View of OPTIMIZATION CHROMATOGRAPHY METHOD TO IDENTIFY THE COMPOUNDS ANTHRACENE OIL OF COKE CHEMICAL PRODUCTION | Chemical Journal of Kazakhstan

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ЕҢБЕК ҚЫЗЫЛ ТУ ОРДЕНДІ

«Ə. Б. БЕКТҰРОВ АТЫНДАҒЫ

ХИМИЯ ҒЫЛЫМДАРЫ ИНСТИТУТЫ»

АКЦИОНЕРЛІК ҚОҒАМЫ

Қ АЗА Қ СТАННЫ Ң

Х ИМИЯ Ж УРНАЛЫ

Х ИМИЧЕСКИЙ Ж УРНАЛ

К АЗАХСТАНА

C HEMICAL JOURNAL of K ^AZAKHSTAN

АКЦИОНЕРНОЕ ОБЩЕСТВО

ОРДЕНА ТРУДОВОГО КРАСНОГО ЗНАМЕНИ

«ИНСТИТУТ ХИМИЧЕСКИХ НАУК

им. А. Б. БЕКТУРОВА»

4 ⁽⁶⁸⁾

ОКТЯБРЬ – ДЕКАБРЬ 2019 г.

ИЗДАЕТСЯ С ОКТЯБРЯ 2003 ГОДА ВЫХОДИТ 4 РАЗА В ГОД

АЛМАТЫ 2019

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ХИМИЧЕСКИЙ ЖУРНАЛ КАЗАХСТАНА

52

UDC544.33; 544.34

ZH. S.AKHMETKARIMOVA¹, G. SH. ZHAKSYBAEVA¹, M. G. МEYRAMOV¹, G. N. MUSINA², ZH. K. BOGZHANOVA²

1Institute of organic synthesis and coal chemistry of the Republic of Kazakhstan, Karaganda, Kazakhstan,

2Karaganda state technical university, Karaganda, Kazakhstan

OPTIMIZATION CHROMATOGRAPHY METHOD TO IDENTIFY THE COMPOUNDS ANTHRACENE OIL

OF COKE CHEMICAL PRODUCTION

Abstract. Anthracene oil is obtained by vacuum fractionation from coal tar from corporation "ArcelorMittal Temirtau". The product was purified from resinous components by column chromatography. The physicochemical characteristics of anthracene oil from corporation "ArcelorMittal Temirtau" are investigated. Using the methods CMS and GLC analysis components of the hydrogenation products were determined . It is found that use the catalyst of iron-containing composite the carrier of carbon allows to increase the degree of conversion of hydrocarbon derivatives.

Key words: hydrogenation, anthracene oil, temperature, hydrogen pressure, catalyst.

Today, in many countries of the world, research and pilot works are conti- nuing on the improvement and improvement of some indicators. These are separate stages in the processing of solid and heavy hydrocarbon feedstock and liquefaction products. This can significantly improve the efficiency of the method as a whole.

In industry, anthracene oil is obtained from coal tar. Coal tar is a complex mixture of organic compounds. The main components are aromatic hydrocarbons and heterocyclic, sulfur, oxygen and nitrogen compounds. By chemical proper- ties, all compounds of the resin are divided into three groups: neutral, acidic and basic.

Anthracene oil is a fraction of a greenish-yellow color obtained during the distillation of coal tar, boiling away within 280-360°C (up to 400°C), its density is 1.09-1.10 g/cm³. It is a complex mixture of high-boiling, mainly aromatic, compounds, the main of which are anthracene (5% content), phenanthrene - anthracene isomer (20%) and carbazole (6%). When cooled anthracene oil stands out soft mass, the main part of which is anthracene. Anthracene oil is used to isolate anthracene, phenanthrene, to produce carbon black. Anthracene oil is one of the best wood preservatives, so it is used for preparing sleeper impregnation oil.

The feedstock was used coal tar received in the company of "ArselorMittal Temirtau" selected distillation. The tar yield in the production of coke is 6-8% of dry coal. Consequently, the released resin is very similar in structure and appea- rance to functional groups and structural fragments with the organic mass of the original coal.

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ISSN 1813-1107 № 4 2019

An analysis method has been developed for the chromatograph used, inclu- ding the selection of a column, the testing of parameters (temperature regimes for the injector, detector and thermostat, pressure and gas flow rates). GLC analysis was carried out on a Crystallux 4000M chromatograph with a PID detector on a ZB-5 30m x 0.32mm x 0.25μm column. with thermostat temperature program- ming with a temperature of 60-28°C at a temperature rise rate of 60°C/min. Data pro-cessing was provided by the program «NetChromv. 2.1". In compiling the data-base of component composition, we used the results of the analysis of standard samples contained in the obtained resin fraction (tetralin, naphthalene, diphenyl, phenanthrene, anthracene), and a similar CMS analysis The СMS study was car-ried out on an HP 5890/5972 MSD instrument manufactured by Agilent (USA), on a DB-5ms capillary column 30m x 0.250mm x 0.50μm, in the temperature range 60-300°С. Substance identification was performed using the NIST98 mass spectral database.

To work out the GLC method for the analysis of coal tar by company

“ArcelorMittal Temirtau”, vacuum fraction was used to extract a fraction with a boiling point of up to 2100°C/10mmHg. Tar mpurities greatly interfere with the analysis. Since they are deposited in the chromatograph injector and in a capillary column, in which the analyzed object is divided into separate components.

Therefore, part of the obtained fraction was purified by the method of column chromatography on silica gel of the brand KSMG/0.15-0.3mm., eluent benzene- hexane 3:1. The resulting solution is evaporated under reduced pressure on a rotary evaporator to the required concentration. Optimal conditions have been established for this object by selection, under which the mixture is divided into individual components (figure 1) on the Crystallux 4000M chromatograph.

It is known that phenols and polyaromatic compounds are present in the sample. Therefore, mixed samples of the starting product with available phenol,

Figure 1 – Chromatogram of coal tar fraction (GLC analysis)

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naphthalene derivatives, hydrogenated and individual polyaromatic hydrocarbons were prepared and analyzed. As a result, the main part of the composition of the fraction was determined.

The remaining components were determined using chromato-mass spectro- metric analysis in close temperature and gas parameters on a DB-5ms column, an analogue of ZB-5 (figure 2) of the instrument HP 5890/5972 "Agilent".

Figure 2 – Chromatogram of coal tar fraction (CMS analysis)

The study found that coal tar from company "ArcelorMittal Temirtau" is polyazeotropic-polyutectic system. Its composition contains resinous substances and pitch (up to 50%). The physicochemical characteristics of anthracene oil of company “ArcelorMittal Temirtau” were studied.

The study of the analysis results allowed to determine that the individual chemical composition of the anthracene fraction of coal tar consists of naphthalene and naphthalene derivatives, polyaromatic hydrocarbons (figures 3, 4).

5.00 10.00 15.00 20.00 25.00 30.00 35.00

0 2000000 4000000 6000000 8000000 1e+07 1.2e+07 1.4e+07 1.6e+07 1.8e+07 2e+07 2.2e+07 2.4e+07 2.6e+07 2.8e+07 3e+07 3.2e+07 3.4e+07 3.6e+07

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Abundance

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3.730 3.846 5.041 5.176

8.748

9.167 11.927

12.551

13.278 13.516

14.533 15.314

15.752 16.192

17.395

17.83118.06418.468 20.083

20.88722.603

23.00025.40327.18128.098

33.619

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56

Component composition of the anthracene oil fraction

Component Time, min Concentration, %

phenol 8,84 0,42

indan 10,55 0,26

inden 10,78 3,02

naphthalene 14,12 46,58

2-benzothiophene 14,29 0,67

1 methylnaphthalene 16,41 5,07

2-methylnaphthalene 16,74 1,95

diphenyl 17,95 1,67

2-Etenylnaphthalene 19,05 0,30

biphenylene 19,57 5,44

acenaften 20,18 1,25

dibenzofuran 20,77 4,28

fluoren 22,08 5,35

dihydrofenanthrene 23,91 0,20

tetrahydrofenanthrene 25,04 0,58

phenanthrene 25,57 9,77

anthracene 25,65 1,54

fluoranthene 31,40 2,29

pyrene 33,01 0,92

Total 91,77

Thus, the following main components are present in the high-boiling anthracene fraction of coal tar with a content of 1% and higher: acenaphthene, biphenylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene. The first three components are concentrated in the absorption fraction and have a signi- ficant effect on the formation temperature. When changing the place of selection in the direction of decreasing temperature, the quality of the absorption oil will improve due to the relative increase in the content of methylnaphthalenes. The intermediate fraction 270–310⁰C, in which acenaphten, diphenylene and fluoren is concentrated, can be used as raw material for further processing to individual products.

Financing source of research was performed in the framework of the program-target research (№BR05236438) with the financial support of the Committee of science of the ministry of education and science of the Republic of Kazakhstan.

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ISSN 1813-1107 № 4 2019 REFERENCES

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Резюме

Ж. С. Ахметкəрімова, Г. Ш. Жақсыбаева, М. Ғ. Мейрамов, Г. Н. Мусина, Ж. Қ. Боғжанова КОКСОХИМИЯ ӨНДІРІСІНДЕ АНТРАЦЕН МАЙЫНЫҢ

КОМПОНЕНТТІК ҚҰРАМЫН АНЫҚТАУДА ХРОМАТОГРАФИЯЛЫҚ ƏДІСТЕМЕНІ ОҢТАЙЛАНДЫРУ

«АрселорМиталл Теміртау» АҚ тас көмір шайырынан вакуумды бөлу арқылы антрацен майы алынды. Өнімді шайырлы заттардан тазарту бағаналы хромато- графиямен жүргізілді. «АрселорМиталл Теміртау» АҚ антрацен майының физико- химиялық көрсеткіштерді зерттелінді.

ГСХ мен ХМС əдістемелерімен гидрлеу өнімінің компонентті құрамы дəйек- тенді. Темірқұрамды композитті катализаторды пайдалану көмірсутегі туындары- ның конверсия дəрежесінің жоғарлауына мүмкіндік беретіні анықталды.

Түйін сөздер: гидрогенизация, антрацен майы,температура, сутегі қысымы, катализатор.

Резюме

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ИДЕНТИФИКАЦИИ КОМПОНЕНТНОГО СОСТАВА

АНТРАЦЕНОВОГО МАСЛА КОКСОХИМИЧЕСКОГО ПРОИЗВОДСТВА Вакуумным фракционированием из каменноугольной смолы АО «Арсе- лорМиттал Темиртау» получено антраценовое масло. Проведена очистка продукта от смолистых компонентов колоночной хроматографией. Исследованы физико- химические характеристики антраценового масла АО «АрселорМиттал Темиртау».

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Ключевые слова: гидрогенизация, антраценовое масло,температура, давление водорода, катализатор.