DE1955285B2 - - Google Patents

Description

130O ⁰ C, the temperature difference to the reaction temperature is so small that too much energy is unnecessarily consumed and the end result is uneconomical. The aromatic content of the hydrocarbons is preferably over 90%; the H / C atomic ratio should be below 1.2, preferably below 1.1. If these conditions are not met, the gasification rate during thermal cracking is so high that the product yield becomes low. The reaction temperature is preferably between 1000 and 1300 ^° C. If it is below 900 ^° C., the degree of conversion is low. If it is over 1500 ^° C, the quality control of tar and pitch becomes difficult and the products are not good.

Table 3
Pitch properties

Softening point 95.3 ° C

H / C atomic ratio 0.56

Benzene-insoluble 38 percent by weight

Quinoline insolubles 10 percent by weight

volatile material 42 weight percent

solid carbon 58 percent by weight

ίο Ash content less than 0.1 percent by weight

Samples of graphite electrodes were made using pitch according to the invention and from Previously common hard coal pitch with medium

The reaction pressure is preferably established between 15 melting point. The preparation of the samples atmospheric pressure and 10 atm. At a pressure of and the properties of the products were as below 300 mm Hg absolute, the reaction speed is carried out or determined as follows:
age too low. If the pressure is above 20 atmospheres, 100 TeUe normal coke (water content 0.13%, volatile

Not only do energy costs increase, but also term components 0.52%, ash content 0.32%, coal there is also a deposit of coke in the reactor 20 material 99.03%, specific weight 2.04) were with added by the condensation of the pitch formed or 30 parts of pitch according to the invention and the

Mixture kneaded at a temperature of 20 to 25 ° C above the softening point of the pitch for about 30 minutes. The kneaded mixture became a strand with a melt under a pressure of 150 to 300 kg / cm ² at a temperature of 30 to 35 C above the softening point of the Peshs

Tar, which of course is unfavorable. The reaction time is preferably between 0.003 and 0.05 seconds. If it is less than 0.001 seconds, the conversion is only slight. Is the time longer than 0.1 seconds, pitch or tar lose their good properties.

The following examples serve to further illustrate the invention.

example 1

1.5 Nm ³ / hour Propane were with 35 Nm ³ / h. Air burned in a combustion chamber with an inner diameter of 20 mm and a length of 200 mm, which is lined with a refractory material. A washing oil exhibiting the properties shown in Table 1 was washed at a rate of 20 kg / hour. introduced into the generated high-temperature ^{gas stream of about 1750 J} C and brought there 0.008 seconds under a pressure of 3 atü at a reaction temperature of about 115O ⁰ C to the reaction. The products obtained are shown in Table 2.

Pressed with a diameter of 7.5 cm. After heating the melt 25 days at a temperature of up to 900 ⁰ C was graphitized 5 days by heating to a temperature of up to 2800 ° C. The properties of the medium softening point hard coal pitch used as a control sample are as follows:

Softening point 72 ⁰ C,
H / C 0.48,

Benzene-insoluble 27%,
Quinoline insolubles 8 %,
volatile matter 62%,
solid carbon 38%,
Ash content 0.1%.

Among the products obtained showed the severity
Fraction (pitch) a boiling point above 400 ⁰ C below 45 The properties of the products were as follows:
Atmospheric pressure and had the values shown in Table 3
specified properties.

Table 1
Properties of the raw material

Initial boiling point 220 ^° C

Final boiling point 320 ° C

Naphthalene content 20.5 percent by weight

Aromatic hydrocarbons above 98% H / C atomic ratio 0.96

50 product
according to
invention Hard coals
bad luck specific weight
Bond strength, kg / cm ^a ...
Compressive strength, kg / cm ^a ..
55 Specific resistance
10 ¹ O-cm 1.71
255
450
I 7.4 1.61
195
350
9.5

Table 2

Product yields

Weight percent

Gas (CO, H ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ ) 3.3

Forecut (initial boiling point of 218 ⁰ C) 4.7

Naphthalene 30.3

Intermediate fraction (218 to 400 ° C) 22.8

Pitch (over 400 ° C) 38.6

Loss 0.3

The properties of the product obtained by the process according to the invention are consistently better.

Example 2

In the same apparatus as in Example 1, a fraction that was obtained in the thermal cracking of a light petroleum hydrocarbons to unsaturated hydrocarbons such as ethylene, propylene or butadiene, had been obtained and had the properties mentioned in the table, with a Gescnwin-

capacity of 30 kg / hour In a high-temperature gas such a pitch was used as a pitch binder for a coal stream of 1750 ° C, which was produced by burning the same material electrodes. The graphite electrode was introduced in the amount of propane and air generated as in Example 1 as in Example 1 using this pitch, and placed at a temperature of. The properties of the product were about 1080 ⁰ C, reaction time 0.3 seconds, among 5 the following:
brought to a pressure of 5 atü to react. the

Products are listed in Table 5 Specific gravity 1.69

The heavy fraction (tar) thus formed boiled bond strength, kg / cm ² 240

under atmospheric pressure over 25O ⁰ C and had the compressive strength kg / cm ^A 430

properties given in Table 6; the contract- io specific resistance 10 ~ ^a Ω · cm 7.7
possibility with an epoxy resin in which the material

used as an admixture was very high. B e i s η i e 1 3

The content of acidic components, sulfur and

Ash was very little. Upon mixing of the material I _{n ame} mixing chamber having an inner diameter

with a resin and a curing agent, it was found to be 15 _by 30 mm and a length of 500 mm, which was possible with such a high stability that a long storage time was _{lined with a} refractory material. The resin products obtained showed _{the tar} J _1n Example 2 used a type having an excellent resistance to water speed of 27 kg / hr. in a scientist, oils and chemicals. steam flow of 60 kg / hour and about 1700 ⁰ C

This tar was used in a Urethanteer, _{ao] eitet The} steam flow was generated using a so-he proved not only urethanes from two regenerative heating system. The tar was allowed to be component-type, but also urethanes of the one-component type in the gas stream for 0.002 seconds at a temperature. _{react from about} 1220 ^° C. at atmospheric pressure;

^{the product Table 4 * 5} described in Table 7 could be obtained. The heavy fraction with one

Boiling point above 48O ⁰ C under atmospheric pressure Raw material properties (ethylene cracker bottom oil) had _the properties listed in Table 8,

The initial boiling point 23O ⁰ C showed a high coking value and high graphical

Final boiling point 350 ⁰ C and was excellent as a raw material for

Naphthalene content 5.8 percent by weight ³ ° carbon and graphite products with good coking

Sulfur content 0.02 percent by weight and suitable for sintering properties.

Aromatic hydrocarbons more than 96 percent by weight Table 7

H / C atomic ratio 0.98 percent by weight

³⁵ gas (CO, H ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ ) 3.0

Table 5 Pre-fraction (initial boiling point up to

218 ° C) 4.8

Product yield naphthalene 13.3

Weight percent _Mitt elfrakt.on (218 to 480 ° C) 44.0

Gas (CO, H _2, CH _4, C ₂ H _2, C ₂ H ₄₎ 4.1 * Severe fraction (pitch) (about 48O ⁰ C) ... 32.2

Pre-fraction (with an initial boiling loss of 2 7

point up to 218 ° C) 4.0

Naphthalene 15.2

Middle fraction (218 to 250 ° C) 25.3 Table 8

Tar (over 250 ⁰ C) 50.9 ⁴⁵ E-softening point 195 ⁰ C

Loss 0.5 H / C ratio 0.52

Normal heptane insolubles ... 97.5 percent by weight

Table 6 Benzene-insoluble 48.0 weight percent

_. ,. _e quinoline-insoluble traces

Tar properties 5 » _volatile material 24.0 percent by weight

Softening point 42 ° C solid carbon 76.0 percent by weight

H / C atomic ratio 0.67 Ash content below 0.1 percent by weight

CS ₂ -Insoluble weight percent sulfur content below 0.5 weight percent

Ash content .... less than 0.1 percent by weight ₅

Sulfur content. Less than 0.05 percent by weight _{. A} graphite electrode as in Example 1 was used

made using this pitch. The own

A pitch obtained by distillation of the product shown in Table 6 was as follows:
described tar was obtained under reduced pressure, has the following properties: 60 Specific weight 1.70

Bond strength, kg / cm * 245

Softening point 96 ^° C., compressive strength, kg / cm ² 460

H / C 0.60, specific resistance IC- ⁴ Ω-cm 7.5

Benzene-insoluble 33 %,

Quinoline Insolubles 4%, 65 Example 4

volatile matter 45%,

iciter carbon 55%, In the lined with a refractory material

Ash content 0.1%. Combustion chamber as in Examples 1 and 2

S '

was used, 0.33 kg / hr. Gas oil with a proportion than the product of Example 1 and better

Density of 0.8433 g / ml introduced, which at 450 ° C properties as a binder.

was preheated and volatilized. With 35 Nm ³ / h.

This oil was burned in the air, and Table 9 was obtained

a gas flow of about 175O ⁰ C. The gas combined 5% by weight

Settlement was as follows: _{Gas (Co>} ^ _CH ^ ^^ ^^ _5?

Pre-fraction (initial boiling point 218 ° C.) 4.2

N ₂ 82.15 volume percent, naphthalene 18.6

CO 2.27 percent by volume, intermediate fraction (218 to 400 ° C) 32.8

CO ₂ 13.53 volume percent, ¹⁰ pitch (above 400 ° C) 36.1

H ₂ 1.85 volume percent loss 0.3

O ₂ 0.20 volume percent. Table 10

_, _DD . _t . ^l5 softening point of 98 ⁰ ° C.

In the high-temperature gas stream obtained, the jj / q ratio became 0 59

at a rate of 251 kg / hour the fraction of benzene-insolubles''.'.'.'.'.'.'.'.'.'. 34 'weight percent

introduced according to Example 2 by thermal quinoline-insoluble 6 percent by weight

Columns of petroleum had been preserved. It became a _{volatile material,} weight percent

a temperature of about 1120 C below normal ao _{solid carbon 56} percent by weight

pressure treated for 0.01 seconds. The _{ash content was below 01} percent by weight

Product with the results shown in Table 9 cooperation received ^r-setting.

The heavy fraction (pitch) which ^{boils above 400 °} C. (a graphite electrode was calculated as in Example 1 at normal pressure) produced that in Table 10 25 using this pitch. The self-reported properties. The properties of the product in this process were as follows: The average fraction obtained can be used as an additive for epoxy resins or urethane resins, without specific gravity 1.69

that difficulties arise, in particular bond strength, kg / cm ^s 245

an improvement in water resistance was noted 30 Compressive strength, kg / cm ² 440

became. The pitch had a higher charring resistivity 10 ~ ⁴ Ω · cm 7.5

^ 644

Claims (1)

1 2 one hydrocarbons of a light coal tar claim: fraction or one = in the thermal cracking of Byproducts obtained from petroleum hydrocarbons Process for the production of pitch and tar tes, the aromatic content of which is more than 80%, in by high-temperature treatment, characterized 5 a heating medium made of inert gases, which is made from to 1300 to characterized that one hydrocarbon-2500 ⁰ C heated steam or one with substances a light Coal tar fraction or an aid of fuel and air or oxygen in the thermal cracking of petroleum hydrocarbons produced combustion flame of the same temperature substances obtained by-product, the aroma of which is introduced and there is 0.001 to 0.1 seconds at a mat content of more than 80% Heating io a temperature of 900 to 1500 ⁰ C and under a medium of inert gases, which can react from steam heated to 1300 to a pressure of 300 mm Hg absolute to 20 at 2500 ^{0 C or a} with fuel and air or oxygen. A raw material is used which is rich in aromatic combustion flames of the same thermal hydrocarbons, e. B. one at the temperature, initiates and there 0.001 to 15 carbon coking as a by-product light-0.1 seconds at a temperature of 900 to oil (washing oil or anthracene oil) or a light oil-1500 ⁰ C and a pressure of 300 mm Hg absolute fraction from the bottom product, which can react as a secondary to 20 atmospheres. product in the thermal cracking of petroleum coals hydrogen, such as gasoline, gas oils or other light distillates, to gaseous fuels and / or olefins, such as ethylene, propylene and butadiene, are obtained as starting material. The aliphatic Hydrocarbons in the raw material are added The invention relates to a method for the production of the thermally cracked method according to the invention, and of pitch or tar through high-temperature treatment, a dealkylation and condensation of the aromatization. see hydrocarbons is brought about. Man Pitch or tar are already used as a binder or in this way tar and pitch can win that Admixture in the manufacture of coal products from aromatic hydrocarbons with very little Graphite electrodes or carbon bricks and tar-side chains are made up and have a high level of thermal energy use resin products such as epoxy or urethane tar. The amount of condensation been det. With regard to the ability to admit, by setting the treatment conditions, baking, the sintering properties and such as temperature, pressure and time, are affected. Graphitizability of the coal material must be a high tar and pitch, which in this way by thermal Aromatic content in the starting material. High temperature cracking are produced The high aromatic content in the starting material is and has a strongly aromatic character also affects the compatibility with resins and the thermally stable; they are also in the chemical resistance in oils and chemicals, size of condensed aromatic rings that as are associated with alkylene chains in tar resins and similar products, proportionately is required. The tar in the coking of evenly and are characterized by a ratio of coal or in the thermal cracking of petroleum 40 moderately narrow molecular weight distribution. Molecular hydrocarbons To obtain gaseous kular weight and molecular structure are result-fuels is generally as its largely under control; the material has such used; however, such a tar does not have a resinous character. It is used as an output only the disadvantage that it contains ash, but material for the manufacture of coal products is also limited in its further usability. 45 is used, so it is with regard to a high one In most cases it is difficult to find the same coking value, good baking and sintering properties Maintain quality. Sometimes it is possible to produce high graphitization properties surprisingly well. To modify such a tar by adding an addition to tar resins, it is in out-heat treatment carried out at about 600 ° C. B's is useful in a significant way; i.e., both the runners up to now it has not been possible to obtain tar, 50 tolerances with the resins as well as the resistance always all demands regarding its stability against water, oils and chemicals shackles are enough. In the graphite electrode are very good. The method according to the invention Industry, the technology of the electric arc, is used for the production of resinous pitch or Furnaces in the steel industry and in the case of electrolytic tar and enables the production of cheaper industrial ones Cells have been shown to have electrodes with higher 55 tar resins, which will be urgently needed in the near future Utility values are required. Be an extension. the usability and the improvement of the pro The heating medium in the inventive method products - both in terms of quality and driving has a temperature in the range from 1300 to quantity - was with conventional tar or pitch products 2500 ⁰ C. When the temperature of the heating medium, which is above 2500 ^° C. through simple distillation or heating, is so great that the temperature difference for treating the initially occurring tar or reaction temperature is so great that the reaction was not obtained, not too unevenly can be, but that enough. also form radicals through dissociation, which the The invention makes it its task to promote bad luck or unevenness of the reaction and to To produce tar that meets the claims in the preceding with an »overreacted part« with an »underreacted industries mentioned are sufficient. th part «lead. In particular, the former leads to The invention relates to a method of initially forming soot so that the end result is not good mentioned type, which is characterized in that is. Is the temperature of the heating medium below