Device (RPAD)12,13.It was suggested that under influence of such processing change of the disperse structure of natural bitumen will take place and, as the result, reduction of its viscosity. The results of these studies are summarized in the Table 8.Table 8.    Impact of oil refining conditions on its viscosity.Oil under investigation Relative viscosity at 40оС, оVUUntreated oil 12,74Oil after treatment with ultrasonic disperser UZDN for 10 minutes11,74Oil after treatment with RPAD during 8 minutes at 7000 rpm11,15Oil after treatment with RPAD during 10 minutes at 10000 rpm10,93As it follows from the Table 8 the optimal mode is oil treatment in the RPAD within 10 minutes with the rate 10,000 rpm. The oil viscosity is reduced from 12,74оVU to 10,93оVU, i.e. by 14,2%. The next stage was performance of studies aimed at increasing the yield of light oil fractions as the result of oil treatment with the use of the RPAD. It was suggested that under influence of such processing change of the disperse structure of natural bitumen will take place and, as the result, reduction of its viscosity. The results of these studies are summarized in the Table 9 and Table 10.Table 9.   Estimation of light fractions prior to RPAD processingviscosity.Oil fraction boiling range, °C % wt.106-200 1,8200-250 3,25250-300 71,55∑ 76,6Table 10.   Estimation of light fractions after RPAD processingOil fraction boiling range, °C % wt.106-200 2,1200-250 3,4250-300 72,6∑ 78,1The tests of the fraction 250-300°C at the pour point temperature were performed. The pour-point of the 250-300°C fraction makes minus 4°C. In order to reduce the pour-point temperature in the 250-300°C fraction synthetic depressor additives was introduced in the amount 0,1% wt. The pour-point decreased to 18оС, i.e. the depressor effect made 14оС.4.  ConclusionsAs the result of the study it was established that treatment in a RPAD within 10 minutes at the rotation rate 10000 rpm provides increase in the light fraction yield by 1,5%. It was found that the optimal mode is oil treatment in a RPAD within 10 minutes at the rotation rate 10000 rpm. The oil viscosity is reduced from 12,74 оVU to 10,93 о VU, i.e. by 14,2%.5.  SummaryAs the result of the comprehensive research performed Alim Feyzrakhnamovich Kemalov, Ruslan Alimovich Kemalov, Dinar Zinnurovich Valiyev and Vasil Ilyasovich Gaynullin Vol 9 (18) | May 2016 | www.indjst.org Indian Journal of Science and Technology 5the viability of use of natural bitumens of the Nagornoye deposit as the target raw material by production of fuel-oil fractions and bitumens of various application shall be noted.6.  Conflict of InterestsThe author confirms that the data provided does not contain the conflict of interests.7.  AcknowledgmentsThe work is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University8.  References1. Kemalov RА, Kemalov AF. Complex investigations of heavy oil of Akanskoye deposits. Neftyanoe khozyaystvo, Oil In-dustry. 2012; 10:114-6.2. Kemalov AF, Kemalov RA. Development of the technology of black oil macromolecular structuring in the process of its oxidation for obtaining the bituminous insulating materi-als. World Applied Sciences Journal. 2013; 23:51-5.3. Kemalov AF, Kemalov RA. Study of disperse polymer sys-tems for producing high-quality polymeric-bituminous materials. Chemistry and Technology of Fuels and Oils. 2012; 48:339-43. 4. Kemalov AF, Kemalov RA. Use of natural bitumen as raw materials for receiving bituminous insulating materials. Neftyanoe khozyaystvo, Oil Industry. 2014, 11, pp. 140-143. 5. Kemalov AF, Kemalov RA. Enhancement of interfacial ad-hesion in bitumen coatings by film-forming agents. World Applied Sciences Journal. 2013; 23:679-84.6. Kamala AF, Kamala RA. Developments of additives the de-pressor dispersing structures to oil fuels. Proceedings of the 2013 International Conference on the Transformation of Education; 2013. p. 94-105.7. Kemalov AF, Kemalov RA. Creation of chair high-viscos-ity oil and natural bitumen’s at the Kazan Federal (Volga region) University – A step to future competitive technol-ogies of development of heavy oil hydrocarbonic raw ma-terials of the republic of Tatarstan.  The Recent Trends in Science and Technology Management, Held by SCIEURO; London. 2013. p. 247-58.8. Soni K. Waste to resource for sustainable development. Indian Journal of Science and Technology. 2016; 9:123-31.9. Kemalov AF, Kemalov RA. Structural and dynamic studies of naphtha crude residue with different chemical nature. World Applied Sciences Journal. 2013; 22:16-22.10. Kemalov AF, Kemalov RA. Relationship between the struc-tural-group composition and physicochemical properties of insulating primers for the protection of oil and gas equip-ment. World Applied Sciences Journal. 2013; 23:892-7.11. Montazeri-Gh M, Mahmoodi-k M. Investigation of the energy management and power train systems effects on hybrid vehicle performance. Int J of Electric and Hybrid Vehicles. 2015; 7(1):40-61.12. Kemalov AF, Kemalov RA. Scientific practical aspects of re-ceiving bi-tuminous emulsion mastics. Technologies of Oil and Gas. 2012; 6:31-9.13. Kemalov RA. The modified special bitumens and paint-work materials on their basis [Diss. Cand. Eng. Sci.]. Kazan State Technology University; 2003.

Estimation of Potential Capability of Natural
Bitumens and High Viscosity Oils for Refining
According to Fuel-Bitumen Scheme

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Estimation of Potential Capability of Natural Bitumens and High Viscosity Oils for Refining According to Fuel-Bitumen Scheme

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