**2. Experimental**

The properties of known oxygen-generating additives which activate the motor fuel combustion are presented in **Table 1** [38]. The table shows reagents which do


The insoluble calcium hydroxide in the alcohol was filtered off, and the absolute ethyl alcohol by reactions (4) and (3) was discharged through a direct refrigerator,

During the hydrolysis of TET the titanium tetrahydroxide, which is insoluble in alcohol, precipitates and can be filtered out; the absolutized alcohol is distilled at a special installation under vacuum, or with air dehydrators under normal conditions. As can be seen from **Table 3** [42], ethanol has the most similar properties with gasoline according to the main indicators (boiling point and octane number). In addition, it is the cheapest and most affordable as a bioethanol—a product of natural raw materials processing, therefore, it was selected for absolutization. The ethanol concentrations were measured by the weight pycnometer method and determined by theoretical data [43]. The volume concentration of alcohol is determined by the areometers (ASP-1, ASP-2) using tabular data. Chromatography of ethanol and gasoline is carried out on by a gas–liquid chromatography, a method for determining oxygen-containing compounds in gasoline (HPCHEM\SEQUENCE \D161124A. S\METHOD\ D4815N.M) by internal standard (ISTD) based on 15 known calibrated substances, including ethanol (**Figures 2–4**). Infrared spectroscopy of ethanol samples is carried out by IR spectroscope (IS 50 FT-IR "NICOLET" Slovensko). Mass spectroscopy of the samples is carried by a mass spectroscope (MX-7304A, AO.SELMI, Sumy, Ukraine, 1 to 210 mass range). Determination of the cetane number of diesel fuel L-0.2-40 and the octane number of petrol A-80, as well as the freezing point of diesel fuel was carried out using the laboratory analyzer "Octane meter" of Shatox sx-100 k type [44]. Also, an assessment of the petrol gasoline by a motor method was carried out at the "OKKO" quality control labora-

**Parameter Units Methanol Еthanol Butanol Gasoline** Molecular formula СН3ОН С2Н5ОН С4Н9ОН С6Н<sup>6</sup> Molecular weight g/mol 32.04 46.07 74.12 78.11 Melting point K 175 159 183 278 Boiling point K 338 351 390 353 Density g/cm<sup>3</sup> 0.791 0.789 0.81 0.879 Saturated vap. pres. kPa, 298 K 16.2 6.5–7.5 0.8 12.7 Vapor density g/l, 298 K 1.3 1.9 2.4 3.2 Water solubility g/100 ml Unlimited Unlimited 7.9 g/100 ml 1800 mg/l Viscosity s�Pа, 298 K 0.544 1.074 – 0.649

1.087Е�4 2.097Е�4 to

Energy density МJ/l 16 19.6 29.2 – Octane number RON – 156 132 104 82.5–98.0 Cetane number MON – 92 89 78 95

*Comparative physico-chemical characteristics of oxygen generating additives—gasoline combustion*

2.571Е�4

– 2.219Е�1

ð Þ СН3СН2О <sup>4</sup>Ti þ 4H2O ! 4СН3СН2ОH þ Ti OH ð Þ4↓ (4)

Tetraethoxytitanium (CH3CH2O)4Ti as a dehydrator acts in different way.

and the calcium hydroxide remained in the flask in the precipitate form.

*Improving the Technology of Synthesis Absolutized Bioethanol*

*DOI: http://dx.doi.org/10.5772/intechopen.92332*

tory in Galich, Ivano-Frankivsk region of Ukraine.

Henry's constant *С*air*=C*H2O,

**Table 3.**

**225**

*activators [42].*

298 K

**Table 1.**

*Octane number of oxygen generating gasoline additives, which is measured by different methods.*

not contain water, including ethyl alcohol and ethers, but in this work it is not described how the ethyl alcohol was absolutized, therefore in different sources it has a different octane number. Consequently, we propose our own method of ethanol absolutization with calcium oxide or tetraethoxytitanium (TET).

Researches of the method of ethanol absolutization by chemically binding water reagents such as calcium oxide and TET are conducted. Alcohols practically do not interact with alkalis, because among the reaction products there is water that decomposes formed alcoholate and a reverse reaction takes place.

$$\begin{aligned} 2\text{CH}\_3\text{CH}\_2\text{OH} + \text{CaO} &\to \text{CH}\_3\text{CH}\_2\text{OC}\text{a}\text{OCH}\_2\text{CH}\_3 + 2\text{H}\_2\text{O} \uparrow\\ &\to 2\text{CH}\_3\text{CH}\_2\text{OH} + \text{Ca}(\text{OH})\_2 \end{aligned} \tag{1}$$

Therefore, fresh prepared (1123 K, 2 h) mineral calcium carbonate, which has the following characteristics, presented in **Table 2**, was used for ethanol absolutization.

After calcination, samples of CaO were cooled in a vacuum desiccator, to reduce air access and to re-carbonize calcium oxide. Only 1 grade with minimum content of impurities was taken for work (**Table 2**).

It was suggested that if you take freshly calcined calcium oxide, then absolutized ethyl alcohol and alcoholates of the corresponding metals can be obtained during an irreversible reaction:

$$\text{C} \text{CH}\_3\text{CH}\_2\text{OH} \cdot \text{H}\_2\text{O} + \text{CaO} \rightarrow \text{Ca(OH)}\_2\downarrow + \text{CH}\_3\text{CH}\_2\text{OH} \tag{2}$$

$$\begin{array}{c} \text{2CH}\_3\text{CH}\_2\text{OH} + \text{CaCO}\_3 \rightarrow \text{CH}\_3\text{CH}\_2\text{O} \text{CaOCH}\_2\text{CH}\_3 + 2\text{H}\_2\text{O} + \text{CO}\_2 \uparrow\\ \rightarrow \text{2CH}\_3\text{CH}\_2\text{OH} + \text{Ca}(\text{OH})\_2 \downarrow \end{array} \tag{3}$$


**Table 2.** *Properties of calcium oxide.* *Improving the Technology of Synthesis Absolutized Bioethanol DOI: http://dx.doi.org/10.5772/intechopen.92332*

The insoluble calcium hydroxide in the alcohol was filtered off, and the absolute ethyl alcohol by reactions (4) and (3) was discharged through a direct refrigerator, and the calcium hydroxide remained in the flask in the precipitate form.

Tetraethoxytitanium (CH3CH2O)4Ti as a dehydrator acts in different way.

$$(\mathrm{CH\_3CH\_2O})\_4\mathrm{Ti} + 4\mathrm{H\_2O} \to 4\mathrm{CH\_3CH\_2OH} + \mathrm{Ti(OH)\_4} \,\mathrm{J} \tag{4}$$

During the hydrolysis of TET the titanium tetrahydroxide, which is insoluble in alcohol, precipitates and can be filtered out; the absolutized alcohol is distilled at a special installation under vacuum, or with air dehydrators under normal conditions.

As can be seen from **Table 3** [42], ethanol has the most similar properties with gasoline according to the main indicators (boiling point and octane number). In addition, it is the cheapest and most affordable as a bioethanol—a product of natural raw materials processing, therefore, it was selected for absolutization. The ethanol concentrations were measured by the weight pycnometer method and determined by theoretical data [43]. The volume concentration of alcohol is determined by the areometers (ASP-1, ASP-2) using tabular data. Chromatography of ethanol and gasoline is carried out on by a gas–liquid chromatography, a method for determining oxygen-containing compounds in gasoline (HPCHEM\SEQUENCE \D161124A. S\METHOD\ D4815N.M) by internal standard (ISTD) based on 15 known calibrated substances, including ethanol (**Figures 2–4**). Infrared spectroscopy of ethanol samples is carried out by IR spectroscope (IS 50 FT-IR "NICOLET" Slovensko). Mass spectroscopy of the samples is carried by a mass spectroscope (MX-7304A, AO.SELMI, Sumy, Ukraine, 1 to 210 mass range). Determination of the cetane number of diesel fuel L-0.2-40 and the octane number of petrol A-80, as well as the freezing point of diesel fuel was carried out using the laboratory analyzer "Octane meter" of Shatox sx-100 k type [44]. Also, an assessment of the petrol gasoline by a motor method was carried out at the "OKKO" quality control laboratory in Galich, Ivano-Frankivsk region of Ukraine.


#### **Table 3.**

not contain water, including ethyl alcohol and ethers, but in this work it is not described how the ethyl alcohol was absolutized, therefore in different sources it has a different octane number. Consequently, we propose our own method of ethanol absolutization with calcium oxide or tetraethoxytitanium (TET).

*Octane number of oxygen generating gasoline additives, which is measured by different methods.*

**Indices MTBE ETBE MTAE DIPE Methanol Ethanol** *tert***-**

*Analytical Chemistry - Advancement, Perspectives and Applications*

Motor octane number (MON) 75–115 102 95–105 98.4 90 95 98

112–130 120 105–115 111.6 120 106 108

110 111 105 105 101 100.5 103

0.06 0.03 0.02 0.03 0.42 0.13 0.07

decomposes formed alcoholate and a reverse reaction takes place.

absolutization.

Research octane number

Octane number index (RON + MON)/2

Saturated vapor pressure, МPа

(RON)

(at 293 K)

**Table 1.**

irreversible reaction:

**Table 2.**

**224**

*Properties of calcium oxide.*

impurities was taken for work (**Table 2**).

Researches of the method of ethanol absolutization by chemically binding water reagents such as calcium oxide and TET are conducted. Alcohols practically do not interact with alkalis, because among the reaction products there is water that

2СН3СН2ОH þ CaO ! СН3СН2OCaOСН2СН<sup>3</sup> þ 2H2O↑

Therefore, fresh prepared (1123 K, 2 h) mineral calcium carbonate, which has

After calcination, samples of CaO were cooled in a vacuum desiccator, to reduce air access and to re-carbonize calcium oxide. Only 1 grade with minimum content of

It was suggested that if you take freshly calcined calcium oxide, then absolutized ethyl alcohol and alcoholates of the corresponding metals can be obtained during an

2СН3СН2ОH þ CaCO3 ! СН3СН2OCaOСН2СН<sup>3</sup> þ 2H2O þ CO2↑

**The component content of calcium oxide Types of CaO obtained from mineral calcium**

Active CaO ≤90 ≤80 ≤70 Active MgO ≥5 ≥5 ≥5 CaCO3 and MgCO3 carbons ≥3 ≥5 ≥10 Impurities SiO2 and Al2O3 ≥1 ≥10 ≥15

СН3СН2ОH � H2O þ CaO ! Ca Oð Þ Н <sup>2</sup>↓ þ СН3СН2ОH (2)

! 2СН3СН2ОH þ Ca Oð Þ Н <sup>2</sup>↓ (3)

**carbonate, CaCO3 123**

the following characteristics, presented in **Table 2**, was used for ethanol

! 2СН3СН2ОH þ Ca OH ð Þ<sup>2</sup> (1)

**Butanol**

*Comparative physico-chemical characteristics of oxygen generating additives—gasoline combustion activators [42].*
