DE1955285C3 - Process for the production of pitch and tar by high temperature treatment - Google Patents

Description

The invention makes it its task to promote bad luck or unevenness of the reaction and to

To produce tar that meets the requirements in the previous 65 an »overreacted part« with an »underreacted part«

the industries mentioned above 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

Table 3 Properties pitch softening point 95.3 ⁰ C

3 H / C atomic ratio 0.56

Benzene-insoluble 38 percent by weight Quinoline insolubles 10 percent by weight

volatile material, ... 42% by weight

solid carbon 58 percent by weight

less than 0.1 percent by weight

1300 "C, the temperature difference TT 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. Are these
Conditions are not met, the gasification rate in thermal cracking is so high that
that the product yield becomes low. The Reaklionstemperatur is preferably between 1000 and 1300 ° C. io ash content it is less than 900 ⁰ C, the degree of conversion is low. If it is above 1500 "C, then the samples of graphite electrodes under quality control of tar and pitch were difficult, use of the pitch according to the invention and of and the products are not good. Hitherto common hard coal pitch with medium The reaction pressure is preferably between 15 melting point The production of the samples atmospheric pressure and 10 atmospheres. At a pressure of and the properties of the products were as absolute as below 300inm Hg, the reaction rate is carried out or determined: too low. If the pressure is above 20 atmospheres, then 100 parts Normal coke (water content 0.13%, not only the energy costs rise, but also term components 0.52%, ash content 0.32%, coal also leads to coke deposits in the reactor 10 material 99.03%, specific weight 2.04) were mixed with by the condensation of the pitch formed or 30 parts of pitch according to the invention and 1 the tar, which is of course unfavorable ng at a temperature of 20 to 25 ° C over the reaction time is preferably between 0.003 and the softening point of the pitch about 30 minutes 0.05 seconds. If it is less than 0.001 seconds, it is kneaded. The kneaded mixture became little under the conversion. If the time is longer than 15 pressure of 150 to 300 kg / cm ² at a temperature of 0.1 seconds, the pitch or tar loses the good from 30 to 35 ° C above * the softening point of the

Pitch pressed from the melt to form a strand with a diameter of 7.5 cm. After heating the melt 25 days at a temperature of up to 900 ⁰ C it was graphiticrt 5 days by heating to a temperature of up to 2800 ⁰ C.

Properties.

L ¹ IC the following examples serve to further explain the invention.

example 1

- \., j Nm ³ / h 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 which had the properties given in Table 1 was used with a vessel speed of 20 kg / hour. inserted into the generated rlochtniperaturgasstrom of about 1750 ° C and hot atmospheres brought di'ii 0.008 seconds under a pressure of 3 a reaction temperature of about 1150 ⁰ C for P.euktion. The products obtained are shown in Table 2.

Among the recovered products, the heavy fraction (pitch) had a boiling point above 400 ° C Atmospheric pressure and had the properties shown in Table 3.

Table 1
Properties of the raw material.

Initial boiling point 220 ° C

Final boiling point 32O ^U C

Naphthalene content 20.5 percent by weight

Aromatic hydrocarbons above 98% H / C atomic ratio 0.96

Table 2

Product details

Weight percent

Gas (CO, H ₃ , CH ₄ , C ₂ H ₃ , C ₁ H ₄ ) 3.3

Forecut (initial boiling point of 218 ⁰ C) 4.7

Naphthalene 30.3

Intermediate fraction (218-400 ° C) 22.8

Pitch (over 400 ° C) 38.6

Loss 0.3

The properties of the hard coal pitch used as a control sample with a medium softening point are the following:

Softening point 72 ⁰ C,
H / C 0.48,

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

The characteristics of the products were as follows:

50 product
according to
Frustration Coal
pcch specific weight
Bond strength, kg / cm ² ...
Compressive strength, kg / cm ⁵ ..
55 Special resistance
10 "Ω-cm 1.71
255
450
7.4 1.61
195
350
9.5

The properties of the according to the invention Process obtained product 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 which had the properties listed in Table 4, with a speed

speed of 30 kg / h, introduced into a high-temperature gas stream of 1750 "C, which had been eratugt by burning the same amount of propane and air as in Example 1, and at a temperature of about 1080 ⁰ C, reaction time 0.3 seconds, below a Brought a pressure of 5 atmospheres to react The products are listed in Table 5.

The heavy fraction (tar) formed in this way boiled under atmospheric pressure above 250 ° C. and possessed the properties given in Table 6; the contract to The possibility of using an epoxy resin in which the material was used as an admixture was very high. The content of acidic components, sulfur and ash was very low. When mixing the material with a resin and a hardening agent resulted in such a high stability that it can be stored for a long time was possible. The resin products obtained showed excellent resistance to water, oils and chemicals.

Was this tar used in a urethane tar, ao so it was found not only with urethanes of the two-component type, but also with urethanes from One-component type as usable.

Table 4
Raw material properties (ethylene cracker soil oil!)

Initial boiling point 230 ^c C

Final Boiling Point 350 ^r 'C

Naphthalene content 5.8 percent by weight

Sulfur content 0.02 percent by weight

Aromatic hydrocarbons greater than 96 percent by weight

H / C atomic ratio 0.98

1955 28a (/

Such a pitch was used as a binder for carbon electrodes used. The graphite electrode was produced as in Example 1 using this pitch. The properties of the product were as follows:

Specific gravity 1.69

Bond strength, kg / cm * 240

Compressive strength, kg / cm ⁸ 430

Specific resistance 10- «Q · cm 7.7

Example 3

In a mixing chamber with an inner diameter of 30 mm and a length of 500 mm, which was lined with a refractory material , a tar of the type used in Example 2 at a rate of 27 kg / hour. in a water vapor flow of 60 kg / hour. and about 1700 ⁰ C is initiated. The steam flow was generated with the help of a regenerative heating system. Was allowed to tar in the gas stream 0.002 seconds at a tempering rate of about 122o C ⁰ be; Reacting to atmospheric pressure, the product described in Table 7 could be obtained in: The heavy fraction with a boiling point above 480 ⁰ C below atmospheric pressure; dismissed the genannlen in Table 8 properties; ι:, showed a high coking value and high graph tierbarkeit and was excellent as a raw material Ii Carbon and graphite products suitable with good coking and Sintereigenschafton.

Table 7

Table 5

Product yield

Weight percent

Gas (CO, H ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₄ ) 4.1

Forecut (with an initial boiling point to 218 ⁰ C) 4.0

Naphthalene 15.2

Middle Fraclion (218 to 250 "C) 25.3

Tar (over 250 ^c C) 50.9

Loss 0.5

Table 6
Tar properties

Softening point 42 ^C C

H'C atomic ratio 0.67

CSj insolubles% by weight

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

Sulfur content .. less than 0.05 percent by weight

A pitch obtained by distilling the tar described in Table 6 under reduced pressure has the following properties;

Softening point 96 ° C,

H / C 0.60,

Benzene-insoluble 33%,

Chinchin-insoluble 4%, volatile matter 45%,

solid carbon 55%,

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

Pre-fraction (initial boiling point up to

218 ° C)

naphthalene

Middle fraction (218 to 480 ^c C)

Heavy fraction (pitch) (above 480 ° C). loss

dismiss 3
195 ^; C.

Weight Process 3.0

4.8 13.3 44.0 32.2

2.7

Softening point

H / 'C ratio

Normal heptane insoluble ...

Benzene insolubles

Quinoline insolubles

volatile material

solid carbon

Ash content below

Sulfur gelialt under

0.52

97.5 percent by weight 48.0 percent by weight traces

24.0 percent by weight

76.0 percent by weight

0.1 percent by weight

0.5 percent by weight

Ash content 0.1%

A graphite electrode was made as in Example I using this pitch. The Liiiien of the product were as follows:

Specific weight 1.70

Bond strength, kg / cm * 245

Compressive Strength, kg / cm ² 460

Specific resistance 10 " ⁴ Ω · cm 7.5

Example 4

In the combustion chamber lined with a refractory material, as in Examples 1 and 2

10

was used, 0.33 kg / hr. Introduced oil with a density of 0.8433 g / ml, which was preheated to 450 ¹ C and volatilized. With 35 Nm '/ hour. This oil was burned in the air, and an oas flow of etsva 1750 C. was obtained. The composition of the oil was as follows:

Nj 82.15 percent by volume.

CO 2.27 percent by volume,

CO ₂ 13.53 percent by volume.

H ₂ 1.85 percent by volume

and

Oj 0.20 volume percent.

15th

In the high temperature gas sirom obtained was at a rate of 25 kg / hour. the faction introduced, which had been obtained according to Example 2 by thermal cracking of petroleum. She was at treated at a temperature of about 1120 C under normal pressure for 0.01 seconds. It became that Product having the composition shown in Table 9 was obtained.

The heavy fraction (pitch) that is over 400C (calculated at normal pressure) has the properties listed in Table 10 as. The in this procedure obtained middle fraction can be used as an additive for epoxy resins or urethanh.ar/c without that difficulties arise, in particular an improvement in water resistance was found would. The pitch had a higher charring percentage as the product of example properties as a binder.

Table 9

and better

GcWtchlsprfiAcnt

5.7

Gas (Co, H ₂ , CH ₄ , C ₂ H ₂ , C ₂ H ₁ )

Pre-fraction (starting point 218'C) 4.2

Naphthalene 18.6

Intermediate fraction (218 to 400 ¹ C) 32.8

Pitch (over 400 "C) 36.1

Loss 0.3

Table 10

Softening point 98.0 ° C

H / C ratio 0.59

Benzene insolubles 34 percent by weight

Quinoline insolubles 6 percent by weight

volatile material 44 weight percent

solid carbon 56 percent by weight

Ash content below 0.1 percent by weight

A graphite electrode was made as in Example 1 using this pitch. The own shafts of the product were as follows:

Specific gravity 1.69

Bond strength, kg / cm ¹ 245

Compressive Strength, kg / cm ¹ 440

Specific resistance 10 * Q · cm 7.5

Claims (1)

one hydrocarbons of a light coal tar Claim: fraction or one in the thermal <^ en of Byproducts obtained from petroleum hydrocarbons Process for the production of pitch and tar tes, the aromatic content of which protrudes more than »u /« De, in by high temperature treatment, characterized by a heating medium made of inert gases, which is characterized by hydrocarbon heated to 2500 ° C water vapor or with Substances of a light coal tar fraction or an aid from fuel and air or building stumps in the thermal cracking of petroleum hydrocarbons produced combustion flame of the same ι emperatur substances obtained by-product, whose flavor consists, introduces and there 0.001 to uj seKunaen oei material content is more than 80% Heating xo a temperature of 900 to lsuu c uno under a medium of inert gases, which reacts from steam heated to 1300 to a pressure of 300 mm Hg absolute to 20atu 2500 ° C or a. .
with the help of fuel and air or oxygen. A raw material is used which is rich in the aromatic combustion flame of the same thermal hydrocarbons, e.g. B. an oei oer temperature exists, initiates and there 0.001 to 15 carbon coking as a by-product accruing leich-0.1 seconds at a temperature of 900 to oil (washing oil or anthraceno!) Or a Leicmoi-1500 ⁰ C and a pressure of 300 mm Hg absolute fraction from the bottom product, which can react as JNeoen to 20 atmospheres. product of thermal cracking before petroleum hydrocarbons ^ such as gasoline, gas oil or other light distillates 20 to gaseous fuels and / or olefins such as ethylene, propylene and buta serves as a 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 as a dealkylation and condensation of the aromaii young. see hydrocarbons is brought about. Ma ,. Pitch or tar is already used as a binder, or can win tar and pitch that way, you Admixture in the production of coal products from aromatic hydrocarbons with very white: - such as graphite electrodes or carbon bricks and tar there are side chains and high thermal products such as epoxy or urethane tar use 30 have stability. The extent of the condensate!, - ,! 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 influenced, The 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 made, wiser, The high aromatic content in the starting material has a strongly aromatic character and smd 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 it is associated with alkylene resins in tar resins and similar products, 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. mole hydrocarbons for obtaining gaseous kular weight and molecular structure are a result Fuels produced is generally considered to be 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 obtain the same coking, 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 also as an admixture to Teerhar.'cn it is in out-heat treatment at about 500C. It is useful in a significant way, i.e., both for the staff up to now it has not been possible to extract tar, 50 bearing wedges with the resins as well as the resistors always all claims regarding its own resistance to water, oils and chemicals business would have been enough. The graphite electrodes 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 ducts - both in terms of quality and driving has a temperature in the range of 1300 to ^{Quantity - was up to 250O 0} C with the usual tar or pitch products. When the temperature of the heating medium ^{th, which is above 250O 0} C by simple distillation or heat-60, is the temperature difference to treatment of the initially occurring tar or reaction temperature so great that the reaction does not Pech byproducts were obtained, not only that it can become uneven, but that it becomes pass. also form radicals through dissociation, which the