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ISSN 2522-1841 (Online) AZ9RBAYCAN KIMYA JURNALI № 2 2018 ISSN 0005-2531 (Print)
UDC 665.6/7:502.171;665.6/7:658.567
PROCESSING OF BY-PRODUCTS OF ETHYLENE PRODUCTION
F.M.Sadigov
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
sadigov.fikret@gmail.com Received 25.12.2017
Production process of benzene of 98.5% purity from light resin formed in ethylene production was studied. A complex catalyst synthesized on the basis of aluminium chloride and toluene developed in the laboratory during processing, was used. Separation process of high pure (98.9%) naphthalene from heavy resin was purposed. The new method is useful for production of bituminous dyes, paints with various properties.
Keywords: ethylene, light resin, heavy resin, benzene, toluene, oil-polymer, catalyst, naphthalene, bitumen.
Introduction
Purposeful use of by-products of the production is one of the main problems in chemical industry. Their rational processing creates opportunities for considerable production of many valuable products in industry. From this point the development and application of a simple technology for processing by-products - light and heavy tar - of ethylene production in EP-300 installation is of great importance as an urgent problem.
It is known that the amount of benzene in crude oil reaches 0.5-1%. Depending on a raw material in pyrolysis the content of benzene is up to 40-50% in a light tar [1, 2]. Due to this the production of benzene from light tar obtained in pyrolysis of oil hydrocarbons in ethy-lene production has a considerable economic effect. Considering this, the complex processing of a light tar in EP-300 installation was performed to establish a production.
Presently, 45% of benzene is obtained from a light tar in the world [3]. For this purpose thermal and hydrodealkylation of benzene-toluene-xylene fraction of hydrostable and hydro treated light tar which requires much energy, material and capital consumption is mainly performed. These processes are performed under high temperature and pressure, require expensive catalysts (Pt, Pa, Co, Mo) and special metal devices [4]. Our method is technologically simpler than the other methods, does not require the use of less energy, material and expensive catalysts and hydrodealkylation stages and economically useful.
Experimental part and discussion
Complex processing of a light tar of EP-300 production. For experimental studies we used a light tar obtained from ethylene production (Sumgait city) in EP-300 installation with boiling temperature of 70-1500C. Chromato-graphic (Chromatograph Agilent 7820A) and mass-spectroscopy (chromato-mass-spectrometer Clarus 500) studies of a light tar showed that it contains many aliphatic, naphthene-aromatic hydrocarbons (benzene and its alkyl derivatives), unsaturated aromatic, bicyclic and other compounds and 35% of benzene in a side chain. In Table 1 hydrocarbon composition of a pyro-condensate is included.
Table 1. Hydrocarbon composition of pyrocondensate
Hydrocarbon composition of pyrocondensate mas %
aliphatic
C5 5.78
C6 1.92
C7 1.01
C8 0.76
C9 0.53
aromatic
benzene 35
toluene 16.5
ethylbenzene 5.84
p-xylene 3.24
styrene 10.96
o-xylene 1.80
isopropylbenzene 0.5
vinyltoluenes 2.99
methylstyrenes 5.69
1,2,3-trimethylbenzene 3.76
alicyclic
cyclopentadiene 1.5
dicyclopentadiene 0.24
During experiment a light tar was separated into fractions by rectification. Table 2 shows the distribution indexes of fractions in pyrocondensate.
Table 2. Distribution of fractions in pyrocondensate; rectification 170 g (200 ml) of pyrocondensate was taken
Fraction, T, 0C Separated
g mas. %, in taken pyrocondensate
g.b.-70 20 11.76
70-105 70 41.18
105-125 50 29.41
125-146 25 14.71
residue 5 2.94
total 170 100
Different methods have been used to increase the amount of benzene in 70-105 fraction: 1) azeotropic rectification of benzene fraction was performed; 2) benzene fraction was frozen at low temperatures and separated. The purity of resultant benzene was brought to 98.5%. To perform catalytic processing of a light tar an effective catalytic system has been developed in the laboratory. The catalyst was synthesized in three-necked flask equipped with a stirrer, aluminium and toluene with a certain mass ratio and water. While intensely mixing the components traditionally obtained gaseous hydrogen chloride (NH4Cl+H2SO4) is added into the flask during the whole experiment. Changing preparation parameters of a catalyst (temperature 60-900C, preparation time of a catalyst from 4 to 6 hours,
ratio of components aluminium (chips) toluene from 1:10 to 1:30) optimum condition of the synthesis: temperature - 700C, preparation time - 2.5 hours, mass ratio of aluminium and toluene was found to be 1:20.
Catalytic processing of a light tar was performed in a three-necked flask equipped with a mixer, thermometer and cooling system. After experiment liquid part was separated and given to chromatographic analysis. Study of reaction laws and determination of optimum mode were performed in the temperature range of 30-900C, contact period 1-6 hours and catalyst concentration of 1.5-5.0 %. Chromato-graphic and experimental data showed that processing of a light resin with complex catalyst decreases saturated and unsaturated aliphatic hydrocarbons, increases benzene and toluene in the light tar and increases ethylbenzene and styrene. The amount of bi-, trialkyl derivatives of aromatic hydrocarbons, bicyclic compounds sharply decreases. In all experiments petroleum polymer resin is formed. Experimental material is given in Tables 2-5.
As Table 3 shows, when temperature rises up to 800C amount of benzene a light resin increases to 43.5%. The impact of experiment time on the process parameters was studied and it was determined that the reaction goes intensely for 5 hours, then reaction rate sharply decreases.
Table 3. Impact of temperature on catalytic processing of pyrocondensate (concentration of catalyst 3.5 %, experiment time - 4 hours)
Temperature 0С Amount, mas %
aliphatic hydrocarbons benzene toluene ethylbenzene styrene output of petroleum polymer resin
30 4.69 34.5 16.5 5.84 9.27 8.5
40 4.57 34.8 16.9 5.84 9.26 9.7
50 4.51 36.2 22.76 5.62 9.19 10.9
60 4.31 39.3 23.40 5.50 9.01 14.9
70 4.19 41.2 23.64 5.48 7.94 17.5
80 4.00 43.5 24.14 5.47 7.83 18.1
90 4.08 38.3 23.95 5.40 7.08 19.0
Table 4. Impact of experiment time on catalytic processing of pyrocondensate (temperature - 800C, concentration of
catalyst - 3.5 %)
Reaction time, hour Amount, mas %
aliphatic hydrocarbons benzene toluene ethylbenzene styrene output of petroleum polymer resin
1 5.07 34.9 15.0 5.80 10.74 7.4
2 4.58 35.5 16.7 5.76 9.00 8.5
3 4.51 37.2 18.7 5.63 8.83 11.2
4 4.10 43.5 24.10 5.45 7.82 18.3
5 3.61 42.0 25.28 5.90 7.61 19.8
6 3.59 41.8 25.10 5.79 7.62 19.5
Table 5. Impact of catalyst concentration on catalytic processing of pyrocondensate (temperature - 800C, experiment
time - 4 hours)
Concentration of catalyst, mas.* % Amount, mas %
aliphatic hydrocarbons benzene toluene ethylbenzene styrene output of petroleum polymer resin
1.5 5.28 34.9 19.21 5.74 8.80 15.1
2.0 4.92 39.0 21.45 5.50 7.98 16.6
3.5 4.10 43.5 24.62 5.47 7.83 18.5
4.5 3.95 42.9 24.53 5.28 7.02 19.0
5.0 3.80 42.7 23.89 5.25 6.94 19.1
*- calculated for light resin
The rise of catalyst concentration from 1.5 to 3.5 mas % in reaction mixture increases benzene and toluene in light resin.
Thus, optimum condition of catalytic processing a light resin was defined: temperature - 80 C, contact time - 4 hours, concentration of catalyst - 3.5%. Under this condition output of benzene is equal to 43.5 %.
According to experiments production process of benzene with 98.5% purity from py-rocondensate was purposed.
Researches on the development and application of production method of high-purity naphthalene from heavy resin in ethy-lene production
Heavy resin is used in the production of carbon black, electrode coke, graphite for atomic reactors, some individual hydrocarbons of fuel components [5-8]. Naphthalene is one of the hydrocarbons which is widely used in petroleum chemical synthesis. Heavy resin which was obtained in ethylene production, was studied to produce pure naphthalene in the laboratory. Chromatographic analysis of a heavy fraction showed that it contains 5-36% naphthalene and its derivatives. First of all heavy resin samples taken in different times (time interval of 3 months) from EP 300 installation were purified from heterogeneous-disperse particles by sedimentation method. It was detected that solid deposit in samples does not exceed 3% and consists of mainly solid residues. Researches showed that heavy resin contains up to 5% (dissolved or emulsion) of water. Treated heavy resin samples were studied by gas-chromatographic and mass-spectroscopic analyses and it was determined that saturated and unsaturated, individual and condensed cyclic compounds predominate in these samples. Among these compounds
naphthalene isomers and their methyl, ethyl, iso-propyl derivatives are of great importance. In heavy resin samples their amount is more than 50%. Samples were fractioned in a topping plant under 0.75-0.85 atm vacuum till 520 K temperature. During distillation the separation of up to 15% saturated and unsaturated hydrocarbon gases with small molecules has been observed.
Then these fractions were distilled under atmospheric pressure, at 180-2000C temperature with dry steam and naphthalene with purity of 98.9% was obtained. As an additional product bicyclodecapentadiene and its methyl, ethyl, isopropyl derivatives existed. This method is economically useful, technologically simple. According to the researches it was determined that heavy resin contains sufficient amount of unsaturated hydrocarbons. This prevents to obtain pure naphthalene. Due to this catalytic processing of heavy resin was studied. First of all the catalyst which was synthesized with aluminium chloride, toluene and hydrogen chloride in processing process was used and conversion reaction of unsaturated hydrocarbons to saturated hydrocarbons was performed. Catalytic processing laws of a heavy resin were studied and optimum mode parameters of the process were determined. The amount of naphthalene in the fraction was brought to 96%.
In modern construction and metal-construction works one of the main tasks is the use of isolation materials to prevent the negative impact of corrosion. It is known that bituminous dyes and paints exhibit good adhesion, high isolation abilities and can stick various materials to each other. Recently bituminous dyes and paints are derived from bottom products of processing petroleum and heavy petroleum products. From this point the properties of bottom products re-
mained after processing of naphthalene and its derivatives - by-product of EP-300 installation in the laboratory - heavy resin fraction were compared to the standard properties of bitumens. Parameters of bottom products conform to the parameters of bitumen. Using various solvents and fillers different samples with adhesion, solidity, stability properties, shapes (bright and non-bright) and capable of covering a surface has been obtained. Many researches have been performed to prevent the main disadvantage -condensation of bituminous dyes and paints. Heavy resin was distilled under 0.7-0.8 atm vacuum pressure and the fraction was collected at the range of 240-2600C. When processing this fraction with still bottom, solvent and filler a new material of bituminous paints is produced.
Development of production methods of non-benzene aromatic compounds and graphite from heavy resin in ethylene production
Due to antiallergenic, bacteriostatic, moistening, anti-inflammatory, antispasmodic properties non-benzene compounds, particularly, mixtures of natural derivatives derived from plants are widely used in perfumery, cosmetics, pharmacy and medicine. These compounds are added into toothpastes, creams, shampoos and other hygiene facilities. Besides, non-benzene aromatic compounds are used as a part of medical facilities, preparations which stimulate cardiac performance, normalize the work of central nervous system. Heavy resin formed as a byproduct during the process in EP-300 installation was selected as a research object. Heavy resin containing non-benzene aromatic hydrocarbons (bicyclo[5,3,0]decapentaene and its methyl, ethyl, isopropyl derivatives) and formed in py-rolysis of gasoline+(C3-C4) mixture was used for experiments. The researches have shown that crude heavy resin samples are not homogeneous and contain the following mixtures: a) dissolved gases (saturated and unsaturated C1-C5 hydrocarbons) up to 12.1 %; b) water (water steam condensate) up to 2.5%; c) deposit (heavy, non-identified resin compounds) up to 3.3%. After separating dissolved gases, water and deposit with physical methods heavy resin samples were analysed by gas-chromatographic (chromato-
graph Agilent 7820A) and mass-spectroscopic (chromato-mass-spectrometer Clarus 500j methods. It was determined that heavy resin samples separated for studies contain 13-18% of non-benzene aromatic hydrocarbons. Each sample was separated in the volume of 300 ml for experiment with measuring tube and their masses were determined (depending on 318-324 g density). Then heavy resin samples were distilled at atmospheric pressure and fractioned in the range of 0-2800C. In experiments fractions were separated in the ranges of 0-1750C, 175-2100C, 210-2350C, 23 5-25 00C and 250-2800C. Analysis of each fraction showed that only at 235-2500C the fraction contains 31.29-42.87% of non-benzene atomatic hydrocarbon mixtures. Only traces of non-benzene aromatic hydrocarbons were observed in other fractions at 175-2100C, 210-2350C and 250-2800C. Non-benzene aromatic hydrocarbons are an exception in bottom product and fraction at 0-1750C. Outcome degree of non-benzene aromatic hydrocarbons in the samples reached 81.97%.
Heavy resin samples formed in pyrolysis of gasoline+(C3-C4) mixture were used for experiments. Separated heavy resin samples were distilled under atmospheric pressure and frac-tioned in the range of 0-3500C. In primary approach still bottom on quality is like black oil. According to quality analysis of still bottom samples, they mainly consist of hydrocarbon mixture with molar mass of 400 g/mol (linear and cyclic paraffin, naphthenes, condensed aromatic and non-aromatic compounds, oil resins, asphaltenes, carbenes, carboids). The traces of technical graphite were also detected in the samples. Still bottom was distilled in the range of 0-5500C repeatedly. After gas oil like liquid fraction is separated, still bottom - black as-phaltum oil with mirror - like surface was obtained. Samples of this solid substance were analysed using D2Phaser X-ray diffractometer and considerable amount of fullerenes were detected in them.
Study of useful applications of low molecular and waste polyethylene
In different stages of production process of polyethylene powdery, fibrous and granule
polyethylene waste by-product is formed. Reprocessing of this waste was put as a goal to use it efficiently. As a research object powdery polyethylene was chosen. Pyrocondensate (light resin) obtained in EP-300 installation was defined as a solvent. It was known that when dissolving polyethylene in pyrocondensate the amount of benzene considerably increases in a non-homogeneous mixture. To study the interaction of py-rocondensate (PC) with powdery polyethylene (PP) the samples in PC:PP different ratios were investigated. It was determined that the ratio is 19:1, for PP 5% solution. Then the impact of time on this mixture was studied and mixed samples were observed for 24, 48, 72, 144, 216 hours. Samples were rectified at the temperature range of 0-900C after the experiment.
Gas-chromatographic analysis of rectifi-cates was performed. It was found that the amount of benzene in the samples kept 72 hours increases namely 15%.
Conclusion
1. Production process of benzene with 98.5% purity from light resin formed in ethylene production was studied. A complex catalyst synthesized on the basis of aluminium chloride and toluene developed in the laboratory during processing, was used.
2. Separation process of high pure (98.9%) naphthalene from heavy resin was purposed. The new method is useful for production of bituminous dyes, paints with various properties.
3. For the first time a mixture of non-benzene aromatic compounds from heavy resin was separated and processed.
4. It was found out that black asphaltum oil-
like solid stillage substance formed from heavy resin distilled under atmospheric pressure in the range of 0-3500C contains considerable amount of fullerenes. 5. It was determined that the amount of benzene can be increased by dissolving it in pyrocondensate for rational use of waste polyethylene.
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ETiLEN iSTEHSALININ YAN MOHSULLARININ EMALI F.M.Sadiqov
Etilen istehsalinda EP-300 qurgusunda alinan yüngül va agir qatranin emal prosesi tadqiq edilmi§dir. Rektifikasiya va dondurma metodlari ila ayrilan benzolun tamizliyi 98.5%-a qadar alinmi§dir. Emal prosesinda laboratoriyada i§lanib hazirlanmi§ alüminium xlorid va toluol asasinda sintez olunmu§, benzol va toluolun pirokondensatin tarkibinda artmasim tamin edan kompleks katalizator istifada edilmi§dir. Agir qatrandan yüksak tamizliyi olan (98.9%) naftalinin ayrilmasi prosesi i§lanib hazirlanmi§dir. Agir qatramn emalinda kub qaliginda amala galan bitum fiziki xüsusiyyatlarina göra bitum boyalar va laklarin istehsalinda tatbiq oluna bilar.
Agar sözlar: etilen, yüngül qatran, agir qatran, benzol, toluol, neftpolimer qatran, katalizator, naftalin, bitum.
ПЕРЕРАБОТКА ПОБОЧНЫХ ПРОДУКТОВ ЭТИЛЕНОВОГО ПРОИЗВОДСТВА
Ф.М.Садыгов
Исследован процесс переработки лёгкой смолы, полученной на установке производства этилена ЭП-300. С использованием ректификационных методов и способа вымораживания удалось выделить бензол 98.5%-ной чистоты. Разработан и применен в процессе переработки катализатор на основе хлорида алюминия и толуола, обеспечивающий увеличение содержания бензола в лёгкой смоле. Установлено, что во всех опытах образуется ценный продукт - нефтеполимерная смола. Предложен процесс переработки тяжелой смолы с целью выделения нафталина высокой чистоты (98.9%). Благодаря своим физическим характеристикам образовавшийся в кубовом остатке битум может быть использован для производства красок и лаков.
Ключевые слова: этилен, лёгкая смола, тяжёлая смола, бензол, толуол, нефтеполимерная смола, катализатор, нафталин, битум.
