MODIFIED WATER - BITUMEN EMULSIONS BY PETROCHEMICAL PRODUCTS

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1825

MODIFIED WATER - BITUMEN EMULSIONS BY PETROCHEMICAL PRODUCTS

Alim Feizrahmanovich Kemalov¹, Ruslan Alimovich Kemalov¹,Lenar Marselevich Khaziakhmetov¹

1Kazan Federal University kemalov@mail.ru

ABSTRACT

Bitumen emulsions (BE) of direct and reverse type, as a new type of binder, were developed in the twentieth century, the industrial application of which began in 1953 in France, and at the same time in Russia. BE is a modern complex organic binder [1,2,3] containing an aqueous phase of from 31 to 50% by weight at minimum viscosity. This fact makes it possible to provide the processing of stone materials excluding drying and heating, which, from the technological point of view, makes it possible to use BE for the protection of road worker labor and environment. Depending on applied emulsifiers, BE may be of anionic and cationic species. In the world practice, cationic BE are produced and used, as the most universal and providing a high degree of СOV adhesion to the surface of mineral materials of acidic and basic nature. The most important indicator of BE quality is the rate of their decay, according to which BEs are classified as fast, medium and slowly decaying, BEC 1, 2, 3, respectively [2,3,4]. The performance characteristics of VBE are regulated by the introduction of modifying additives, both in the dispersed phase and in the dispersion medium. In Russia, similar studies related to the modification of VBE by the products of oil origin have not been carried out [2,3,4].

Keywords: bitumen, emulsion, emulsifier, stabilizing additive, physical - chemical properties

INTRODUCTION

At present, in order to increase the profitability of bitumen production, it is necessary to conduct the studies on the interrelation between the group chemical composition of bitumens and the physical- chemical properties of COV. For this purpose, the study of the possibilities concerning the integrated use of petrochemical products (PCP) to regulate the operational characteristics of the COV and BE will make it possible to convert secondary-type PCPs into primary ones, to create the prerequisites for import substitution by the use of expensive emulsifiers, dispersants and BE stabilizers, to increase the profitability of bitumen, COV and BE production significantly. Thus, the primary tasks are the tasks on the development and substantiation of the principles and technological methods aimed at the obtaining of products with specified properties, to expand the raw materials base and the areas of KOV and BE application. It was established earlier that the use of PCP isoprene type (I-PCP) as a complex modifier (Table 1) of BE, which includes the functions of Dinoram SL, the dispersant and the stabilizer physically and chemically effective [2].

METHODS

The rate of decay as the main characteristic of BE is determined by the mixing with the mineral particles a certain porosity called the decay index (DI), the ratio of sand mass (g) spent on the decay of 100 grams of BE. In the production cycle of BE preparation, an important step is to control BE concentration [1,2,3,4]. Appropriate methods were developed to determine the content (wt.%) of water in oils and petroleum products. The most interesting among them is the method of humidity determination in oils and petroleum products using NMR H1 spectroscopy [3,4], which is based on the principle of spin-echo NMR signals excitation by radio-frequency pulses with the period of oscillations starting from the complex methods by Carr-Parsella-Meibum-G Jill (KPMG) and the registration of the spin-echo amplitudes in the reference and test samples of KOV and BE. The fundamental factor is the structural and dynamic effects based on the process BE components diffusion at the interfaces of water/bitumen phases [1,3,4].

RESULTS

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Some physical-chemical parameters of PCP: density ρ420, kg/m³: 1067; kinematic viscosity at 50 ⁰С mm²/s: 7.8; flash point, ⁰С: 108. Then the fractional composition of the I-PCP sample is considered.

Table 1 - Fractionation data of I-PCP

Fraction evaporation temperature, ⁰С Fractional composition, % wt.

b.p.-75 12,65

75-90 7,97

90-110 2,91

110-120 7,08

120-135 50,63

135-140 16,96

140-160 1,13

Residue after distillation Complete distillation

The raw material for the production of BE with the participation of I-PCP is the sample of bitumen of BND 90/130 grade, obtained by the evacuation of heavy oil residue (HOR) from the mixture of Tuymazinsky oil deposit (Table 2).

Table 2 - Physical and chemical characteristics of bitumen of BND 90/130 grade

Indicator name Standard by GOST

22245-90 Actual value

1. Needle penetration depth at 25 ⁰С, 0,1 mm 91-130 115

2. Softening point, ⁰С No less than 43 46

3. Extensibility at 25 ⁰С, cm No less than 65 84

4. Extensibility at 0 ⁰С, cm No less than 4,0 0,5

5. Temperature of brittleness, ⁰С No more than - 17 - 14

6. Flash point, ⁰С No less than 230 230

7. Penetration index from –1,0 to +1,0 -0,8

The content of the aqueous and bitumen phase (wt. %) during the preparation of BE makes 50:50.

Evaluation of dispersant, emulsifying and modifying actions of I-PCP can be traced by the data of Table 3

Table 3 - Basic characteristics of composite BE

Sample Content, % wt. RI, Conditional, Adhesion,

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number I-PCP emulsifier g/100g viscosity, sec points

1 0,5 0,5 390 23 4-5

2 1 0,5 380 21 5

3 2 0,5 320,4 21,9 4

4 3 0,5 313 23,4 4

5 4 0,5 307,8 24,2 3

6 5 0,5 295,4 27 3

7 6 0,5 287,4 25,3 3

8 7 0,5 280 23,8 3

9 8 0,5 - - -

10 9 0,5 - - -

11 10 0,5 - - -

12* - 0,5 482,50 26,4 2

13 0,5 0,25 337,8 21,4 5

14 1 0,25 319,15 19,6 4

15 2 0,25 312,20 20,4 4

16 3 0,25 305,10 21,8 3

17 4 0,25 301,258 22,6 3

18 5 0,25 293,70 25,6 3

19 6 0,25 289,81 23,4 3

20 7 0,25 286,2 20 3

21 8 0,25 - - -

22 9 0,25 - - -

23 10 0,25 - - -

24* - 0,25 460 24 2

* BE samples without I-PCP

Dashes indicate that the prepared BE are prone to premature decay. The maxima in the extremums of RI values are characterized by the interval of 0.5-2% wt. I-PCP, which is characterized by the minimum of relaxation times T2a and T2b. The simbateness was also found for RI values from the content of I-PCP for Dinoram SL with the concentration in BE of 0.25% wt., so the extremum of the RI values corresponds to the content of I-PCP in the range 0.5-2% wt. It was found that the content of I-PCP makes more than 7 wt., causes an intensive coagulation of the dispersed phase of COV in BE samples, which is the result of the premature decay of BE. Presumably, I-PCP forms stable complexes

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with the bitumen phase of BE. For the structurally dynamic I-PCP in the composition of KOV and BE, the pulse NMR N¹ method was used. The thermograms (Fig. 1.2) show the dependences of the nuclear relaxation characteristics of I-PCP.

0 100 200 300 400 500 600 700

0 10 20 30 40 50 60 70 80 90

Температура

T2, мс

T2a T2b

Figure 1 – The thermogram of the relaxation (spin-spin) characteristics determination for I-PCP at phase changes.

0 20 40 60 80 100

0 10 20 30 40 50 60 70 80 90

Температура

P, %

Pa Pb

Figure 2 - The thermogram of I-PCP proton phase population determination at phase changes

500 100150 200250 300350 400450 500550 600650 700

0 1 2 3 4 5 6 7 8

Содержание ОСИ 1, % масс.

Т2, мс

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1829 500

100150 200250 300350 400450 500550

0 1 2 3 4 5 6 7 8

Т2, мс

T2a T2b

I-PCP content, % wt.

Figure 3- Relaxation (spin-spin) characteristics of modified BE at phase changes (for Dinoram SL concentration - 0.25)

0 100 200 300 400 500 600 700 800

0 1 2 3 4 5 6 7 8

Содерж ание ОСИ 1, % масс.

Т2, мс

T2a T2b

500 100150 200250 300350 400450 500550 600650 700

0 1 2 3 4 5 6 7 8

Т2, мс

T2a T2b

I-PCP content, % wt.

Figure 4 - Relaxation (spin-spin) characteristics of modified BE in the course of phase changes (for Dinoram SL concentration - 0.5)

The content of water and bitumen phase (% wt.) in the preparation of BE makes 50:50, concentration:

Dinoram SL - 0.5 and 0.25% wt., I-PCP - from 1 to 10 [2]. The nuclear relaxation characteristics are shown on Fig. 3.4.

In further studies, the influence of I-PCP concentration change on the properties of KOV after the decay of BE [1,2,3,4] was studied, thus the physical-chemical characteristics of emulsified COVs after the decay of BE were determined. Table 5 presents the physical-mechanical characteristics of emulsified KOVs with different concentrations of I-PCP obtained after BE decomposition. The obtained data of Table 5 and 6 correlate, in accordance with ASTM D 2872 they confirm the high compatibility of KOV components, the decrease of heterogeneity, and thus the increase of the adhesion strength characteristics of the obtained KOV [2,3,4,10], thereby they confirm the results of physical-mechanical properties determination and the value of mass loss after heating, regardless of Dinoram SL concentration.

DISCUSSION

According to the classification by A.S. Kolbanovskaya - V.O. Mikhailov [10], the initial bitumen (Table 2) refers to group 3: the amount of asphaltenes is less than 25%, and the amount of resins is less than 36%. As Dinoram SL BE, Dinoram SL of Akzo Nobel company is taken, which is a fat polyamine cation-active surfactant. The studies were conducted (Fig. 5) on the evaluation of the surface tension at the boundary: "Bitumen solution in CCl4 - water" at different concentrations of Dinoram SL (the temperature makes 20 ⁰C).

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0 10 20 30 40 50 60

0,0001 0,001 0,01 0,1 1 10 Концентрация эмульгатора, % мас.

Поверхностное натяжение, Дин/см

Figure 5 – Surface tension of Dinoram SL

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1831 Table 5- Physical-mechanical characteristics of emulsified KOV with different concentrations of I- PCPs obtained after BE decomposition

* Original bitumen

Table 6 - Physical and mechanical characteristics of emulsified KOVs with different concentrations of I-PCP obtained after the decomposition of BE subjected to artificial oxidative aging

* Original bitumen

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Thus, the increase of Dinoram SL concentration in BE contributes to the exponential nature of surface tension decrease. It was found that BE formation occurs at a surface tension value of less than 20 Din/cm and the concentration of Dinoram SL more than 0.1% by weight. Along with this, an extreme character of value dependence is established concerning the conditional viscosity of BE on the content of I-PCP [2].

Regardless of Dinoram SL concentration, the increase in the conditional viscosity is observed for the content of I-PCP from 5 to 7% by weight. A simbitality has been detected. At the temperature of up to 80

°C there is the increase of T2a time with a slight fluctuation of T2b time. In this regard, the dependences of the populations of the phase Pa and Pv population are inversely proportional due to the characteristic phase approach. It should be noted that BEs with different contents of I-PCP are characterized by two times of spin-spin relaxation. It should be noted that the long period of nuclear spin-spin relaxation T2a refers to the protons of water and emulsifier partially distributed in it. The short relaxation time T2b refers to COV protons leaving BE. This is confirmed by the population values of phase hydrogen protons corresponding to the spin-spin relaxation times (Figures 6,7) [1,2,3,4].

0 10 20 30 40 50 60 70

0 1 2 3 4 5 6 7 8

P,%

Pa Pb

0 10 20 30 40 50 60 70

0 1 2 3 4 5 6 7 8

P,%

Pa Pb

I-PCP content, % wt.

Figure 6 - Characteristics of modified BE according to the populations of hydrogen protons during phase changes (for the concentration of Dinoram SL - 0.25%)

0 10 20 30 40 50 60 70 80

0 1 2 3 4 5 6 7 8

Содерж ание ОСИ 1, % масс.

P, %

Pa Pb

0 10 20 30 40 50 60 70

0 1 2 3 4 5 6 7 8

P,%

Pa Pb

I-PCP content, % wt.

Figure 7 - The characteristics of modified BE according to populations by hydrogen protons during phase changes (for Dinoram SL concentration - 0.5%)

At a concentration of Dinoram SL 0.5%, a direct proportional character of the relaxation characteristics T2a and T2b is established. The reduction of Dinoram SL concentration to 0.25% is characterized by an extreme nature of

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1833 relaxation characteristics T2a and T2b at the same content of I-PCP. The extrema in the values of the relaxation characteristics T2a and T2b for BE with a smaller Dinoram SL content are observed when the content of I-PCP is equal to 2%, while the molecular mobility and the phase state change according to the values of the hydrogen protons Pa and Pb populations are observed (Fig. 6), which characterizes the course of KOV and BE structuring processes. This fact correlates with the physical and mechanical properties of BE samples (Table 4). The content of I-PCP in the composition of the KOV and BE affects the relaxation processes as evidenced by complex thermal analysis.

The concentrations of Dinoram SL 0.25 and 0.5% wt. testify to the extreme dependence of NMR parameters at the content of I-PCP from 0.5 to 2% wt. The analysis temperature increase from 140 to 160 С КОV is characterized by extreme values of relaxation periods and the population of hydrogen protons, which shift with the content of I-PCP - 2%, wt. Similarly, the character of the dependences is observed according to the effect of I-PCP content for BE with the concentration of Dinoram SL making 0.25%. The consequence of I-PCP component influence on KOV properties is the change of the physical=chemical characteristics, such as softening temperature (Traz) and adhesion, as well as the changes in the relaxation characteristics: T2a and T2b and the populations of COV and BE protons, regardless of Dinoram SL concentration. It should be noted that the effect of I-PCP components on the properties of COV and BE is manifested at temperatures from 60 to 800 C. Thermal analysis data on the evaluation of the relaxation characteristics behavior indicate that the most significant changes are noted for the times T2a and T2b. The parameter T2c varies insignificantly, which refers to asphaltenes. It is known [2,3,4,5] that three times of nuclear spin-spin relaxation are observed in TNO and bitumens. It is natural that the times T2a and T2b refer to the proton-containing groups of maltens: oils and resins, the time T2c refers to asphaltenes. At the introduction of I-PCP in the composition of TNO and bitumen, the largest change of the nuclear relaxation parameters is observed for long and average nuclear relaxation times T2a and T2b. I-PCP has an effect on the malttenic part of bitumen, and it is very important that it is not limited to high temperatures. This fact makes it possible to use I-PCP in the industrial production of bitumen, BE and COV compositions at low temperatures (down to - 4 °C), which is also important in operating conditions [1,2,3].

It was found that the introduced PCPs make a negligible effect on asphaltenes [11, 12, 13]. So the molecular mobility of I-PCP is commensurable, and symbasic with the maltene part of TNO and bitumens.

CONCLUSIONS

The most important data on the evaluation of I-PСP effect on VBE properties are obtained during the analysis of the adhesion-strength capacity [2], so COV samples have the maximum values with I-PCP content: 0.5-2%, regardless of Dinoram SL concentration in BE. With I-PCP content of 4%, the increase of Traz is observed in KOV composition. The results of malacometric characteristics determination: ductility and penetration are of interest. For Dinoram SL 0.25% - 0.5%, the direct proportionality of the changes is noted in the values of ductility and penetration: for I-PCP of 1% the value of ductility increases. For Dinoram SL - 0.25 - 0.5% ductility increases symbasically, the same character is observed at the adhesion-strength interaction of I-PCP with a sample of bitumen. It is important to note a complex overall integral effect: the effect of I-PCP on the molecular mobility of bitumen components. I-PCP exhibits plasticizing ability increasing the molecular mobility in COV and BE, thereby regulating the molecular mobility of bitumen asphaltenes, COV and BE. This fact is confirmed by the results of I-PCP influence on nuclear relaxation characteristics at complex thermal analysis [2,3,4].

SUMMARY

The results of conducted studies of modified KOV and BE indicate that the content of I-PCP can be regulated by the performance characteristics of BE, which can be attributed to the class of slowly decaying BE.

ACKNOWLEDGEMENTS

The work is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University.

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