DE2166203B2 - Process for the production of pitches suitable for electrode binding agents or impregnating agents. Eliminated from: 2121458 - Google Patents

Description

the oil content unterwonen using as product aroma pitch are not only recovered for use as electrical _m tables oils and pitch that denbinder as an electron adapted solubility in solvents, | t trodenbindemittel not useful are. but it also develops far better binding properties

g · According to GB-Fb 1 178 528 one will sound like what makes it possible with regard to the

|| Cracking a petroleum fraction obtained residual fraction 5 flexural strength, compressive strength, the specific elek- ^ at 350 to 500 C, in particular 400 to 450 ° C, thermal resistance and the thermal expansion ■ g heat treated under pressure, also only sion coefficients noticeably improved electrodes

gg to obtain products with insufficient properties in their

ft ^ Γ ^^ Ι ^as . Electrode binders can be obtained. Furthermore, when using the resulting

S- Finally, according to DT-AS 1 282 655, an io _Pec hs is used as an impregnating agent for electrodes with satisfactory

g | _gene obtained by distillation of coal tar d improved properties with only low Λ pitch with a softening point of 55 to 65 ° C or no repetition of the impregnation and ψ as a starting material for a three-stage heat-firing operations.
Treatment under relatively mild conditions. The reason for achieving the invention

α, in which the starting material is successively 15 of such an excellent pitch, probably Ψ ^! 1, · Τ, ηον · « _ηί ³ . The heat treatment zone can be _{attributed to the} fact that in the heat treatment of the carbon material used as the starting material

s | in countercurrent to the third zone distilling off and / or oil gasers with a considerable amount

Ss oil is sent. This process is relatively expensive to use on low-boiling substances under increased

I dig and despite mild conditions leads to disturbances 20 _{not only} reactive components within the pressure

% by coking. high-boiling substances, but also those in-

; j; The aim of the invention is therefore a method for within the low-boiling substances under

Production of pitch, which react effectively as an electrode generation of pitch, with the reaction ; V binder for generating electrodes with higher simultaneously due to the presence of the low-

I mechanical ^ strength and lower specific 25 boiling substances in the reaction system in liquid ckktnscheni resistance as well as smaller thermal ger form to reduce the production of quinoline

I Coefficient of expansion than before with conventionally insoluble fractions and to prevent over-I Lich pitch can be used as a binder. moderate increase in the molecular weight of the

i Finally, according to the invention, a tea-quinine-insoluble portion is controlled, where-

;? Treatment aimed at, after the pitch in high 30 due to the properties of the resulting pitch

heap of at least 60 percent by weight (based on effectively improved.

on the tar) without coking difficulties In this way, according to the invention

can be. according to the method obtained pitch quinoline insoluble

,. Developed for this purpose borrowed proportions according to the invention with relatively lower molecular weight

The method for producing pitch is thereby 35 weight than the conventionally obtained pitch, characterized that as a bituminous substance coal- Such a result can according to the conventional tar and / or a process produced by cracking petroleum cannot be achieved in which the tar : Provided natural gas tank with a dynamic viscosity initially for the extraction of oil from a distillation

from 20 to 100 cP at 50 ° C and with 5 to 30 Ge and the residue from which as percent by weight of a 0 to 270 ° C boiling 40 the low-boiling substances fraction and 25 to 45 percent by weight of a 0 which is used as starting material,
to 360 ° C boiling fraction is used and further, according to the invention can

{that the heat treatment at a temperature of pitch except as an electrode binder and impregnating agent

.] 320 to 470 ° C under a pressure of 1 to 20 atu tel for burned electrodes for various purposes Additive for coking coal batches,
point of at least 60 ° C and 20 to 45 Ge The pitch obtained according to the invention has over-

weight percent benzene-insoluble components and 3 to Licherweise a softening point of at least 20 percent by weight of quinoline-insoluble components from -60 ° C and can according to its properties is separated. 50 wish over a wide range through variation

In the context of the present heat treatment conditions as well as the in the description and in the claims a conditions for the after the heat treatment Understood the value of the distillation carried out according to the mercury process can be set. In general JIS (Japanese Industrial Standard) K 2421-66, the softening point of the pitch is in is obtained. 55 range from 60 to 150 ° C, although it is possible

According to the invention, pitches with the pitch with a higher softening point of 150 to given properties obtained in high yield. 300 ° C.

Although the increase in benzene-insoluble compounds according to the invention as starting material is increasing

parts to an increase in quinoline-insoluble tars using tars include coal tar and oil gas parts, the increase is much smaller than in the ⁶ ° tar produced by thermal or catalytic cracking of the conventional processes. Even if that has been obtained from petroleum, with the specified benzene-insoluble content above 30 percent by weight, properties.

at least 23 percent by weight of the coal and oil gas are particularly preferred

/ S resin component are retained, which brings the particular advantage with a dynamic viscosity of 50 to 200 cP that the pitch is effective as 65 at 50 ⁰ C and with 15 to 25 percent by weight of a binder used to produce electrodes from 0 to 270 ⁰ C boiling fraction as well as 30 to can be. 40 percent by weight of one boiling from 0 to 360 ° C

In addition, the fraction obtained according to the invention has. According to the invention, coal tar

5 6

and Ölgasteer individually or in a mixture with one another in which the specified percentages are used will. are weight related.

According to the method according to the invention, the B e i s ρ i e 1 1 Starting tar under increased pressure from 1 to 20 atm

heated to 320-470 ° C, whereby heavy fraction 5 Crude coal tar was used for removal of then Nen and relatively low-boiling, unstable condensed water through a falling film distillation Ring compounds sent condensation polymerization tower at a temperature of 84 ° C,

experience and thus be turned into bad luck. The dried tar had a dynamic viscous

During this step, the Reaktionstempera- tat (at 5O ⁰ C) of 102.4 cps and contained 17.1 ° / o door 320 to 470 ⁰ C of importance: a sub-io a boiling at 0-270 ⁰ C fraction and 36.8 ° / o 320 ⁰ C temperature does not yield satisfactory lying one at 0 to 36O ⁰ C boiling fraction. De: tar constricting reaction, while a hinaus- was about 470 ⁰ C then brought rise to coking in the reactor provided in an autoclave passing with a pressure regulator and temperature for 5 hours are tor. Preferably, the reaction can be heated to 400 ° C. at a pressure of 9 atmospheres. The temperature of 380 to 430 ⁰ C carried out 15 generated gaseous constituents were in one of the. Condenser condenses and the liquid back

It is necessary that the reaction takes place while the gas is not condensed from the reaction

increased The ~ \ is carried out, whereby the um- system was taken out. So treated

substances to be added within the tar in flu- tar was used to separate pitch and oil

siger phase can be maintained to ensure 20 isothermal expansion distillation,

development of an effective conversion into bad luck. The yields of pitch, oil and gas thus obtained

A treatment under atmospheric or atmospheric conditions and the properties of the pitch are given in Table 1

reduced pressure must be avoided, as a reproduced,

such treatment would allow relatively never- ThU I

three-boiling unstable condensed ring compound 25 laoeue

conditions are not implemented, so no condensate yields

tion polymerization for conversion into pitch experienced- Pitch 64.0 ⁰ Zo

ren what the formation of pitch with high quality oil 35.1%

prevented. On the other hand, if the pressure exceeds 20 atmospheres gas 0.9%

no better results will be obtained, 30 _. , _u , _o ,

while the ap properties of pitch associated with increased pressures

parative and work-related difficulties - | ™? \ f ET IA 0 /

that are. Suitable pressures for carrying J ^ ige substances 45.8 · /.

The reaction is therefore especially in the range of Chmo inunloshcher Anted 7.2 · /.

from 5 to 15 atm. The reaction time can be over 35 benzene content 32.0 · /.

a wide range, depending on the reaction ~. · 1 ο

conditions and characteristics of the example to be achieved

Pechs, \ ariieren, usually the reaction Dried coal tar as in Example 1 was in

but finished in about 1 to 20 hours. heat-treated in the same way in example 1,

The heat treatment leads to the production 40 only that which is used in the heat treatment

of qi.s, oil and pitch. The gas is changed from the conditions as given in Table 2

System removed for use as a fuel source that has been changed. Table 2 also shows the properties

and the resulting mixture of oil and pitch is listed th of the obtained pitch,

distilled for separation. The pitch obtained in this way has ", b 11 2

a softening point of at least 6O ⁰ C and 45 laoene

contains 20 to 45 percent by weight benzene-insoluble conditions

Parts and 3 to 20 percent by weight quinoline insoluble temperature 360 ° C

borrowed shares. Pressure 5 atm

The pitch obtained according to the invention can last 18 hours.

used effectively as a binder for electrodes 50. ,

will. Electrode examination revealed yields

den that the using the after the inven- v? 44.'6 ⁰ / °

pitch produced according to the method as ρ _n 'o _{0 /} °

Binder produced electrodes higher mechanical '

Strengths such as flexural and compressive strength as well as properties of the pitch

a lower specific electrical resistance, softening point 76.0 ° C

and a smaller coefficient of thermal expansion volatile substances 48.2%

as electrodes, which with conventional quinoline-insoluble content 8.4%

unfortunate bad luck. Benzene-insoluble portion 35.2%

The 60th obtained in the method according to the invention

oil has excellent thermal resistance Example 3 and is used as a good absorbent since

unstable components due to the heat treatment. Dried coal tar as in Example 1 was shown in

turned into bad luck. heat-treated in the same way as in Example 1, only

The process of the invention can be batch 65 that the evidence applied in the heat treatment and, as a continuous process, the conditions given in Table 3 were changed leads to be. became. Table 3 also shows the properties of the

The following are examples of the pitch obtained to illustrate the invention.

Tabel ?

conditions

Temperature 460 ° C

Pressure 20 atm

Duration 2 hours

Exploit

Bad luck 71.2 «/ ο

oil 26, Ο ° / ο

Gas 2.8%

Properties of bad luck

Softening point 85.3 ° C

Volatile substances 44,3 ° / o

Quinoline-insoluble fraction 10.5%

Benzene-insoluble content 36.1%

Example 4

Crude oil gas was dried in the same manner as in Example 1 to obtain dried Tar with a viscosity at 50 ° C of 28.7 cP and with a content of 20.3 ° / o from 0 to 270 ° C boiling fraction and 35.0% of a fraction boiling at 0 to 360 ° C. The dried tar was then subjected to a heat treatment in the same way as in Example 1, only that the Heat treatment applied conditions as shown in Table 4 were changed. In table 4 also shows the properties of the pitch obtained.

Table 4

conditions

Temperature 385 ° C

Pressure 9 atm

Duration 5 hours

Exploit

Bad luck 59.3 per cent

oil 39.6 per cent

Gas 0.7%

166 2Ü3

Properties of bad luck

Softening point 79.8 ° C

Volatile substances 47.2%

Quinoline-insoluble content 8.4%

Benzene-insoluble content 34.2%>

For comparison purposes, tar was treated in the following way:

Comparative example I.

Coal tar as in Example 1 was distilled at 310 ° C under atmospheric pressure and the residue further distilled further at 345 ⁰ C under reduced pressure of 0.15 kg / cm ^2. In this way, pitch and oil were obtained in a yield of 54.9% and 45.1% (based on the weight of the starting coal tar). The properties thereof are shown in Table 5 below.

Table 5

bad luck

Softening point 67.7 ° C

Volatile substances 50.7%

Quinoline-insoluble fraction 4.1%

Benzene-insoluble content 18.2%

oil

Specific gravity 1.08

Temperature for 20% distillation 240.5 ° C Temperature for 50% distillation 325 ° C. Temperature for 80% distillation 360 ° C

Comparative example II

The pecli obtained in Comparative Example I was further kept under atmospheric pressure for 5 hours heated to 400 ° C. The properties of the pitch obtained are shown in Table f below reproduced.

Table 6

Softening point 82 ° C

Quinoline-insoluble fraction 17.1%

Benzene-insoluble fraction 37.0%

Claims (1)

1 Ω 2 ^ * the difference between the two is of particular importance Claim for the desired properties of the pitch. For example, if electrodes with improved Process for the production of pitches 5 of the electrical resistance suitable for electrode properties in terms of strength, density and binding or impregnating agent using to be produced by heating a bituminous substance under pitch as a binding agent, it is increased pressure to an elevated temperature It is necessary that the pitch contains at least a 30-weight percent benzene-insoluble part, a mineral substance, a coal tar and / or a cracking of petroleum produced oil gas with io and that for the difference between Benzene-insoluble a dynamic viscosity of 20 to 1000 cP and a quinoline-insoluble content responsible at 50 ° C and with 5 to 30 percent by weight of a component (so-called / S-resin) at least from 0 to 270 ° C boiling fraction and 25 to 20 percent by weight,
to 45% by weight, one from 0 to 360 ° C. Nevertheless, it was conventional boiling fraction is used and that the 15 process difficult to meet such demands - heat treatment at a temperature of 320 low pitch, as an attempt to increase 470 ° C under a pressure of 1 to 20 atü hung the benzene-insoluble fraction to more than with the production of gas, oil and pitch through 30 percent by weight with a corresponding increase and a pitch is associated with a hung of the quinoline-insoluble fraction by distillation. Softening point of at least 60 ° C and 20 20 It has therefore been suggested the properties of up to 45 percent by weight of benzene-insoluble proportions of pitch by further heating the pitch with or and 3 to 20% by weight of quinoline insolubles without air bubbling or heating Shares is separated. bad luck with certain additions to verbes sern, creating pitch with a softening point of 25 at least 60 ° C and 20 to 40 percent by weight ben- zol-insoluble fractions as well as 5 to 20 weight cent quinoline-insoluble fractions can be obtained. The invention relates to a method for Although now the pitch obtained in this way on the Production of pitches suitable for electrode binding or -impreg- 30 solubility in solvents by heating a usable type of pitch is sufficient, it still leads to bituminous substance under increased pressure on an electrode that is not completely satisfactory. This means,
high temperature. the solubility in solvents is important, In the tar processing plants, however, the tar is not the only decisive factor in determining whether or not Usually a distillation under atmospheric conditions - a pitch that is useful for an electrode binder. or subjected to reduced pressure to obtain properties or not, and the quality lighter, medium and heavier fractions for industrial pitch, which as such a binding agent to the Einstrial Purposes as well as a residue, which is supposed to come as bad luck, must finally be on hand is won. This pitch is determined from a check of the electrodes themselves contained in the tar high-boiling substances. That resul- 40 and be established. Animal pitch is used as a binder for the production of In addition, this was established by conventional Pitch with 15 to 20 weight per electrodes obtained from electrodes as impregnating agents for fired processes and used as an additive to coke carbon percentages that are insoluble in benzene and 5 to 8 batches by weight to produce coke. The percentage of quinoline-insoluble parts as impregnation The pitch produced by the aforementioned process is medium for burned electrodes for improvement but used in terms of required properties of their physical properties. Included not necessarily satisfactory. the burned electrodes with the pitch The properties of pitch are generally impregnated and further fired. However, the pitch obtained, according to the process, which is characterized by its solubility in solvents, can be used, and in fact usually the benign 50 satisfactory improvements can only be achieved if the tariff-soluble and the benzene-insoluble portion are indicated if the impregnation with pitch and the subsequent which the latter in turn are repeated several times in a quinoline-soluble burning sensation,
and dividing a quinoline-insoluble fraction. Recently, the generation of electrical Required by the above-mentioned distillation processes, the better mechanical strengths are obtained. Tenes pitch generally has a softening point above 60 ° C. and a lower specific electrical resistive softening point and contains 7 to 20% and a smaller percentage of thermal expansion percentages insoluble in benzene and 3 to Electrodes have voltage coefficients that are less than 8 percent by weight of quinoline-insoluble fractions. Using conventional pitch as a binder to increase the benzene-insoluble content results in tel or impregnating agents being obtained
a pitch with such properties inevitable 60 According to the known methods of treatment to a greater quinoline-insoluble fraction. If, on the other hand, no attempts are made to obtain the quinoline-insoluble part of products from cracking residues or pitches, which would reduce the amount of products used in the manufacture of electrodes, then the benzene-insoluble part would also have fully satisfactory properties.
borrowed proportion with a simultaneous increase in the benzene So, according to US-PS 3,318,801 oil cracking back- soluble fraction. 65 stands with a softening point of 16 to 121 ° C In many cases, however, when the viscosity is relatively high, the specific amount is a relatively short one the shares, d. H. Both the benzene-insoluble heat treatment at about 340 to 425 ° C with back part as well as the quinoline-insoluble fraction as well as the management of the