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Kornienko Yulua

Faculty of ecology and chemical technology

Department of Chemical Technology of Fuel

Speciality: Chemical technology of fuel and carbon materials


Theme of master's work:

Interaction karbazol with alkal in heterogeneous process

Scientific advisers: Butuzova Ludmila, Frolova Irina

About author

Introduction

Coal tar has huge resources of valuable products. These substances primarily include carbazole, anthracene and phenanthrene, the total content of them in the resin is 7-8%. These substances are mainly concentrated in raw anthracene released during crystallization of anthracene fraction which is obtained by primary distillation of resin.

The relevance of the theme: carbazole can be isolated from anthracene group in the pure form. This is of great practical importance, as carbazole is widely used in the manufacture of polyvinylcarbazole, which is used in the manufacture of electrographic materials. Modification of carbazole indenter kumaronovyh tars improves their quality. Carbazole is an initial rawmaterial for the production of valuable dye - gidronov blue (stronger then indigo), sulfur dyes of khaki. Carbazole is used for obtaining tetranitrokarbazol (nirozan) - an effective insecticide. Based on the carbazole it can be obtained vinylcarbazole, polymerization of which results in valuable heat-resistant plastics. Promising area for using is the formation of carbazole based materials for light-sensitive layers (hologram), where the carbazole is needed in small amounts, but high purity. A reaction of from ation potassium karbazolyata is a base for the educingion of pure carbazole of anthracene fractions. This reaction was the object of studing.

Karbazole educing isolation of anthracene fraction can be made by the following methods: physical and chemical. Traditional physical methods are rectification and extraction [1].

Chemical methods of educing separation, usually have more expense than physical ones. We have to utilize waste products, including inorganic materials, which are not easily utilized. They are the following:

  1. Methods, which are based on the difference in the of rates sulfonation of difficult sharing components.

  2. Educing methods of impurities heterocyclic compounds, which are based on the specifics of their interaction with molten potassium hydroxide [2, s.239] [3,s.368], [4].

  3. Methods, which are based on high reactivity collinear polycyclic aromatic hydrocarbons [5;] [6,7, s.194].

  4. Methods, which are based on the ability of different aromatic polycyclic hydrocarbon formation complexes.

The experiment

In Institute of Physical and Organic Chemistry and Coal Chemistry behalf of Litvinenko National Science Academy of Ukraine carbazole reaction with alkali was carried out in heterogeneous conditions. For the experiment we must weigh previously calculated amount of carbazole and alkali in a predetermined ratio. The alkali should be placed in the capsule to prevent contact with air.

The experiment was conducted in a round flask of 250 cm3, which is equipped with a glass reflux condenser and fluoroplastic anchor mixer. Reflux condensez served for fixing the faucet. Heating was carried out using an oil bath. Bath temperature throughout the experiment was maintained at 120 - 125 °C.

The download reagents was following: carbazole, solvent - at room temperature and at a temperature of 110 °C alkalis was contributed in a flask, encapsulated with teflon, while starting a stopwatch. The moment of introduction of alkali was regarded as the beginning of the reaction. The process was carried out at the boiling point of the solvent and without removing water from the reaction mass. Speed of stirring (~ 800 1/min) provided passage of the reaction in the kinetic field.

Sampling was performed after 5, 15, 30, 45, 60, 120, 180 minutes after the start of the reaction. Samples were taken using a special probe (a glass tube 4 mm in diameter soldered to its end of the porous glass plate). Sampling was carried out with the mixer off and the withdrawal of heating. The analysis of samples carried out by spectrophotometry.

The results

Table 1 - Dependence of optical density on time at the ratio of karbazole: alkali = 1:2

№ experience

Load,g

Optical density D

karbazole alkali 0 15 min 30 min 45 min 60 min 2 h 3 h 4 h 5 h

1

 0,16752 0,254 0,740 0,700 0,635 0,620 0,579 0,579 0,579 0,579 0,579

2

 0,16636 0,270 0,735 0,654 0,620 0,600 0,585 0,585 0,585 0,585 0,585

3

 0,16735 0,244 0,740 0,710 0,670 0,615 0,570 0,565 0,570 0,570 0,570

4

 0,16920 0,267 0,750 0,705 0,660 0,630 0,590 0,590 0,590 0,590 0,590

5

 0,16965 0,267 0,725 0,690 0,640 0,620 0,570 0,570 0,570 0,570 0,570

Table 2 - Dependence of optical density on time at the ratio of karbazole: alkali = 1:4

№ experience

Load,g

Optical density D

karbazole alkali 0 15 min 30 min 45 min 60 min 2 h 3 h 4 h 5 h 6 h

1

 0,16656 0,528 0,760 0,050 0,050 0,050 0,050 - - - - -

2

 0,16620 0,525 0,735 0,535 0,420 0,330 0,265 0,095 0,040 0,040 0,040 0,040

3

 0,16695 0,525 0,740 0,490 0,420 0,355 0,280 0,160 0,080 0,060 0,050 0,050

Table 3 - The dependence of the optical density on time at the ratio of karbazole: alkali = 1:10

№ experience

Load,g

Optical density D

karbazole alkali 0 5 min 15 min 30 min 45 min 60 min 2 h

1

 0,16715 0,6616 0,750 0,580 0,215 0,055 0,030 0,020 -

2

 0,16910 0,6800 0,765 0,570 0,185 0,045 0,045 0,020 0,020

3

 0,16740 0,7149 0,735 0,310 0,105 0,028 0,030 0,020 0,020

Table 4 - Dependence of optical density on time at the ratio of karbazole: alkali = 1:11

№ experience Load, moth/L

Optical density D

karbazole alkali 0 5 min 10 min 15 min 30 min 45 min 60 min 2 h 3 h 4 h 5 h

1

 0,0159 0,00130 0,955 0,855 0,763 0,700 0,664 0,481 0,412 0,176 0,015 0,013 0,013

Table 5 - The dependence of the optical density on time at the ratio of karbazole: alkali = 1:12

№ experience Load, moth/L

Optical density D

karbazole alkali 0 5 min 10 min 15 min 30 min 45 min 60 min 2 h 3 h 4 h 5 h

1

 0,0167 0,00119 0,999 0,815 0,770 0,709 0,569 0,464 0,360 0,090 0,020 0,013 0,007

Scientific novelty: The transition from the melt into the solution, the transfering of reaction in the organic phase. This reduces the temperature of the reaction from 250-400 °C to 110 °C and decreases reaction time from 6-8 hours to 2 hours.

The practical impertance of the results: The disadvantages of the method of alkaline smelt are the need to work at high temperatures, high consumption of alkali, which is difficult to utilize, strong corrosion of equipment, technical difficulties with melts of alkali. The method studied in this master's work, may replace the alkaline melt on heterogeneous process that will allow to practice it in the laboratory and industrial conditions.

Conclusions

As a result of the work done we may make the following conclusions:

  1. Karbazole is the raw material for the production of many valuable products;

  2. Reaction of formation of karbazolyata is the base for the educing of pure carbazole from anthracene fraction;

  3. On tables it can be seen that the greater the amount of alkali, the faster the reaction, the greater the initial rate of chemical reaction and the extent of its passage.

The advantages of the process in the heterogeneous conditions in the environment of the solvent compared with alkaline melts are:

  1. Reducing the temperature of the reaction to 110 ° C, compared with 240 ° C with alkaline water;

  2. Reduced reaction time: 2 hours instead of 8 hours.

Current work on master's thesis has not been finished yet. The final completion will be in december 2010. Full text of the work and materials on the topic can be obtained from the author or his head.

References

  1. Гуревич Б. С., Сизова Е. М., Исаенко М. М. – Кокс и химия, 1977, №1, С. 36 – 38.

  2. Брон Я. А. Переработка каменноугольной смолы. – М.: Металлургия, 1963 – 272с.

  3. Химические продукты коксования углей Востока СССР. Свердловск, Среднеуральское кн.. изд., 1965. Вып 3.

  4. Пистрова П. Д., Харлампович Г. Д., Беднов В. М. – Химия твердого топлива, 1973, №2, с. 140 – 143.

  5. Lang K. – Ang. Chem., 1951, Bd. 63, № 15, S. 345 – 349.

  6. Полякова И. М. – Кокс и химия, 1938, № 2 – 3, с. 75 – 81.

  7. Клар Э. Полициклические углеводороды. Пер. С англ.. В. В. Ершова – М.: Химия, 1971 – т. 1, 455с.

© DonNTU Yulua Kornienko, 2010

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