Investigation of straw oil and polymer quality produced in the process of its regeneration has been carried out. The conclusions about using polymers as a material for base end products are made. Flow scheme of technological treatment of straw oil wastes is suggested

Lozbin, V. I.

Mochalnikov, S. V.

Nevedrov, А. V.

Papin, А. V.

Solodov, G. А.

Electronic archive of Tomsk Polytechnic University

plexon concentration was changed were carried out. Theobtained data are presented in figure 3. It is seen from thisfigure that at ОМED concentration equal to 4...8 mg/lcorrosion rate has the smallest values. Therefore theseconcentrations may be taken as operating ones.The influence of two component inhibitor ОМED – zinc sulfate on fouling in aqueous environments Besides corrosion decrease and prevention of hardness salt deposits, the important property of any inhibitor is an ability to suppress vital activity of animalcular organisms, developing in aqueous environments andforming the great bulk of fouling on heat exchangingsurfaces. Therefore, after weighing the samples of stainless steel, from their surface smears were taken, put on aslide and visually examined under a microscope. Theresults of investigations showed that two componentinhibitor ОМED – zinc sulfate does not stimulate fouling processes in aqueous environment.Thus, the results of investigations, carried out in laboratory environment, indicate the composition of organophosphorous complexon ОМED (salt of 1oxyethylidenediphosphonic acid with 2dimethylaminomethylphenol) and zincsulfate being the effective inhibitor of corrosion and salt precipitate in aqueous environment. Therefore it may be applied for twobath process of circulating water in systems of recyclingcooling of industrial enterprises.Bulletin of the Томsк Pоlytеchnic University. 2007. V. 310. № 1136REFERENCES1. Pavluhina L.D., Rakcheeva L.V. et al. Circulating water treatment inthe system of water rotation at ОАО «Voskresensk mineral fertilizers»// Modern technologies of water preparation and equipment protection from corrosion and scale formation: Reports, theses of the conference. – Moscow, 2003. – P. 57–61.2. Alferova L.A., Nechaev A.P. Development of closed systems of industrial enterprises and systems water consumption // Chemistry andtechnology of water. – 1990. – V. 12. – № 6. – P. 534–542.3. Belichenko Yu.P., Gordeev L.S. et al. Closed systems of chemical industries water supplying. – Moscow: Chemistry, 1996. – 270 p.4. Talalai A.V., Shukailo B.N., Kolomiets P.V. Stabilization treatmentof circulating and extraction water and deposits removal from thesurfaces of heating and cooling // Modern technologies of water preparation and equipment protection from corrosion and scale formation: Reports, theses of the conference. – Moscow, 2003. –P. 55–56.5. Gavrilov N.B. Highperformance complex programs of reagent treatment of reverse cooling cycles on the basis of domestic reagents //Modern technologies of water preparation and equipment protection from corrosion and scale formation: Reports, theses of the conference. – Moscow, 2003. – P. 49–54.6. Sorochenko V.F. Maintenance of water rotating cycles without scaleformation with minimal environmental risk // Chemistry andtechnology of fuels and oils. – 1998. – № 4. – P. 50–52.Arrived on 22.05.2006In the process of coal coking considerable quantityof resin is generated which contains in its compositionenormous quantity of organic compounds the large amount of which is difficult to be obtained in other technological processes. Such condenced compounds as acenaphthene, dibenzofuran, fluorene and others are inresin in quantities more than 1 % (per resin). At the same time there is a real requirement for these compoundsas raw materials in different branches of applied chemistry and pharmaceutical chemistry.The technology of coaltar resin reprocessing at domestic enterprises of byproductcoking industry is mainly carried out at singlecolumn rectification deviceswith target fraction selection according to columnheight. Stripping fraction is usually selected from the17th tray. More than 140 individual compounds are in itscomposition [1]. The greater bulk is presented by23 components of aromatic series with boiling temperatures 218...293 °С. Moreover, about 40 nitrogenatedcompounds and 16 components of phenolic series are inthe fraction. Quality of straw oil is determined by absorbing capacity (quantity of methylnaphthalenes), tendency to crystallization when cooling and tendency topolymerization at high temperatures, for which highboiling components: acenaphthene, diphenylene dioxide, fluorene are responsible [2–4].Highboiling compounds emission by means of additional rectification of straw oil solves the problem ofboth straw oil quality improvement and raw materialsfor emission of individual highboiling components. InUDC 662.749.33HIGHBOILING COMPONENTS IN STRAW OIL V.I. Lozbin, S.V. Mochalnikov, G.А. Solodov, А.V. Papin, А.V. NevedrovKuzbas State Technical University, KemerovoEmail: sna.httt.kuzstu@ruInvestigation of straw oil and polymer quality produced in the process of its regeneration has been carried out. The conclusions about using polymers as a material for base end products are made. Flow scheme of technological treatment of straw oil wastes is suggested.a flowsheet of a benzene department of a modern byproduct coke plant this problem is solved by a straw oilregenerator: while regenerating, oil quality is improvedand polymers in which the considerable part of highboiling compounds is concentrated are removed.Straw oil regeneration is carried out from time to time as polymers are accumulated in reverse oil and itsdensity increase.The results of straw oil quality research are presented below. Polymers characteristics at the beginning andat the end of regeneration cycle are also given. Main oilquality indexes are density and breakup. Density is themost prime and operating characteristic permitting forcontrol of straw oil condition. Temperatures of breakupcharacterize content of naphthalene fraction residualsto 230 °С; content of components responsible for oil absorbing capacity to 230...270 °С; content of highboiling components – acenaphthene, diphenylene dioxide,fluorene to 270...300 °С.Table 1. Quality of straw oil and polymersOil and polymers breakup is determined by distillation in Wurtz bulb at temperature checking at yield ofboiling mixture vapor phase. It might be supposed thatthe main quantity of highboiling components presenting in oil is removed at distillation in the temperaturerange 270...300 °С.In raw straw oil quantity of the product boiling awayin the range 270...300 °С (1–4, table) is 4...6 % (bymass).In reverse (experiment 5–9) and refiltered oil (10–13)highboiling fraction yield is nearly twice as high as rawstraw oil. In a polymer this fraction yield reaches 50 %.Noted decrease of 270...300 °С fraction yield to30 % and lower (pos. 16–18) is accounted for cyclic carrying out of regeneration process: experiments 14–15are referred to the beginning of the cycle and 16–18 ones are referred to the end of this cycle which lasts approximately 8–10 days.In the process of trapping and distillation of benzenehydrocarbons resin straw oil undergoes the series ofchanges: it is compacted, looses the considerable part oflight distillates, temperature of crystallization rises.Series of factors depending on oil composition, content of elements in coke oven gas promoting its sealing,oil application conditions in technological system influence the rate of polymerization of resin oil components.Instability of resin straw oil fractions increases at totalmagnification of a part of polynuclear aromatic compounds having greater reactivity and tendency to compacting than mononuclear and bicyclic structures.Fractions with boiling temperature 280...285 and285...295 °С are polymerized most intensively. Densityand viscosity of these fractions increases considerablythat decreases oil quality on the whole [5].Fractions boiling away to 270 °С are the most resistantto polymerization that improves technological propertiesof straw oil and allows decreasing its discharge intensity.Chromatographic analysis of straw oil from different partsof flowsheet and also polymers has been carried out.The content of highboiling components: acenaphthene, diphenylene dioxide, fluorene (table 2) is ofgreatest interest.Table 2. Content of highboiling components in straw oil andpolymers*Σ HBC – sum of components which boiling temperature is higherthan 270 °СThe data presented in the table allow us to determine a raw materials base for obtaining acenaphthene,diphenylene dioxide, fluorene. Low content of fractions270...300 °С (table 1) does not permit to consider strawoil as material for emission of listed components without pretreatment.№AcenaphtheneDiphenylenedioxide FluoreneAnthracene+phenanthereneΣ HBC*Raw straw oil123420,0520,3719,2518,6811,3211,2010,9010,537,096,426,235,930,060,050,080,0938,7138,0436,4635,22Reverse oil5678922,2824,8530,0924,8126,0214,9015,7816,7315,8815,437,666,856,466,476,580,410,170,140,09–47,2547,6451,4148,1848,02Refiltered oil1011121323,1222,9722,5323,3415,0915,8513,3312,636,496,545,445,180,070,09––44,7745,4541,3041,20Polymeres1415161718235,9034,4135,5536,2735,9228,8834,6228,0128,6027,4019,4217,0810,4711,5110,490,730,750,430,460,1084,9386,8774,4776,8473,91№№Density,kg/m3Water,%Breakup, %270…300 °С 230 °С 270 °С 300 °СRaw straw oil 123410591059105610590,40,30,3 0,81,62,41,40,979,088,084,087,085,092,088,093,06,04,04,06,0Reverse oil56789106610641076106310590,10,10,10,20,201,00,42,51,776,082,079,081,082,092,093,091,089,090,016,011,012,08,08,0Refiltered oil1011121310551053105610490,110,42,01,60,81,80,67,980,080,086,085,093,090,095,091,013,010,09,06,0Polymers141516171811381144110511051100–––1,20,10,51,01,21,40,221,021,052,045,056,075,072,082,074,078,054,051,030,029,022,0Chemistry137Such pretreatment is carried out in regenerator. Inthis case, highboiling components content increases in1,5...2 times in comparison with fresh and reverse oil.Sum total of the components boiling away at morethan 270 °С reaches 80 wt. % and more in polymers.Maximal quantity of target component (fluorene) is observed in the products segregated at the beginning of regeneration cycle (pos. 14, 15). At the end of the cycledecrease of total yield of highboiling components isobserved mainly due to flourene yield reduction.Polymer selection at the initial cycle of regenerationis optimal from the position of recycling for flourene extraction (pos. 14, 15). In case of polymer recycling intoanother individual components selection time is not ofconsiderable importance.Generalizing the materials obtained by researchingof straw oil and polymers composition regenerationprocess laboratory investigations in developing oftechnology of flourene extraction from polymer shouldbe divided into two stages.The first is the 270...310 °С long distillate extractionfor forerunning and properly polymers removal.The second one is a long distillate rectification at control of products composition at different temperatures.The 270...310 °С long distillate extraction was carried out in Wurtz bulb. Distillation material balance ispresented in table 3.Table 3. Polymers breakupA long distillate was cooled and centrifuged for crystal phase and oil extraction. Crystals and oil were undergone the chromatographic analysis.The results of the analysis showed that naphthalene,dimethylnaphthalenes, diphenyl, acenaphthene, dioxidee diphenylene and fluorene entered into the composition of oil and crystals. Increased content of highboiling component in crystals differs them from oil thatindicates that flourene concentration in solid phase occurs already on the stage of crystallization.Crystal part of 270...310 °С fraction separated afteroil extraction was subjected to rectification. Rectification was carried out at the laboratory packedFraction Wt. %Recovery to 270 °СLong distillate 270...310 °СVat residue >310 °С186022Bulletin of the Томsк Pоlytеchnic University. 2007. V. 310. № 1138Figure. Flow scheme of polymers technological recyclingPolymer FractionationFraction to 270°ɋ270…310 °ɋfractionVatresidueIntoɉɆ cycle Centrifugation To utilization Crystals OilRectification  AcenaphthenefractionDiphenylene dioxide fractionFluorene fraction rectifying column with Levin head. Column effectiveness is 50 theoretical plates. Owing to close boiling temperatures of main components high reflux ratio is recommended at extraction. It was achieved by selectingball refluxes of different diameters (from 40 to 60 mm)with natural air cooling. Vapor phase temperature wasmeasured in immediate vicinity of the place of productselection.Composition of products distilled at rectification wascontrolled by sampling in the range of 270...300 °С witha 5° step and analysis at chromatograph ЛХМ8МД.The results of the analysis are presented in table 4.Table 4. Individual components content at rectification oflong distillate crystal partThe obtained data allow us to restrict roughly temperature intervals of individual components extractionsat batch rectification by the following limits:acenaphthene – 270...280 °С;diphenylene dioxide – 280...290 °С;fluorene – 290...300 °С.Thus, flow scheme of polymers technological recycling may be presented in the following way (figure).Conclusion1. In the given conditions yield and composition ofstraw oil fractions from different parts of flowsheetare examined.2. It was mentioned that polymers of benzene extraction from regeneration cycle of straw oil are the mostacceptable as raw material for acenaphthene, diphenylene dioxide and fluorine extraction.3. Laboratory researches of long fraction 270...300 °Сcomposition at its rectification were carried out.4. Flow scheme of technological recycling of byproduct – coking industry wastes obtaining individualcompounds – acenaphthene, diphenylene dioxideand fluorine was suggested.ComponentComponent content, wt. %, at selection temperature, °С260 265 270 275 280 285 290 295 297 300Diphenyl+dimethylnaphthaleneAcenaphtheneDiphenylene dioxideFluoreneAnthracene86,712,483,416,639,160,911,089,01,572,026,585,214,856,044,018,98 1,17,892,21,594,34,2Chemistry139REFERENCES1. Mariich L.I., Ambrozevich F.N. About straw oil quality // Coke andChemistry. – 1981. – № 9. – P. 32–35.2. Kolyandr L.Ya., Andreeva V.S., Zbykovski I.I. On the issue of production of effective absorbent for benzene hydrocarbons trapping //Coke and Chemistry. – 1982. – № 5. – P. 30–33.3. Gogoleva T.Ya., Kuzmina E.Ya., Volkov E.L. Ways of straw oil quality improvement // Coke and Chemistry. – 1980. – № 9. –P. 54–55.4. Gogoleva T.Ya., Kovalev A.P. Investigation of absorptive and polymerization capacity of resin straw oils // Coke and Chemistry. –1984. – № 9. – P. 27–29.5. Yakovleva T.P., Vail E.V. Composition and physicalchemical properties of resin straw oil // Coke and Chemistry. – 1984. – № 1. –P. 24–33.Arrived on 22.05.2006

High-boiling components in straw oil

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