SE185308C1 - - Google Patents

Description

KLASS INTERNATIONELLSVENSK C 09 f22 h:7/01 PATENT- OCH REGISTRERINGSVERKET Ans. 741111961 den 18/7 1961 ESSO RESEARCH AND ENGINEERING Co., ELIZABETH, N.J., USA San att framstalla ett beekbindemedel, avsett for anvlindning vid tillverkning av kolelektroder 13ppfinnare: L F King och C T Steele Prioritet begard fron den 26 juli 1960 (USA) Foreliggande uppfinning haul& sig till ett satt att framstalla kollialtiga material, vilka lampa sig som bindemedel for kolelektroder, och till en komposition, vilken är anvandbar som bindemedel fOr sadana. CLASS INTERNATIONAL SWEDISH C 09 f22 h: 7/01 PATENT AND REGISTRATION AGENCY Ans. 741111961, 18/7 1961 ESSO RESEARCH AND ENGINEERING CO., ELIZABETH, NJ, USA San to produce a beech binder, intended for use in the manufacture of carbon electrodes 13Inventors: LF King and CT Steele Priority requested from 26 July 1960 (USA). to form a composition for producing carbonaceous materials, which act as binders for carbon electrodes, and for a composition which can be used as a binder for such electrodes.

De fiesta kolelektroderna framstAllas vanligen av brand koks, som ken utgoras av petroleum koks, koks av olika koltyper och liknande. Eftersom koksen joke har nagon formaga att binda sig spiv, maste den blandas med ett bindemedel. Vid framstallning av elektroderna males koksen, blandas med ett Iampligt bindemedel, pressas och varmes fOr forkolning av bindemedlet. Most carbon electrodes are usually made of fire coke, which consists of petroleum coke, coke of various types of carbon and the like. Since the coke joke has someone able to bind to the spit, it must be mixed with a binder. In preparing the electrodes, the coke is ground, mixed with a suitable binder, pressed and heated to char the binder.

Bindemedlets art och kvalitet är av mycket stor betydelse. Petroleumtjaror och -beck ha hit-tills icke visat sig anvandbara av manga orsaker, sasom att de framstallda elektrodernas mekaniska hallfasthet blir ojamn och deras elektriska ledningsformaga varierar. Icke heller hogaromatiska tjdror erhallna vid krackningsprocesser, ha kunnat ge tillfredsstallande beck pa vanligt satt. The nature and quality of the binder are of great importance. Petroleum tar and pitch have hitherto not proved useful for many reasons, such as that the mechanical strength of the electrodes produced becomes uneven and their electrical conductivity varies. Nor are highly aromatic tethers obtained in cracking processes, able to give satisfactory stains in the usual way.

Koltjarebeck anvandes nastan uteslutande som bindemedel vid framstallning av amorf a och grafiterade elektroder, block, cylindrar, pulver och andra kolprodukter. Becket blandas med pulver eller grus av petroleumkoks eller liknande material, varefter blandningen pressas, strangpressas eller formas for erhallande av onskad form fore branningen. Koltjarebeck är sarskilt fOrdelaktigt, emedan det har hog halt bensenolosliga, hartsartade amnen, som bilda koks vid forkolning vid relativt lag temperatur. Bildningen av denna koks mellan de korn av fast, kolhaltigt material, som bildar huvudmassan kittar ihop kornen till en tat produkt med hog ledningsformaga. Koltjarebeck was used almost exclusively as a binder in the production of amorphous and graphitized electrodes, blocks, cylinders, powders and other carbon products. The pitch is mixed with powder or gravel of petroleum coke or similar material, after which the mixture is pressed, extruded or shaped to obtain the desired shape before combustion. Koltjarebeck is particularly advantageous, because it has a high content of benzene-insoluble, resinous substances, which form coke on charring at a relatively low temperature. The formation of this coke between the grains of solid, carbonaceous material, which form the main mass, putty the grains together into a tat product with a high conductivity.

Enligt foreliggande uppfinning framstalles ett beckbindemedel fOr kolelektroder lampligen i tva. According to the present invention, a pitch binder for carbon electrodes is suitably prepared in two.

Dupl. kl. 12 h: 2; 21 h: 20/01; 21 h: 20/0 steg ur en speciell petroleumrest, som bestar av en aromatisk tjara erhallen genom angkrackning av motorbrdnnolja. Aterstoden utgores av den bottenfraktion, som uttages frau det fraktioneringstorn, vilket anvandes for fraktionering av de angkrackade produkterna. Under det forsta steget enligt uppfinningen framstalles ett rela, tivt olosligt basmaterial, som har hog mjukningspunkt och Mgt okoksningsvarde# genom lamplig varmebehandling, foretradesvis nedbrytande destillering eller langvarig upphettning, medan det andra steget innebar flussning av detta basmaterial med en mindre andel av en lattare eller mer lagkokande kolvatefraktion till den onskade mjukningspunkten vid anvandning av nedbrytande destination och avgasning vid langvarig upphettning under overtryck. I vissa fall karma de bagge stegen genomforas i samma apparat. Det fOrsta steget kan utgiiras av en luftoxidation i stallet for den namnda, feredragna behandlin en, churn den joke anses vara fullt likvardig med denna. Dupl. at 12 h: 2; 21 h: 20/01; 21 h: 20/0 steps out of a special petroleum residue, which consists of an aromatic tar obtained by steaming engine fuel oil. The residue is the bottom fraction taken from the fractionation tower used to fractionate the cracked products. During the first step according to the invention, a relatively insoluble base material is produced which has a high softening point and Mgt coking value # by suitable heat treatment, preferably degrading distillation or prolonged heating, while the second step involved fluxing this base material with a smaller proportion of a lighter or more boiling boiling hydrocarbon fraction to the desired softening point when using decomposing destination and degassing in case of prolonged heating under overpressure. In some cases, the ram steps are carried out in the same apparatus. The first step can be carried out by an air oxidation in place of the said, preferred treatment, churn the joke is considered to be fully equivalent to this.

Icke flagon enstegsprocess synes kunna ge ett lampligt elektrodbindemedel, am man utgar frail de afomatiska petroleumtjarresterna. Om salunda bindemedlets kokstal och halt av bensenolosligt aro tillrackligt hbga, blir mjukningspunkten alitfOr hog medan de ovriga vardena bli alltfOr laga, am mjukningspunkten ligger Morn det ratta intervallet. Enligt fOreliggande uppfinning framstalles vidare ett beckbindemedel f Or kolelektroder av en petroleumrest for efterliknande av bindemedel av koltjarebeck, genom en tvastegsprocess, vars forsta steg kraver hog temperatur for framstallning av de bensenolosliga hartser eller amnen, som aro viktiga i bindemedlet och anses vara de basta elektrodbindemedlen. Man Onskar c:a 30 viktprocent bensenolosligt och minst c:a 15 %. 2— — Ett utbyte av aromatiska tjaror av c:a 15-25 - volymprocent raknat pa ingaende material och beroqndet av dettas karaktar erhalles vid angkrackning av motarbrannoljor till en omsattning av c:a 40-45 % till Crkolvaten och lattare kolväten. Den aromatiska tjaran har hog asfaltenhalt av c:a 12-25 viktprocent. Dessa asfaltener eller hartser i becket eller bindemedlet, vilka aro losliga i bensen men olOsliga i petroleumeter, bidra till laindningsformagan. A non-flawed one-step process seems to be able to give a suitable electrode binder, starting from the afomatic petroleum tar residues. If the boiling point of the binder and the content of benzene-insoluble aro are sufficiently high, the softening point will always be too high while the other values will be too high, while the softening point will be the right range. According to the present invention, a pitch binder is further prepared for carbon electrodes from a petroleum residue for mimicking coal tar pitch binders, by a two-step process, the first step of which requires a high temperature for the preparation of the benzene-insoluble resins or substances which are important in the binder and are considered the best electrode binders. . We want about 30% by weight of benzene-insoluble and at least about 15%. 2— - A yield of aromatic tar of about 15-25% by volume calculated on any material and the dependence of its character is obtained on the cracking of engine fuel oils to a turnover of about 40-45% to the hydrocarbons and lighter hydrocarbons. The aromatic tar has a high asphalt content of about 12-25% by weight. These asphaltenes or resins in the pitch or binder, which are soluble in benzene but insoluble in petroleum ether, contribute to the winding shape.

Halten av kinolinolosligt Or lag for bindemedel eller beck framstallda ur aromatiska tjdror enligt fOreliggande uppfinning, vanligen c:a 2 viktprocent, vilket innebar en fordel. Det kinolinlosliga materialet i bindemedlet Or smaltbart och har hog hindningshallfasthet efter stelning. Det kinolinlosliga materialet anses vara mycket Overlagset det kinolinolOsliga. The content of quinoline - insoluble Or layer for binder or pitch prepared from aromatic acids according to the present invention, usually about 2% by weight, which was an advantage. The quinoline-soluble material in the binder is fusible and has a high membrane resistance after solidification. The quinoline soluble material is considered to be very superior to the quinolinol soluble.

Det andra steget i den nedbrytande destillationen innebar flussning eller aerblandning med ett lattare material, som kan utgOra en del av den ursprungliga, aromatiska tjaran, ett destillat av denna eller ett restflode fran fraktionering av katalytiskt krackat material. Vid provning av becker brukar man destillera dem till c:a 360° C och sedan hestamma mjukningspunkten for restflOdet. Den fraktion, som destilleras vid denna teraperatur, bor icke overstiga 6 viktprocent. Detta begransar halten av latt material i flussen till c:a 20 viktprocent pa basis av 30 viktprocent flussolja i den slutliga blandningen Detta utgor den ena klara, byre gransen fOr det flussmaterial, som kan anvandas. The second step in the decomposing distillation involved fluxing or aeration with a lighter material, which may be part of the original aromatic tar, a distillate thereof or a residual flood from fractionation of catalytically cracked material. When testing pitchers, they are usually distilled to about 360 ° C and then strained to the softening point of the residual flow. The fraction distilled at this temperature should not exceed 6% by weight. This limits the content of light material in the flux to about 20% by weight on the basis of 30% by weight of flux oil in the final mixture. This constitutes one clear, clear limit for the flux material that can be used.

Det beckbindemedel, som framstalles enligt foreliggande uppfinning, kan anvandas vid framstallning av fardigbranda elektroder eller soderbergselektroder och Or sarskilt lampligt for elektroder avsedda att anyandas vid framstallning av aluminium, ehuru uppfinningen icke Or begransad hartill. The pitch binder prepared according to the present invention can be used in the manufacture of prefabricated electrodes or soderberg electrodes and is particularly suitable for electrodes intended to be used in the manufacture of aluminum, although the invention is not limited thereto.

Enligt ett specifikt exempel bildas den aroroatiska tjara, vilken anvandes som utgangsmaterial, som en hogkokande restprodukt eller restflode frau angkrackning av motorbrannolja for framstallning av olefiner, diolefiner, aromatiska, flytande kolvaten och liknande. According to a specific example, the aromatic tar, which is used as a starting material, is formed as a high-boiling residual product or residual river from the cracking of motor fuel oil to produce olefins, diolefins, aromatic, liquid hydrocarbons and the like.

Tva soin restflede erhallna, aromatiska tjaror, Vilka kunna anvdndas som utgangsmaterial enligt fOreliggande uppfinning, ha foljande egenskaper: Spec. vikt °API Densitet vid 16°C Flampunkt (Oppen skal) °C .. Two residual aromatic tars, which can be used as starting materials according to the present invention, have the following properties: Spec. weight ° API Density at 16 ° C Flash point (Open shell) ° C ..

Viskositet 99° C, SSU —1,6 1,089 149 9—4,0 1,110 160 213 Kol, vikt-% 89,90,4 Vate, viktprocent 7,2 6,8 Atomforhallande H/C 0,96 0,90 Svavel, viktprocent.. 1,9 2,0 Aska,» 0,003 0,01 Asfaltener» 17 22 ASTM-destillation Begynnelsekpkt 270 300 Temperatur for overdest. av 5% 297 324 Temperatur for_ Overdest. av 10% 308 3 Temperatur for overdest. av 20% 324 357 Temperatur f Or oVerdest. av % 342 37 Temperatur for overdest. av 40%. 363 388 Temperatur for overdest. av 50% 384 412 Uppfinningen omfattar aromatiska resttj dror med varden som ligga mellan del de bagge kolum>nerna angivna v5rdena Qchi vissa tall utanfor dessa.- Angkrackningen Or valkand och bestar i krackning narvaro av c:a 60-85 molprocent vattenanga av motorbrannolja med en begynnelsekokpunkt av c:a 204-274° C och en slutkokpunkt av c:a 399 440° C vid en utloppstemperatur i slingan av c:a 649-788° C och omedelbar kylning med en olja med ett kokpunktsintervall av c:a 260-357° C till en temperatur av c:a 282-293°C. Motorbrannoljan har en densitet av 0,873 vid 15° C; en molvikt av c:a 290, en halt av aromatiska ringer av c:a 11,3 viktprocent och en halt av nafteniska ringar av c:a 32,2 viktprocent. Viscosity 99 ° C, SSU —1.6 1,089 149 9—4,0 1,110 160 213 Carbon,% by weight 89,90,4 Water, weight percent 7,2 6,8 Atomic ratio H / C 0,96 0,90 Sulfur , weight percent .. 1.9 2.0 Ash, »0.003 0.01 Asphaltenes» 17 22 ASTM distillation Starting point 270 300 Temperature for overdest. of 5% 297 324 Temperature for_ Overdest. of 10% 308 3 Temperature for overdest. of 20% 324 357 Temperature f Or oVerdest. of% 342 37 Temperature for overdest. of 40%. 363 388 Temperature for overdest. of 50% 384 412 The invention comprises aromatic residues with the value which lie between the values of the bag columns> Qchi certain numbers outside these.- The steam crack Or valkand and consists in cracking in the presence of about 60-85 mol% water vapor of motor fuel oil with an initial boiling point of about 204-274 ° C and an end boiling point of about 399,440 ° C at an outlet temperature in the loop of about 649-788 ° C and immediate cooling with an oil having a boiling point range of about 260 -357 ° C to a temperature of about 282-293 ° C. The engine fuel oil has a density of 0.873 at 15 ° C; a molecular weight of about 290, a content of aromatic rings of about 11.3% by weight and a content of naphthenic rings of about 32.2% by weight.

De gasformiga pro dukterna, som innehalla vate, mattade kolvaten, definer, diolefiner och liknande, uttas som toppfraktion, varefter de flytande kolvatena fraktioneras for avskiljande av en aromatisk bensin, som kokar vid ca 38-238° C, en mer hOgkokande, aromatisk fraktion, som kokar vid c:a 188-299° C och kan aterforas till Ongkrackningsenhetens kylzon. Den som rest erhallna, aromatiska tjaran utgor c:a 15-25 % raknat pa det ingaende materialets volym. The gaseous products, which contain hydrogen, matte hydrocarbons, defines, diolefins and the like, are taken out as the top fraction, after which the liquid hydrocarbons are fractionated to separate an aromatic gasoline, which boils at about 38-238 ° C, a more boiling, aromatic fraction. , which boils at about 188-299 ° C and can be returned to the cooling zone of the Non-cracking unit. The aromatic tar obtained is about 15-25% based on the volume of the incoming material.

Den aromatiska tjaran anvandes som ingaende och varmebehandlas sedan vid en tempera- tur Over c:a 316° C, foretradesvis mid c: a 399 482° C, exempelvis genom nedbrytande destillering eller mild koksning till bildning av ett flyktigt material, vilket uttages som toppfraktion och kondenseras, och en hogkokande, polymer komponent, vilken stannar kvar och i huvudsak Or bensenoloslig. Den varmebehandlade, aromatiska tjaran flussas eller blandas sedan ater med en lagkokande vatska till onskad mjukningspunkt. Delta flussmedelkan utgoras av en del av den som utgangsmaterial anvanda, aromatiska tjaran. The aromatic tar is used as a starting material and then heat-treated at a temperature above about 316 ° C, preferably at about 399,482 ° C, for example by decomposing distillation or gentle coking to give a volatile material, which is taken as a top fraction. and condensed, and a high boiling polymer component, which remains and is substantially benzene insoluble. The heat-treated, aromatic tar is then flushed or mixed again with a law-boiling liquid to the desired softening point. Delta flux can be a part of the aromatic tar used as a starting material.

Om varmebehandlingen genomfores under Overtryck, intrader en kondensation och polymerisation av en del ay det latta materialet pa grund av den langa kontakttiden. Ur driftssynpunkt fOredras langvarig upphettning vid konstant temperatur jamte avdrivning. Ett moderat tryck av c:a 4,5-106 kplcm2 kan tillampas. En slinga for termisk krackning ansluten till en uppvarmningstrumma kan anvandas fifor att Ulla den varmda, aromatiska, ingaende tjaran yid konstant temperatur. De yid upphettning under tryck erhallna produkterna destilleras for sepaTering ay restflodet fran latta toppfraktioner. - -g. If the heat treatment is carried out under Overpressure, a condensation and polymerization of some of the light material occurs due to the long contact time. From an operational point of view, prolonged heating at constant temperature as well as evaporation is preferred. A moderate pressure of about 4.5-106 kplcm2 can be applied. A thermal cracking loop connected to a heating drum can be used to heat the heated, aromatic, incoming tar at constant temperature. The products obtained under pressure under distillation are distilled for separation of the residual stream from light top fractions. - -g.

Tillrackligt med lagkokande material avlagsnas for erhallande av en restflodesprodukt med onskad nijukningspunkt for ett bindemedel av petroleum-b ecktyp. Sufficient layer-boiling material is deposited to obtain a residual flood product with the desired reflux point for a petroleum pitch binder.

Enligt ett utforande av nedbrytande destillering satsades 700 ml av den aromatiska tjaran av den enligt ovan yid angkrackning erhallna typen i en rundbottnad destillationsblasa ph 2 1 av rostfritt stal anordnad i en varmemantel. Destillationskolven var forsedd med ett tatt lock av »Pyrex»-glas med fyra oppningar med standardkona. Dessa oppningar anyandas for tva terrnoelement (angans och blasans temperaturer), en med kvicksilver forseglad omrorare, ett destillationsutlopp och ett flussinlopp, som ersatte ett av terinoelementen under tillsattningen av flussMedlet, vilken kunde geras isoterm. According to a process of decomposing distillation, 700 ml of the aromatic tar of the type obtained by the above cracking were charged into a round bottom distillation bubble pH 2 of stainless steel arranged in a heating mantle. The distillation flask was fitted with a four-hole "Pyrex" glass lid with a standard cone. These openings are used for two thermocouples (steam and bubble temperatures), a mercury-sealed stirrer, a distillation outlet and a flux inlet, which replaced one of the thermocouples during the addition of the flux, which could be made isothermal.

Angtemperaturen i blisan holis vid c:a 2743770 C och blasans temperatur holls vid c:a 3434540 C. Va.rme tillfordes med en gasbrannare. The steam temperature in the blister holis at about 2743770 C and the blister temperature is maintained at about 3434540 C. Heat is supplied with a gas burner.

Den nedbrytande destillationen gick med en hastighet av c:a 5-30 ml/min under c:a 25-60min, tills den onskade restprodukten hade erhallits. For detta andamal bestamdes den procentuella mangden uttagen toppfraktion. Den erforderliga mangden flussolja, som i detta fall ntgjorde en del av den tillforda aromatiska tjaran, tillsattes gedan genom flussinloppet, varefter upphettningen och omroringen fortsattes under ca 15 min. Varmemanteln runt blasans ovre del togs bort omedelbart fore flussningen till forhindrande av avdrivning av ytterligare toppfraktion. The decomposing distillation proceeded at a rate of about 5-30 ml / min for about 25-60 minutes, until the desired residual product had been obtained. For this purpose, the percentage of top fraction taken was determined. The required amount of flux oil, which in this case formed part of the supplied aromatic tar, was then added through the flux inlet, after which the heating and stirring were continued for about 15 minutes. The heating mantle around the upper part of the bladder was removed immediately before the flow to prevent evaporation of further top fraction.

Flussvatskan kan utgOras av: inga.ende, aromatisk tjara av den ovan beskrivna typen, fraktioneringsrestflo de fran katalytisk krackning med en begynnelsekokpunkt av c:a 232°C och en temperatur for overdestillering av 50 % av c:a 435° C, eller godtycklig annan, hogkokande, flytande rest eller destillat, av vilket hogst 20 % destillerar Over vid 360° C. The effluent can be composed of: single aromatic tar of the type described above, fractionation residues from catalytic cracking with an initial boiling point of about 232 ° C and a temperature for over-distillation of about 435 ° C, or arbitrary other, high-boiling, liquid residue or distillate, of which 20% is distilled by distillation Over at 360 ° C.

Vid en nedbrytande destillering i ett karl av rostfritt stal erhollos foljande resultat: Tabell 1. In the case of a decomposing distillation in a stainless steel vessel, the following results are obtained: Table 1.

Destillat volymprocentTid i min. begynnelsepunkt0,0 5, 12,0 17,2 23,7 28,0 32,7 37,6 43,0 48,2 53,3 slutpunkt Best (raknat pa blasans be- skickning) 36,2 viktprocent Utbyte (raknat pa beskick ningen i Masan) 96,5 viktprocent Restflodets kokstal 64,3 Vid ett forsOk blandades ca 72,8 viktdelar av restflOdet enligt tabell 1 med 27,2 viktdelar num-- ohedel (ingaende, aromatisk tjara) och Mils blandningen c:a 15 min vid c:a 427° G.,Det erhallria blocket hade en mjukningspunkt av .c:a 1039 C; en-halt av bensenolosligt av-26,4 viktprocent och ett kokstal av c:a 52,7 viktprocent. Distilled volume percentageTime in min. starting point0.0 5, 12.0 17.2 23.7 28.0 32.7 37.6 43.0 48.2 53.3 end point Best (calculated on bladder condition) 36.2% by weight Yield (calculated on mission in Masan) 96.5% by weight The residual flow of the residual river 64.3 In one experiment, about 72.8 parts by weight of the residual flood according to Table 1 were mixed with 27.2 parts by weight of num-- ohedel (ingent, aromatic tar) and the Mils mixture approx. min at about 427 ° C. The obtained block had a softening point of about 1039 ° C; a content of benzene insoluble of -26.4% by weight and a coke ratio of about 52.7% by weight.

Enligt ett annat exempel var halten restflode c:a 37,6 viktprocent. 78,4 viktdelar av detta rest-node bolls 15 mm vid c:a 427° C after tillsats av c:a 21,6 viktdelar flussolja, varvid becket lick mju1Lningspunkten c:a 113° C, halt av bensenolosligt 32,3 viktpro cent och kokstalet c: a 54,5 viktprocent: -Vid tillampning av flussningsmetoden synes destillationshastigheten icke vara kritisk. Slutkokpunkten är emellertid kritisk. En11gt ett exempel, dA. det aromatis1ca ingaendet varmdes till en temperatur i blasan av c:a 480° C och destillationstiden var c:a 45 min, blev mangden rest- ' node 27,9 viktprocent. Vid anvandning av 37,3 viktprocent hardningsolja kunde aterstoden icke blandas till bildning av en homogen pro dukt. En-. ligt ett annat exempel, da temperaturen- i bissan var c:a 451° C och destillationstiden c:a 30 min,_ blev mangden restflode 31,2 viktprocent, vilket restflode blandades till ett beckbindemedel under anvandning av 36 viktprocent hardningsolja. Detbildade becket hade mjukningspunkten c:a 122°C, halt av bensenolOsligt c:a 32,5 viktprocent och kokstalet c:a 55 viktprocent. According to another example, the residual flood content was about 37.6% by weight. 78.4 parts by weight of this residual ball 15 mm at about 427 ° C after the addition of about 21.6 parts by weight of flux oil, the pitch licking the melting point about 113 ° C, content of benzene-insoluble 32.3% by weight and the boiling point about 54.5% by weight: -When applying the fluxing method, the distillation rate does not seem to be critical. However, the final boiling point is critical. One example, dA. the aromatic mixture was heated to a temperature in the bubble of about 480 ° C and the distillation time was about 45 minutes, the amount remaining was 27.9% by weight. Using 37.3% by weight of curing oil, the residue could not be mixed to form a homogeneous product. One-. In another example, when the temperature in the bissant was about 451 ° C and the distillation time was about 30 minutes, the amount of residual flow was 31.2% by weight, which residual flow was mixed into a pitch binder using 36% by weight of hardening oil. The pitch formed had a softening point of about 122 ° C, a content of benzene soluble about 32.5% by weight and a coke ratio of about 55% by weight.

Med produktens kokstal avses den icke forflyktigade rest i viktprocent, som erhalles, sedan at prov liar hallts i en degel och hallits vid c:a. 550° C under c:a 2,5 h. The cooking number of the product refers to the non-volatile residue in percentage by weight, which is obtained after the sample has been kept in a crucible and kept at approx. 550 ° C for about 2.5 hours.

Det anvanda flussmedlet utgjordes av en del av den ingaende aromatiska tjaran. Reaktionsbldnd-- ningen omrordes hela tiden. HOgst c:a 70 viktpro-1 cent aromatisk tjara bor uttas som toppfraktion under den nedbrytande destilleringen, eftersom det har visat sig, att det, om mar an c:a 70 % av den aromatiska tjaran tages ut som toppfraktion nnder den nedbrytande destilleringen, icke ar mojligt att med framgang flussa eller blandar resten med en vatska till bildning av en homogen produkt och tillfredsstallande bindemedel. The flux used consisted of a part of the incoming aromatic tar. The reaction mixture was stirred constantly. A maximum of about 70% by weight of aromatic tar should be taken as the top fraction during the decomposing distillation, since it has been found that if about 70% of the aromatic tar is taken out as the top fraction during the decomposing distillation, it is not possible to successfully fluff or mix the residue with a liquid to form a homogeneous product and satisfactory binder.

Foljande resultat enligt tabell 2 erhollos vid nedbrytande destillering av en aromatisk -Ora: yid c:a 274-377° C angtemperatur och en temperatur i blasan av 343-454° G till den angivna mangden restflode raknad i procent pa den ingaende, aromatiska tjarans vikt. Upphettningstiden var c:a 30-60 min. Uppgiftema omfatta, aven flussande made!, som besta av de vid destillering erhallna restflodena flussade med ingaende aromatisk tjara. Ett studium av tabellen visar, att dessa blandningar ligga mycket nara de god-, tagna normerna for sadant koltjarebeck, vilket anvandes corn elektrodbindemedel. Det totala ntbytet av bindemedelsbeck ra.knat pa den ingaende, aromatiska tjaran var ungefar 43,3 viktprocent. The following results according to Table 2 are obtained by decomposing distillation of an aromatic -Ora: yid about 274-377 ° C ang temperature and a temperature in the bubble of 343-454 ° G to the specified amount of residual flow calculated as a percentage of the incoming aromatic tar. weight. The heating time was about 30-60 minutes. The tasks include, even fluxing made !, which consists of the residual rivers obtained by distillation flushed with no aromatic tar. A study of the table shows that these mixtures are very close to the accepted standards for such coal tar pitch, which used corn electrode binder. The total yield of binder pitch calculated on the incoming aromatic tar was about 43.3% by weight.

Angtemp era- tur °C 285 298 307 313 320 329 334 3 351 352 353 353 - - Tahell 2. Angtemp era- tur ° C 285 298 307 313 320 329 334 3 351 352 353 353 - - Tahell 2.

Flussningsmetod Stenkolstjare- beek (godkand som binde- medelsbeck) Utbyte av aterstod i viktprocent (raknat pa ingaende tjara) 34,7 33,3 32,1 34,8 33,2 Blandningens. sammansattning i viktprocent Restflode 68,7 68,6 67,7 68,68,2 Flussmedel (aromatisk tjara) 31,3 31,4 32,3 31,31,8 Fysikaliska varden Mjukningspunkt °C 93 102 198 109 83 Kokstal viktprocent 53 57 53 Bensenolosligt viktprocent 23 24 36 24 Beckbindernedel franastallda av varmebehandlade, aromatiska tjaror enligt foreliggande uppfinning ha de egenskaper, som anges i foljande tabell 3. Fluxing method Coal tar stream (approved as binder stream) Yield of residue in weight percentage (calculated on incoming tar) 34.7 33.3 32.1 34.8 33.2 Mixture. composition in weight percent Residual flow 68.7 68.6 67.7 68.68.2 Flux (aromatic tar) 31.3 31.4 32.3 31.31.8 Physical values Softening point ° C 93 102 198 109 83 Boiling percentage weight percentage 53 57 53 Benzene-soluble weight percent 23 24 36 24 Beck binder parts made from heat-treated aromatic tar according to the present invention have the properties set forth in the following Table 3.

Tabell 3. Table 3.

A 33 Mjukningspunkt °C 107 101 C vikt-% 91,9 92,3 H vikt-% 5,9 6,1 Atomforhallande C/H 1,31 1,38 Kokstal 53,9 52,6 Bensenoldsligt vikt-% 16,25,6 S, % 1,7 1, Aska, % 0,08 0,03 Bindemedlet enligt spalt B anvandes for framstallning av en elektrod. Den branda petroleumkoksen siktas vanligen och olika kornklasser anvandas. Den grova kornklassen av brand koks, som kan utgoras av en petroleumkoks, blandas med det upphettade bindemedlet, varefter de Ovriga, finare koksfraktionerna tillsattes. Blandningen formpressas och varrnes langsamt, exempelvis upp till 24 h till c:a 1000° C, och hales sedan vid denna temperatur under endast c:a 1 h for forkolning eller fOrkoksning av bindemedlet. En elektrod framstalldes under anvandning av bindemedlet enligt spalt B. Denna elektrod uppfyllde minimikraven pa tryckhallfasthet och elektrisk motstand. Elektroderna kunna aven framstallas pa annat satt. A 33 Softening point ° C 107 101 C wt% 91.9 92.3 H wt% 5.9 6.1 Atomic ratio C / H 1.31 1.38 Boiling point 53.9 52.6 Benzene solids wt% 16, 25.6 S,% 1.7 1, Ash,% 0.08 0.03 The binder according to column B was used to make an electrode. The hot petroleum coke is usually sieved and different grain classes are used. The coarse grain class of fire coke, which may be a petroleum coke, is mixed with the heated binder, after which the other, finer coke fractions are added. The mixture is compression molded and heated slowly, for example up to 24 hours to about 1000 ° C, and then kept at this temperature for only about 1 hour before charring or coking the binder. An electrode was fabricated using the adhesive of column B. This electrode met the minimum requirements for compressive strength and electrical resistance. The electrodes can also be manufactured in other ways.

Beckbindemedlet kan aven framstallas enligt foreliggande uppfinning genom varmebehandling vid c:a 427-482° C under c:a 5-150 min eller Iangre tid. Denna varmebehandling sker lampligen under eft tryck av c:a 3,1-142 kplcm2. De varmebehandlade produkterna avdrivas sedan vid lagre tryck for kervinning av en restflodesIraklion, vilken lampar sig for anvandning som b eckbindemedel. The pitch binder can also be prepared according to the present invention by heat treatment at about 427-482 ° C for about 5-150 minutes or longer. This heat treatment takes place suitably under a pressure of approx. 3.1-142 kplcm2. The heat-treated products are then evaporated at lower pressures to recover a residual river irraclion, which is suitable for use as a pitch binder.

Vid arbete under overtryck intrada liknande, kemiska reaktioner, ehuru det lattare eller mer Mgkokande materialet medverkar i hogre grad till kondensations- eller polymerisationsreaktionerna pa grund av den lagre kontakttiden. Man foredrar aft halla restflOdet vid konstant ternperatur under langre tid och driva av de latta produkterna. When working under overpressure, similar chemical reactions are introduced, although the lighter or more soft-boiling material contributes to a greater extent to the condensation or polymerization reactions due to the lower contact time. It is preferred to keep the residual flow at a constant temperature for a long time and to drive off the light products.

Restflodet Mills under tryck vid 416-460° C under olika forsok. Upphettningstiden var c:a 100120 min, cla temperaturen lag over 371° C. Vid 416° C erholls endast en svag krackning vid ett maximitryck av 8 kp/cm2. Vid en maxiinitemperatur av 454° C var krackningen starkare, vilket medforde ett maximitryck av 78 kp/cm2 och c:a 14 viktprocent bensenolosligt. Asfaltenhalten och kokstalet okade aven med Okande tryck och temperatur. Residual flood Mills under pressure at 416-460 ° C during various experiments. The heating time was about 100120 min, cla the temperature was just over 371 ° C. At 416 ° C only a slight cracking was obtained at a maximum pressure of 8 kp / cm2. At a maximum temperature of 454 ° C, the cracking was stronger, which resulted in a maximum pressure of 78 kp / cm 2 and about 14% by weight of benzene insoluble. The asphalt content and boiling point also increased with increasing pressure and temperature.

Produkterna Iran arbete vid hogre temperatur och tryck, 454° G och 78 kp/cma, vakuumdestillerades och gay 62 viktprocent restflode med en mjukningspunkt av 87° C, eft kokstal av 50 viktprocent och c:a 25 viktprocent bensenolosligt, och ett utbyte av 55 viktprocent restflode med mjukningspunkten 104° C, kokstalet 54 viktprocent och 31 viktprocent bensenolosligt. Dessa produkters vatehalt (5,5-5,9 %) var lagre an vatehalten for beck framstallt genom flussning av restflodena frail nedbrytande destillering enligt ovan. I detta hanseende narmade sig de salunda behandlade produkterna mera koltjarebeck an andra tidigare framstallda bindemedel. The products Iran work at higher temperature and pressure, 454 ° G and 78 kp / cma, were vacuum distilled and gay 62% by weight residual flood with a softening point of 87 ° C, after a boiling point of 50% by weight and about 25% by weight benzene insoluble, and a yield of 55 % by weight of residual flood with a softening point of 104 ° C, a boiling point of 54% by weight and 31% by weight of benzene insoluble. The water content of these products (5.5-5.9%) was lower than the water content of pitch produced by fluxing the residual rivers from decomposing distillation as above. In this respect, the products thus treated approached coal tar pitch more than other previously produced binders.

Utbytet av material, restflode, med Mgt kokstal blir mycket hOgre vid behandling under tryck och vid konstant temperatur On vid andra forfaranden, som ha undersokts tidigare, sasom nedblytande destillering. The yield of material, residual flow, with Mgt boiling point is much higher in treatment under pressure and at constant temperature On in other processes, which have been investigated previously, such as degrading distillation.

Varmebehandling vid konstant temperatur jamte avdrivning ger ett hogre utbyte av bindemedelsbeck, dvs. c:a -60 viktprocent, an andra provade metoder. Lang uppehallstid pa c:a 150 -180 min vid c:a 460° C resulterade i agglomerering samt utfallning och utskiljning av stora kokspartiklar. En slinga for termisk krackning kan anvandas for att upphetta den ingaende, aromatiska tjaran till c:a 427-450° C, varefter upphettningstrumman anvandes for atsadkommande av erforderlig reaktionstid. Heat treatment at constant temperature along with evaporation gives a higher yield of binder pitch, ie. about -60% by weight, other methods tested. Long residence time of about 150 -180 minutes at about 460 ° C resulted in agglomeration as well as precipitation and precipitation of large coke particles. A thermal cracking loop can be used to heat the incoming aromatic tar to about 427-450 ° C, after which the heating drum is used to provide the required reaction time.

Ett annat forsok genomfordes i en anlaggning med en slinga fOr termisk krackning. Den ingaende, aromatiska tjaran leddes genom ugnen, uppehallstid c:a 13 min, och forangades i separatorn till bildning av bindemedelsbeck som restflode. Slingans utloppstemperatur var c:a 463° C och tryck vid utflodet ma 4,5 kp/cm2. Vid undersokning av restflOdet erhollos de i foljande tabel1 4 angivna resultatn. Another experiment was carried out in a plant with a loop for thermal cracking. The incoming aromatic tar was passed through the oven, residence time about 13 minutes, and evaporated in the separator to form binder stream as a residual flood. The outlet temperature of the loop was about 463 ° C and the pressure at the outflow was 4.5 kp / cm2. When examining the residual flow, the results given in the following Table 14 were obtained.

Tabell 4. Table 4.

Mjukningspunkt —18 107 C, vikt-% 92,0 H, vikt-% 6,0 Atomforhallande C/H 1, Kokstal 54,0 Kinolinoloshgt 0,49 Bensenolosligt S, vikt-% 1,7 Aska vikt-% 0,054 FOr Caning av halten bensenolosligt Ur det nodvandigt att genomfora langvarig upphettning i den upphettningstrumma, som bildar en del av slingan fOr termisk krackning, sã att reaktionstiden okas. Det i tabell 4 beskrivna bindemedlet lampar sig for framstallning av kolelektroder. Tre elektroder framstallda av detta beck uppfyllde kraven pa lagsta tryckhallfasthet och elektrisk resistivitet. Softening point —18 107 C, wt% 92.0 H, wt% 6.0 Atomic ratio C / H 1, Coke ratio 54.0 Quinoline solvate 0.49 Benzene soluble S, wt% 1.7 Ash wt% 0.054 For Caning of benzene insoluble content It is necessary to carry out prolonged heating in the heating drum which forms part of the loop for thermal cracking, so that the reaction time is increased. The binder described in Table 4 is suitable for the production of carbon electrodes. Three electrodes made of this pitch met the requirements for the lowest compressive strength and electrical resistivity.

Vid nedbrytande destillering antydde de genomforda forsoken, att de bensenolosliga hartserna eller materialen bildades vid c:a 427-454° C, da latta komponenter kontinuerligt logos ut som toppflo de. Upon decomposing distillation, the experiments performed indicated that the benzene-insoluble resins or materials were formed at about 427-454 ° C, as light components were continuously logged as top liquids.

Upphettning av ingaende, aromatisk tjara till konstant temperatur och under tryck saint avdrivning torde utgora de basta medlen for framstallning av elektrodbeckbindemedel, emedan utbytet av material med Mgt kokstal blir mycket hOgre an vid andra provade metoder. Heating of inert, aromatic tar to constant temperature and under pressure saint evaporation should be the best means for producing electrode pitch binder, since the yield of material with high coke ratio is much higher than in other tested methods.

Claims (11)

PatentansprAk:Patent claim: 1. Satt att framstalla ett beckbindemedel, avsett for anvandning vid tillverkning av kolelektroder, kannetecknat darav, att en som rest-node erhallen, aromatisk tjara, vilken har bildats som restflode frail angkrackning av motorbrannolja vid hog temperatur for framstallning av omattade och aromatiska kolvaten, varmebehandlas vid en temperatur Over c:a 316° C under tillracklig tid for avlagsnande av hogst c:a 70 viktprocent av den aromatiska tjaran, varefter eft lagkokande kolvate inblandas fOr installning av bindemedlets mjukningspunkt, eller att namnda som restflode Iran angkrackningen erhallna, aromatiska tjara Mlles vid en temperatur Over c:a 371° C under tillracklig tid for att Moja dess halt av bensenolosligt material och under ett tryck av minst c:a 4,5 kp/cm', varefter den krackade, aromatiska tjaran avdrives vid lagre tryck fOr atervinnande av en bottenfraktion, vilken par sig for anvandning som beckbindemedel.A process for producing a pitch binder intended for use in the manufacture of carbon electrodes, characterized in that an aromatic tar obtained as a residual node, which has been formed as a residual flood from the cracking of motor fuel oil at high temperature for the production of unsaturated and aromatic hydrocarbons, heat-treated at a temperature Above about 316 ° C for a sufficient time for removal of harvest about 70% by weight of the aromatic tar, after which after boiling boiling carbonate is mixed in for installation of the binder softening point, or that said as residual flood Iran obtained the cracking, aromatic tar Melt at a temperature above about 371 ° C for a sufficient time to moja its content of benzene-insoluble material and under a pressure of at least about 4.5 kp / cm ', after which the cracked aromatic tar is evaporated at lower pressure for recovery of a bottom fraction, which pairs for use as a pitch binder. 2. Satt enligt patentanspraket 1, kannetecknat darav, att den som restflOde frail angkrackningen erhallna aromatiska tjaran varmebehandlas vid en temperatur Over c:a 316° C under tillracklig tid for avlagsnande av hogst c:a 70 viktprocent av den aromatiska tjaran, varefter ett lagkokande 308 — kolvate inblandas for installning av bindemedlets mjukningspunkt.2. Set according to claim 1, characterized in that the aromatic tar obtained as a residual flow from the cracking is heat-treated at a temperature above about 316 ° C for a sufficient time to remove at most about 70% by weight of the aromatic tar, after which a law-boiling 308 - carbonate is mixed in for installation of the binder softening point. 3. satt enligt patentanspraket 2, kannetecknat darav, att det agkokande kolvatet utgor en del av den som restflode erhallna, aromatiska tjaran, vilken bildas vid krackningen.3. set according to patent claim 2, characterized in that the boiling hydrocarbon forms part of the aromatic tar obtained as a residual flood, which is formed during the cracking. 4. Satt enligt patentanspraket 2, kannetecknat darav, att det lagkokande kolvatet anvandes i en mangd av c:a 30-35 viktprocent pa 70-65 viktprocent pa 70-65 viktprocent varmebehandlat restflode.4. A kit according to claim 2, characterized in that the boiling boiling carbonate is used in an amount of about 30-35% by weight of 70-65% by weight of 70-65% by weight of heat-treated residual flow. 5. Satt enligt patentanspraket 2, kannetecknat darav, att restflodet upphettas till 343-454° C (vatsketemperatur) under en tid av c:a 1 h for avdrivning corn toppflode av upp till c:a 69 % av restflodet.5. Set according to claim 2, characterized in that the residual flood is heated to 343-454 ° C (liquid temperature) for a period of about 1 hour to drive off corn top flow of up to about 69% of the residual flood. 6. Salt enligt patentanspraket 5, kannetecknat darav, att det lagkokande kolvatet utgOr en del av den tillforda, som restflode erhallna, aromatiska tjaran.Salt according to patent claim 5, characterized in that the low-boiling carbonate forms part of the aromatic tar obtained as a residual flood. 7. SRL enligt patentanspraket 2, kannetecknat darav, att varmebehandlingen innebar nedbrytande destillation vid ungefar atmosfdrstryck.7. SRL according to claim 2, characterized in that the heat treatment involved decomposing distillation at approximately atmospheric pressure. 8. Sat enligt patentanspraket 2, kannetecknat darav, att krackningen genomf Ores vid en ternperatur Over c:a 649° C. " 9. Skit enligt patentanspraket 1, kannetecknat ddrav, att den som restflode vid angkrackningen erhallna aromatiska tjaran Mlles vid en temperatur Over c:a 371° C under tillracklig tid for att hOja dess halt av bensenolosligt material och under ett tryck av minst c:a 4,5 kplem2, varefter den krackade, aromatiska tjaran avdrives vid lagre tryck fOr atervinnande av en bo ttenfraktion, vilken ldmpar sig for anvandning som beckbindemedel.8. According to patent claim 2, characterized in that the cracking takes place at a temperature above about 649 ° C. "9. Shit according to claim 1, characterized in that the aromatic tar obtained as a residual flood during the steam cracking at a temperature above about 371 ° C for a sufficient time to increase its content of benzene-insoluble material and under a pressure of at least about 4.5 kplem2, after which the cracked aromatic tar is evaporated at lower pressure to recover a boat fraction, which for use as a pitch binder. 9. Satt enligt patentanspraket 9, kannetecknat darav, att avdrivningen genomfores vid ett tryck av under c:a 6,6 kp/cm2.9. Set according to patent claim 9, characterized in that the stripping is carried out at a pressure of below about 6.6 kp / cm2. 10. Satt enligt patentanspraket 2, kannetecknat darav, att den som restflode Iran angkrackningen erhallna aromatiska tjaran varmebehan.dlas under tillrackligt rang tid for avlagsnande av hogst c:a 70 viktprocent av den aromatiska tjaran och bildning av en relativt olOslig aterstod med hog mjukningspunkt och Mgt kokstal saint att man darefter med denna kterstod blandar en aromatisk flussmedelsvatska med lag kokpunkt i tillracklig mangd for installning av den salunda bildade, homogena produktens mjukningspunkt till onskad niva, vilken honnogena produkt har en till minst c:a 15 viktprocent uppgaende halt av bensenolosligt material.10. According to patent claim 2, it can be characterized in that the aromatic tar obtained from the residual flood in Iran is treated for a sufficiently long time for removal of no more than 70% by weight of the aromatic tar and formation of a relatively insoluble residue with a high softening point and A large boiling point is then obtained by mixing with this kter residue an aromatic flux liquid water with a low boiling point in sufficient quantity for installation of the softly formed, homogeneous product softening point to the desired level, which homogeneous product has a content of benzenol insoluble material up to at least 15% by weight. . 11. Komposition, framstalld medelst sattet enligt nagot av patentanspraken 1-11. Anforda publikationer:11. A composition according to any one of claims 1-11. Request publications: