NO802509L - BEKSAMMENSETNING. - Google Patents
BEKSAMMENSETNING.Info
- Publication number
- NO802509L NO802509L NO802509A NO802509A NO802509L NO 802509 L NO802509 L NO 802509L NO 802509 A NO802509 A NO 802509A NO 802509 A NO802509 A NO 802509A NO 802509 L NO802509 L NO 802509L
- Authority
- NO
- Norway
- Prior art keywords
- pitch
- composition
- organic compounds
- halogenated organic
- additive
- Prior art date
Links
- 239000000203 mixture Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims description 4
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 4
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims 7
- 239000011295 pitch Substances 0.000 description 58
- 239000000654 additive Substances 0.000 description 26
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- 230000000996 additive effect Effects 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000004939 coking Methods 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Civil Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Gyroscopes (AREA)
- Ceramic Products (AREA)
Description
Foreliggende oppfinnelse angår beksammensetninger The present invention relates to pitch compositions
som gir oksydasjonsresistente karbonlegemer.which gives oxidation-resistant carbon bodies.
En rekke patenter som innbefatter bruk av kull-tjære eller petroleumsbek krever at beksammensetningen A number of patents involving the use of coal-tar or petroleum pitch require that the pitch composition
skal kunne karboniseres. Eksempler på karboniseringspro-sesser innbefatter forkoksning og grafitisering. Under karboniseringsprossen er normalt at man taper mellom 25 og 65% av bindemidlet, og det eksakte tap vil være avhengig av beksammensetningens innhold av flyktige forbindelser. Tapet av flyktige forbindelser til atmosfæren vil dessuten være uonskelig ettersom de utgjor en luftforurensnings-kilde. Det er vanlig praksis i industrien å angi ovennevnte vekttap ved den del eller fraksjon av utgangsmateri-alet som blir igjen etter karboniseringen, og denne fraksjon eller del av beksammensetningen blir ofte kalt "for-■ kosningsverdien". Denne egenskapen er spesielt viktig hvis beksammensetningen skal brukes som et bindemiddel for et koksfyllstoff for fremstilling av forkoksede karbonlegemer. must be carbonizable. Examples of carbonization processes include coking and graphitization. During the carbonisation process, it is normal to lose between 25 and 65% of the binder, and the exact loss will depend on the pitch composition's content of volatile compounds. The loss of volatile compounds to the atmosphere will also be undesirable as they constitute a source of air pollution. It is common practice in the industry to indicate the above-mentioned weight loss by the part or fraction of the starting material that remains after carbonization, and this fraction or part of the pitch composition is often called the "pre-■ cooking value". This property is particularly important if the pitch composition is to be used as a binder for a coke filler for the production of coked carbon bodies.
Et problem i forbindelse med brente karbonlegemer som fremstilles fra beksammensetninger, er deres relativt hoye oksydasjonshastighet, og dette er spesielt fremtredende når disse legemer brukes som ildfaste materialer eller som elektroder. Denne oksydasjons hastigheten skyl-des faktorer såsom karbonlegemets porositet, dets spesifik-ke overflate samt de uorganiske urenheter som er tilstede i karbonlegemet. A problem in connection with burnt carbon bodies produced from pitch compositions is their relatively high rate of oxidation, and this is particularly prominent when these bodies are used as refractories or as electrodes. This rate of oxidation is due to factors such as the porosity of the carbon body, its specific surface and the inorganic impurities present in the carbon body.
Den teknikk som hittil har vært anvendt for å nedsette denne oksydasjonshastigheten innbefatter trykkim-pregnering eller belegging av tidligere brente karbonlege- . mer med vandige oppløsninger av oksydasjonsresistente materialer såsom fosfater, silikater etc., hvoretter karbonlegemet igjen brennes for å avdrive fuktigheten. Selv om den tidligere kjente teknikk krevet trykkbehandlingsutstyr og store volumer av et ofte kostbart impregneringsmiddel, så maktet man ikke å hemme oksydasjon i den indre del av karbonlegemet. The technique that has so far been used to reduce this oxidation rate includes pressure impregnation or coating of previously burned carbon alloys. more with aqueous solutions of oxidation-resistant materials such as phosphates, silicates, etc., after which the carbon body is again burned to drive off the moisture. Although the previously known technique required pressure treatment equipment and large volumes of an often expensive impregnating agent, it was not possible to inhibit oxidation in the inner part of the carbon body.
Det er også kjent (britisk patent 865.320) at man kan tilsette oksydasjonshemmende forbindelser til blandingen av koksfyllstoff og beksammensetning for brenningen. Denne teknikk har den ulempe at den krever relativt store mengder (fra 4-20 vektdeler av additivet til 100 vektdeler av den karbonholdige blandingen) av additivet, og sistnevnte er relativt kostbart i forhold til basismaterialet. Så store mengder additiv kan også.ha skadelige effekter hvis det karbonlegeme man får etter brenningen skal brukes som en elektrode. Dessuten kan additivet som normalt er ubrennbart, og som utgjor en vesentlig del av elektroden, forurense produktet etter-hvert som elektroden blir forbrukt og man skulle få et eventuelt residuum. It is also known (British patent 865,320) that oxidation-inhibiting compounds can be added to the mixture of coke filler and pitch composition for burning. This technique has the disadvantage that it requires relatively large amounts (from 4-20 parts by weight of the additive to 100 parts by weight of the carbonaceous mixture) of the additive, and the latter is relatively expensive compared to the base material. Such large amounts of additive can also have harmful effects if the carbon body obtained after burning is to be used as an electrode. In addition, the additive, which is normally non-combustible, and which forms a significant part of the electrode, can contaminate the product as the electrode is used up and a possible residue should be obtained.
Det er folgelig en hensikt ved foreliggende oppfinnelse å tilveiebringe en beksammensetning som ved en karbonisering gir et karbonlegeme med forbedret oksydasjonsmotstand. It is therefore an aim of the present invention to provide a pitch composition which upon carbonisation produces a carbon body with improved oxidation resistance.
Foreliggende oppfinnelse angår en beksammensetning som består av: The present invention relates to a pitch composition which consists of:
(A) et bekmateriale og(A) a pitch material and
(B) en effektiv mengde av en aktiv komponent som (B) an effective amount of an active component which
innbefatter minst én gruppe av halogener te includes at least one group of halogens
organiske forbindelser som dekomponerer ved temperaturer mellom mykningspunktet og kar-boniseringstemperåturen for bekmaterialet, organic compounds that decompose at temperatures between the softening point and the carbonization temperature of the pitch material,
og hvor nevnte komponent utgjor minst 2% av nevnte sammensetning. I et annet aspekt angår oppfinnelsen en fremgangsmåte for fremstilling av nevnte beksammensetning. and where said component constitutes at least 2% of said composition. In another aspect, the invention relates to a method for producing said pitch composition.
Ifolgeforeliggende oppfinnelse får man fremstilt en beksammensetning med modifiserte egenskaper ved at beken tilsettes en forbindelse (eller forbindelser) valgt den gruppe av forbindelser som er angitt ovenfor. Tilsetningen til beken utfores ved temperaturen ved hvilken nevnte bek har en redusert viskositet slik at den lett kan rbres. Den temperatur ved hvilken nevnte komponent vil tilsettes beken vil fortrinnsvis være mellom myknings punkt et for bekmaterialet, og den temperatur ved hvilken de lavtkokende kompo-nentene i beken går tapt, for derved at man i det minste delvis kan hindre deres tap. Sistnevnte temperatur vil være mellom 250 og 300°C. Forbindelsen inkorporeres i beken ved at man kun rbrer additivet inn i beken. Forbindelsen bor tilsettes i en slik tilstand at den lett lar seg fordele bekmaterialet, og skulle additivet være fast ved. tilsetningstemperaturen, så bor det være i en finfordelt form (ca. 100 mesh), og skulle det være en gass så kan denne tilsettes ved hjelp av én eller flere dyser inne i den smeltede bekmassen. Vanligvis vil additivet utgjore mindre enn ca. 2 vekt-% av blandingen, mer typisk vil det utgjore, mindre enn ca. 1 vékt-%. According to the present invention, a pitch composition with modified properties can be produced by adding a compound (or compounds) selected from the group of compounds indicated above to the pitch. The addition to the pitch is carried out at the temperature at which said pitch has a reduced viscosity so that it can be easily removed. The temperature at which said component will be added to the pitch will preferably be between softening point one for the pitch material, and the temperature at which the low-boiling components in the pitch are lost, so that their loss can be at least partially prevented. The latter temperature will be between 250 and 300°C. The compound is incorporated into the stream by simply stirring the additive into the stream. The compound should be added in such a state that it can easily distribute the pitch material, and should the additive be solid. the addition temperature, then it should be in a finely divided form (approx. 100 mesh), and should there be a gas, this can be added using one or more nozzles inside the molten bitumen. Usually, the additive will make up less than approx. 2% by weight of the mixture, more typically it will amount to less than approx. 1% by weight.
De forbindelser som-er nevnt tidligere brukes ofte som flammeresistente midler som viser en hemming av. ettergloding, og kan generelt beskrives som forbindelser som dekomponerer ved temperaturer mellom mykningspunktet og karboniseringstemperaturen for bekmassen. En slik be-grensning vil sikre at komponenten kan fordeles i sin "aktive" form i hele bekmassen, og at denne "aktive" form eksisterer for bekmaterialet blir karbonisert. Ved karbonisering forstås her at karbondannelsen er i en slik tilstand at fordelingen og "aktiviteten" på forbindelsene blir hemmet ved dannelsen av en koksfase. Dannelsen av en slik koksfase vil i alt vesentlig være fullstendig ved ca. 500°C, og folgelig.bor tilsetningen av forbindelsen til bekmassen og dens fordeling i dens "aktive" form i bekmassen bor således skje ved en temperatur under denne karboniseringstem-peratur. The compounds mentioned earlier are often used as flame retardants which show an inhibition of post-annealing, and can generally be described as compounds that decompose at temperatures between the softening point and the carbonisation temperature of the pitch. Such a limitation will ensure that the component can be distributed in its "active" form throughout the pitch mass, and that this "active" form exists before the pitch material is carbonized. By carbonisation, it is understood here that the formation of carbon is in such a state that the distribution and "activity" of the compounds is inhibited by the formation of a coke phase. The formation of such a coke phase will essentially be complete at approx. 500°C, and consequently the addition of the compound to the pitch mass and its distribution in its "active" form in the pitch mass must therefore take place at a temperature below this carbonisation temperature.
Forbindelsene vil typisk ha kokepunkter over ca. 40°C. Eksempler, på slike forbindelser er klorinerte gummi-typer (såsom "Parlon" (TM)), 1-klornaftalen, heksaklorbenzen, pentakloretan og 1,2-dikloretan etc. Man kan imidler-tid bruke lignende forbindelser på en analog måte, eller at .de kan dannes in situ,(f.eks. ved å tilfore klorgass til den smeltede bekmassen). Den resulterende beksammensetning en vil normalt inneholde mindre enn 0,4 vekt-% klor. Bruken av store overskudd av den aktive forbindelsen vil imid-lertid eliminere de fordeler man oppnår ved å bruke foreliggende oppfinnelse. Folgelig må mengden av komponent i bekmassen bestemmes relativt nbyaktig for en gitt komponent-bekkombinasjon. Sammensetninger som kan brukes i foreliggende oppfinnelse er kommersielt i anvendelse som flammeresistente midler, f.eks. av den type som selges under varemerket "Phosgard" og har folgende generelle formel: The compounds will typically have boiling points above approx. 40°C. Examples of such compounds are chlorinated rubber types (such as "Parlon" (TM)), 1-chloronaphthalene, hexachlorobenzene, pentachloroethane and 1,2-dichloroethane etc. One can, however, use similar compounds in an analogous way, or that .they can be formed in situ, (e.g. by adding chlorine gas to the molten pitch mass). The resulting pitch composition will normally contain less than 0.4% by weight chlorine. The use of large excesses of the active compound will, however, eliminate the advantages obtained by using the present invention. Consequently, the amount of component in the pitch mass must be determined relatively closely for a given component-pitch combination. Compositions which can be used in the present invention are commercially in use as flame retardants, e.g. of the type sold under the trademark "Phosgard" and has the following general formula:
Beksammensetningen fremstilles ved å oppvarme beken til en temperatur over dens mykningspunkt for derved å' gjore den rorbar. Hvis additivet er et fast stoff, må det finmales for tilsetning til beken for derved lettere å kunne fordele det i hele bekmassen. Additivet blir så rort inn i bekmassen og rbringen vil normalt fortsette i et par timer inntil man antar at additivet er jevnt fordelt i hele massen. I de tilfeller når additivet er gassformet og forbindelsen dannes in situ, så kan dette gjores ved at man f.eks. tilsetter klorgass til den smeltede bekmassen ved hjelp av én eller flere egnede dyser samtidig som massen rores, hvorved man muliggjor en reaksjon mellom gassen og bekkomponentene, hvorved den foronskede forbindelse dannes in situ. The pitch composition is produced by heating the pitch to a temperature above its softening point in order to thereby make it stirrable. If the additive is a solid substance, it must be finely ground for addition to the pitch in order to be able to distribute it more easily throughout the pitch mass. The additive is then stirred into the pitch mass and the stirring will normally continue for a couple of hours until it is assumed that the additive is evenly distributed throughout the mass. In cases where the additive is gaseous and the compound is formed in situ, this can be done by e.g. adds chlorine gas to the molten pitch mass using one or more suitable nozzles at the same time as the mass is stirred, whereby a reaction between the gas and the pitch components is made possible, whereby the forked compound is formed in situ.
Beksammensetningen fremstilt ifolge foreliggende oppfinnelse vil inneholde en effektiv mengde av den aktive komponenten som vil utgjore mindre enn 2 vekt-% av sammensetningen. Minimums effektiv mengde vil normalt ikke være mindre enn 0,1%. Denne sammensetningen når forkokses (eller på'annen måte karboniseres), vil gi et karbonlegeme med bed-ret oksydasjonsmotstand. I praksis vil tilsetningsmengden bli bestemt ved suksessive forsok, og vil i de fleste til feller være mindre enn ca. 0,8 vekt-% av bekmassen. Det skal bemerkes at de forskjellige forbindelser som faller innenfor de ovennevnte definisjoner ikke nødvendigvis trenger å utelukke hverandre i bruk, men at man kan bruke forskjellige kombinasjoner av forbindelser hvis dette er fordelaktig. The pitch composition produced according to the present invention will contain an effective amount of the active component which will constitute less than 2% by weight of the composition. The minimum effective amount will normally not be less than 0.1%. This composition, when coked (or otherwise carbonized), will give a carbon body with improved oxidation resistance. In practice, the amount of addition will be determined by successive trials, and will in most cases be less than approx. 0.8% by weight of the bitumen. It should be noted that the various compounds falling within the above definitions need not necessarily be mutually exclusive in use, but that different combinations of compounds may be used if this is advantageous.
Det er også vanligvis andre fordeler man oppnår ved å fremstille relativt oksydasjonsresistente karbonlegemer fra beksammensetningen ifblge foreliggende oppfinnelse. En av de mest onskelige og ofte fremtredende egenskaper ved beksammensetninger ifolge foreliggende oppfinnelse, er at man får et oket utbytte av karbonholdig mater-iale fra en gitt mengde av bek ved at.man tilsetter ovennevnte additiv. Når en slik beksammensetning forkokses, vil man vanligvis oppnå en okende forkoksningsverid på beksammensetningen. Skjont det er tilsetningsmengdér som tilsvarer et maksimum i karboniseringsverdi for sammensetningen, så skal det bemerkes at disse mengder kan være relativt distinkte og forskjellige fra de respektive- tilsetningsmengdér som gir minimal■oksydasjonshastighet. Den mengde av additiv som derfor vil bli brukt i praksis vil være avhengig av de foronskede egenskaper. There are also usually other advantages achieved by producing relatively oxidation-resistant carbon bodies from the pitch composition according to the present invention. One of the most desirable and often prominent properties of pitch compositions according to the present invention is that an increased yield of carbonaceous material is obtained from a given amount of pitch by adding the above-mentioned additive. When such a pitch composition is coked, an increasing coking rate of the pitch composition will usually be achieved. Although there are addition quantities which correspond to a maximum in carbonation value for the composition, it should be noted that these quantities can be relatively distinct and different from the respective addition quantities which give a minimum rate of oxidation. The amount of additive that will therefore be used in practice will depend on the properties sought.
Avhengig av det additiv man bruker kan man dessuten oppnå, ytterligere fordeler ved hjelp av foreliggende sammensetning. Bruken av f.eks. "Phosgard" (TM) som et additiv, vil således resultere i at man bruker mindre mengder bek for å danne tilfredsstillende uttrekkbare elektroder. Depending on the additive used, further advantages can also be achieved by means of the present composition. The use of e.g. "Phosgard" (TM) as an additive will thus result in using smaller amounts of pitch to form satisfactory extractable electrodes.
Det er ikke helt ut forstått hvorledes tilsetningen av så små mengder av additivet i så hoy grad kan påvirke oksydasjonshastigheten. En teori som er foreslått for å forklare dette fenomen, er at det skjer en reaksjon mellom additivet og de bestanddeler i bekmassen som har en ten-dens til å katalysere oksydasjonen av karbonlegemet. Det er dessuten mulig at additivet endrer strukturen på det resulterende karbonlegemet og således gjor det mer motstands-dyktig mot oksydasjon. It is not fully understood how the addition of such small amounts of the additive can affect the oxidation rate to such a high degree. A theory that has been proposed to explain this phenomenon is that a reaction takes place between the additive and the constituents in the bitumen which have a tendency to catalyze the oxidation of the carbon body. It is also possible that the additive changes the structure of the resulting carbon body and thus makes it more resistant to oxidation.
Eksempel 1Example 1
Dette eksempel illustrerer effekten på bek-blandingen ved å tilsette "Phosgard" .(TM). Nevnte "Phosgard" (TM) og beken ble veiet i et beger og blandingen opp-varmet til ca. 190°C for å lette roring. Blandingen ble rort ved variabel hastighet ved 190.-10°C i ca. li time. This example illustrates the effect on the pitch mixture of adding "Phosgard" .(TM). Said "Phosgard" (TM) and the beaker were weighed into a beaker and the mixture heated to approx. 190°C to facilitate rowing. The mixture was stirred at variable speed at 190-10°C for approx. li hour.
En rekke forskjellige kvaliteter av bek med varierende innhold av kinolinopplbselige stoffer (Q.I.) A number of different qualities of pitch with varying contents of quinoline soluble substances (Q.I.)
og jerninnhold ble behandlet ved hjelp av enne teknikk. Hver tjærekvalitet ble behandlet med varierende mengder and iron content were treated using this technique. Each tar grade was treated with varying amounts
av "Phosgard" (TM) for å undersbke variasjonen i bekens egenskaper som en funksjon av additivtilsetningen. of "Phosgard" (TM) to examine the variation in the properties of the stream as a function of additive addition.
Blandingen av bek og additiv ble forkokset iThe mixture of pitch and additive was coked in
små digler som inneholdt 5 g av blandingen idet man brukte en 24 timers karboniseringssyklus med en oppvarmingshastig-het på 40°C pr. time. Den resulterende koksen ble veiet for å oppnå forkoksningsverdien på den behandlede beken. small crucibles containing 5 g of the mixture using a 24 hour carbonization cycle with a heating rate of 40°C per hour. The resulting coke was weighed to obtain the coking value of the treated stream.
Koksen ble knust og 2 g av en 40/60 fraksjon ble tilsatt et ror. Denne proven ble renset med nitrogen i 30 minutter for å fjerne fuktighet og oksygen. Med nitro-gengjennomstrbmning ble roret plassert i en ovn hvis mid-deltemperatur var 950 - 5°C Da proven hadde fått jevn temperatur, ble nitrogentilfbrselen stoppet, og karbondi-oksyd ble fort gjennom proven i 2 timer. Deretter ble kar-bondioksydstrbmmen stoppet og' nitrogen ble igjen fort gjennom proven i 30 minutter for å rense den for gjenværende gassformede oksydasjonsprodukter. Proven ble så tatt ut av ovnen, avkjblt og igjen veiet. Den midlere karbondiok-sydoksydasjonshastigheten kan således beregnes ut fra de to veiningene. Denne form for oksydasjon er antatt å være den prinsipielle oksydasjonskilden inne i karbonanoden under elektrolytisk fremstilling av aluminium, og som bidrar til tap av elektrodestyrke. Karbondioksydoksydasjonen anses også å være ansvarlig for' det akselererte forbr^két-av-bindemiddel på interfasen mellom karbonet og bindemfd-let ved interfasen mellom anoden og saltet. The coke was crushed and 2 g of a 40/60 fraction was added to a stirrer. This sample was purged with nitrogen for 30 minutes to remove moisture and oxygen. With nitrogen flow, the pipe was placed in an oven whose average temperature was 950 - 5°C. When the sample had reached a uniform temperature, the nitrogen supply was stopped, and carbon dioxide was passed through the sample for 2 hours. The carbon dioxide stream was then stopped and nitrogen was again passed through the sample for 30 minutes to purge it of residual gaseous oxidation products. The sample was then taken out of the oven, cooled and weighed again. The average carbon dioxide oxidation rate can thus be calculated from the two weighings. This form of oxidation is believed to be the principal source of oxidation inside the carbon anode during the electrolytic production of aluminium, and which contributes to the loss of electrode strength. The carbon dioxide oxidation is also considered to be responsible for the accelerated consumption of binder at the interface between the carbon and the binder at the interface between the anode and the salt.
Resultatene av overnevnte forsbk er angitt i tabell I som illustrerer variasjonen med hensyn til forkoksningsverdi og karbondioksydoksydasjons hastigheten i forhold til Q.I. og jerninnholdet, foruten at tabellen viser de forskjellige konsentrasjoner av additiv som tilsvarer optimal forkoksningsverdi og optimal karbondioksyd-reaksjonshastighet for en gitt bekkvalitet. Det fremgår videre av tabell I at det i visse tilfeller (f.eks. bek (b) og (c)) så eksisterer det optimale konsentrasjons-nivåer av "Phosgard" (TM) og at et overskudd av additiv kan ha en skadelig effekt på karbondioksydoksydasjonshastighet-en. På lignende måte får man nedsatt okning i forkoksnings-ver dien med bkende tilsats av addivet.utover optimalnivå-et. The results of the above-mentioned experiments are given in Table I which illustrates the variation with regard to coking value and carbon dioxide oxidation rate in relation to Q.I. and the iron content, besides that the table shows the different concentrations of additive which correspond to the optimum coking value and optimum carbon dioxide reaction rate for a given pitch quality. It is further apparent from table I that in certain cases (e.g. pitch (b) and (c)) there are optimal concentration levels of "Phosgard" (TM) and that an excess of additive can have a harmful effect on the carbon dioxide oxidation rate. In a similar way, a reduced increase in the coking value is obtained with gradual addition of the additive beyond the optimum level.
Eksempel 2 Example 2
Dette eksempel viser forandringer i egenskaper forThis example shows changes in properties for
en elektrodebek som ble behandlet ifolge foreliggende oppfinnelse. Kulltjærebek inneholdende 25% Q.I. (identisk med bek (d) i eksempel l) ble behandlet med 0,4 vekt-% "Phosgard" (TM). an electrode pitch that was treated according to the present invention. Coal tar pitch containing 25% Q.I. (identical to pitch (d) in Example 1) was treated with 0.4% by weight "Phosgard" (TM).
Prover av beken med og uten "Phosgard" (TM) ble blandet med koks i en mengde som tilsvarte ca. 70% av koks-bekblandingen for fremstilling av-en Sbderbergpasta med akseptable strbmningsegenskaper. Den nbdvendige mengde ble bestemt ved en forlengningsprbve, og ble betegnet "bindemiddelkravet". Ved tilsetning av "Phosgard" (TM) kunne man observere at det bindemiddel som var nbdvendig for å få en akseptabel pasta kunne nedsettes med ca. 6,25%. Samples of the brook with and without "Phosgard" (TM) were mixed with coke in an amount corresponding to approx. 70% of the coke-pitch mixture for the production of a Sbderberg paste with acceptable flow characteristics. The required amount was determined by an elongation test, and was termed the "binder requirement". When "Phosgard" (TM) was added, it could be observed that the binder required to obtain an acceptable paste could be reduced by approx. 6.25%.
Sbderbergpastaen ble brent.i 48. timer ved en temperatur på 970°C for fremstilling av prbveelektroder, og forkoksingsverdien på beken i pastaen ble bestemt. Disse prove- elektrodene ble så bedbmt for sin motstand mot luftoksydasjon. En prdveelektrode som var 50 mm lang og hadde en diameter på 4 mm ble opphengt fra en torsjonsvekt i en vertikal rorovn gjennom hvilken man pumpet luft med en temperatur på ca. 525°C og en mengde på 4 liter pr. minutt, noe som tilsvarer en lineær hastighet på 22 cm/sek. Vekten ble avlest hvert 5. minutt inntil elektrodens vekt var avtatt med 30%. Oksydasjonshastigheten kan så ut--2-1 The Sbderberg paste was fired for 48 hours at a temperature of 970°C for the production of test electrodes, and the coking value of the pitch in the paste was determined. These sample electrodes were then tested for their resistance to air oxidation. A pressure electrode which was 50 mm long and had a diameter of 4 mm was suspended from a torsion balance in a vertical tube furnace through which air was pumped with a temperature of approx. 525°C and a quantity of 4 liters per minute, which corresponds to a linear speed of 22 cm/sec. The weight was read every 5 minutes until the weight of the electrode had decreased by 30%. The oxidation rate can look like this--2-1
trykkes i gramcentirneter time og er angitt i tabell II. En tilsetning av "Phosgard" (TM) nedsatte luftoksy- . dasjonshastigheten i vesentlig grad. Andre egenskaper ved elektroden såsom motstand og luftpermeabilitet ble målt og deres verdier er angitt i tabell II nedenfor. is printed in gram-centimeters per hour and is indicated in table II. An addition of "Phosgard" (TM) decreased air oxygen- . dation rate to a significant extent. Other properties of the electrode such as resistance and air permeability were measured and their values are given in Table II below.
Prover identiske med de som er beskrevet ovenfor ble gjennomfort med en 19% Q.I. bek (bek (c) fra eksempel l) som inneholdt 0, 0,6 og 1,2 vekt-% tilsatt "Phosgard" Samples identical to those described above were run with a 19% Q.I. pitch (pitch (c) from example l) which contained 0, 0.6 and 1.2% by weight of added "Phosgard"
(TM). Disse resultatene er også angitt i tabell II. Det fremgår at den motstand, luftpermeabilitet og luftoksyda-sjonshastighet man oppnådde viser tilsvarende kvalitative variasjoner og hvor man i hvert tilfelle får en forbedring ved en tilsetning av "Phosgard" (TM) til en optimalverdi, hvoretter denne forbedring avtar ved ytterligere tilsetning av "Phosgard." (TM) (F.eks. mellom (c) .2 og (c) .3, noe som fremgår av verdiene for motstand, luftpermeabilitet og luftoksydasjon). Det fremgår bl.a. at verdiene for luftpermeabiliten og luftoksydasjonshastigheten er hbyere ved 1,2% "Phosgard" (TM) enn i dens fravær. (TM). These results are also given in Table II. It appears that the resistance, air permeability and air oxidation rate achieved show corresponding qualitative variations and where in each case an improvement is obtained by adding "Phosgard" (TM) to an optimum value, after which this improvement decreases with further addition of "Phosgard" ." (TM) (E.g. between (c) .2 and (c) .3, which is evident from the values for resistance, air permeability and air oxidation). It appears i.a. that the values for the air permeability and the air oxidation rate are higher with 1.2% "Phosgard" (TM) than in its absence.
Eksempel 5 Example 5
Effekten av "Phosgard" (TM) tilsetning til petroleumsbek ble provet i en serie eksperimenter hvor forskjellige mengder."Phosgard" (TM) ble tilsatt beken på samme måte som beskrevet i eksempel 1. Bekadditivbland-ingen ble så forkokset på samme måte som beskrevet i eksempel 1, hvorved man fikk forkoksningsverdiene av de behandlede blandinger. Resultatene er angitt i tabell IV nedenfor og viser en okende forkoksningsverdi som tilsvarer- et bkende innhold av "Phosgard" (TM). The effect of "Phosgard" (TM) addition to petroleum pitch was tested in a series of experiments where different amounts of "Phosgard" (TM) were added to the pitch in the same way as described in example 1. The pitch additive mixture was then coked in the same way as described in example 1, whereby the coking values of the treated mixtures were obtained. The results are set out in Table IV below and show an increasing coking value corresponding to an increasing content of "Phosgard" (TM).
Eksempel 4 Example 4
En 19% Q.I. kulltjærebek (bek (c) fra eksempel l) ble blandet med en klorinert gummi som selges under varemerket "Parlon S-30" og forkokset som beskrevet i eksempel 1. Forkoksingsverdien, tettheten og karbondioksyd-reaksjonshastigheten ble målt. Dette forsbket ble gjen-tatt ved å bruke heksaklorbenzen, pentakloretan, 1-klornaftalen og 1,2-dikloretan som additiver til beken..Resultatene er angitt i tabell V og angir hvorledes forkoksningsverdien og karbondioksydreksjonshastigheten er på-virket av additivet. A 19% Q.I. coal tar pitch (pitch (c) from Example 1) was mixed with a chlorinated rubber sold under the trademark "Parlon S-30" and coked as described in Example 1. The coking value, density and carbon dioxide reaction rate were measured. This experiment was repeated using hexachlorobenzene, pentachloroethane, 1-chloronaphthalene and 1,2-dichloroethane as additives to the pitch. The results are given in Table V and indicate how the coking value and the carbon dioxide reaction rate are affected by the additive.
Det tor være innlysende at man lett kan utfore modifikasjoner i sammensetninger og fremgangsmåter slik disse er beskrevet her uten at man derved forlater, opp-finnelsens intensjon. It should be obvious that one can easily carry out modifications in compositions and methods as described here without thereby abandoning the intention of the invention.
Claims (8)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA349,882A CA1124010A (en) | 1980-04-15 | 1980-04-15 | Pitch composition |
Publications (1)
Publication Number | Publication Date |
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NO802509L true NO802509L (en) | 1981-10-16 |
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ID=4116710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO802509A NO802509L (en) | 1980-04-15 | 1980-08-22 | BEKSAMMENSETNING. |
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JP (1) | JPS56147887A (en) |
AU (1) | AU6116080A (en) |
CA (1) | CA1124010A (en) |
DE (1) | DE3030479A1 (en) |
FR (1) | FR2480295A1 (en) |
GB (1) | GB2074147B (en) |
NO (1) | NO802509L (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5133781A (en) * | 1990-12-21 | 1992-07-28 | Texaco Inc. | Compatibilization of asphaltenes in bituminous liquids using bulk phosphoalkoxylation |
US5703148A (en) * | 1993-09-09 | 1997-12-30 | Total Raffinage Distribution S.A. | Asphalt-polymer compositions, process for making same and uses thereof |
FR2714672B1 (en) * | 1993-12-30 | 1996-03-22 | Total Raffinage Distribution | Improved bitumen compositions, their preparation process and their applications. |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US2247375A (en) * | 1937-12-16 | 1941-07-01 | Atlantic Refining Co | Treatment of bituminous materials |
GB865320A (en) * | 1957-09-10 | 1961-04-12 | Union Carbide Corp | Improvements in and relating to oxidation resistant articles |
-
1980
- 1980-04-15 CA CA349,882A patent/CA1124010A/en not_active Expired
- 1980-08-07 AU AU61160/80A patent/AU6116080A/en not_active Abandoned
- 1980-08-12 DE DE19803030479 patent/DE3030479A1/en not_active Withdrawn
- 1980-08-22 NO NO802509A patent/NO802509L/en unknown
- 1980-09-17 GB GB8030026A patent/GB2074147B/en not_active Expired
- 1980-12-08 FR FR8025986A patent/FR2480295A1/en active Pending
- 1980-12-23 JP JP18270280A patent/JPS56147887A/en active Pending
Also Published As
Publication number | Publication date |
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GB2074147A (en) | 1981-10-28 |
AU6116080A (en) | 1981-10-22 |
JPS56147887A (en) | 1981-11-17 |
DE3030479A1 (en) | 1981-10-22 |
CA1124010A (en) | 1982-05-25 |
GB2074147B (en) | 1984-03-14 |
FR2480295A1 (en) | 1981-10-16 |
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