DE1771160B - Process for the production of shaped coke bodies - Google Patents

Description

The invention relates to a method for producing shaped coke bodies from a mixture of carbonaceous material and a relatively small amount of a plasticizer in which the mixture is preheated, then briquetted under pressure and at elevated temperature and finally the briquettes obtained are coked.

It is known, for example, from French patent specification 1 105 772 in conjunction with the British one Patent 648 539 to briquette coal in a mixture with a plasticizer and the coke obtained briquettes. It is also known, for example from British patent specification 654 to treat petroleum coke with a plasticizer. According to the known procedures it is not possible, coke shaped bodies of practically uniform size suitable for metallurgical purposes and strength, precisely adjustable porosity and density and with low ash content.

The invention was based on the object of developing a method that would allow the production of coke shaped bodies of the kind described in a continuous way and in a shorter time than the known "By-product coke" required for its production.

The subject of the invention is thus a method of the type described above, which thereby is marked that

1. First a mixture of 15 to 85 parts of baking charcoal with a content of at least 15% volatiles, 85 to 15 parts of uncalcined petroleum coke with a volatile matter content, with the exception of water, of 8 to 20%, the by coking a difficult-to-liquefy hydrocarbon, and, related on the weight of the coal and petroleum coke, 1 to 8, preferably 2 to 6, parts of one Plasticizer, which is practically neither vaporizable at a temperature below 254 ° C is still thermally decomposable, with the proviso that the average Total content of coal and petroleum coke

3 4

volatiles 2O ° / o tet not exceed low temperatures of about 260-538 ^C C that may take place. Care must be taken here because-2. then the plasticizer at least no oxidation occurs and the content of fugitive is partly with the coal and the petroleum coke ^Ιι ψ. ^S _t ^toffe _ ⁿ * <**, is set to a value below the anverschmolzen by the mixture does not ^{uh 5} 8 ^{e, rten} areas is reduced. Preferably _longer than 15 minutes in a practically inert *? ⁿ .? ^ie . ^{This Mat} 5 "J" ¹ J ¹ " ^La 8 ^e ψ * ' ^a later in the atmosphere to a temperature of at least connection with the test for the content of 149 ° C and a maximum of 260 ° C, ie for some substances even closer explained "Korn" to

; ~ nr sT ^K f ^le St

Mixing it with the P, astinzierungsmittel, J- ^ ™ ^ ^ ™ οΐϊ ^ η £ warms wira, aais _{drigeiii of medium and high} volatile content

3. then that can still act in the plastic state and substances.

at a temperature between 149 and 260 ° C. ₁₅ The invention is illustrated in more detail below with reference to the mixture in a practically inert flow diagram shown in the drawing at a pressure above.

35,2kg / cm ² to Formkörpera with a seemingly According to FIG. 1, the particulate Ausbaren density of at least 0.85 g / cm ³ and starting materials typically in separate Tricheiner porosity of at most 37% compressed _ao ternl stored 2 and 3 and are made by means of, and that controlled conveyor in the desired quantity

4. mixed finally the moldings obtained in ratios necessary, entwas-heating ^ert be at a temperature * or partially dried virtually inert atmosphere at uniform ^ln «^ hoppers available materials. If the Mavon are coked between 538 and 1093 ° C. ^a * £ na ^ t sufficiently dry, st, it will or that

Mixture before being imported into a grinding plant 5 initially introduced into a drum dryer 4. In the

The mixture of coal and petroleum coke can be used in the grinding plant 5 as the starting materials or also smaller amounts of up to about 25 weight- the mixture crushed, ground or grinded Percent, based on the total particulate 3o and here with additional mixing to one Mixture, brought to inert itself during the coking particle size of less than 3.2 mm. Self-trial Essentially non-merging, however, the particle size can also be coarser Substances are added, for example anthracite, or further than the specified. To the limit Coke breeze calcined petroleum coke or bad or setting the size of the in the following fusing or oxidized petroleum coke or also 35 process steps processed particulate When the coke is subsequently used to reduce material, a sieve 6 can be provided. A decorative one Ores Essential for grinding to exceptionally small particle sizes, successful implementation of the method according to which, for example, all of the material a of the invention is the use of plastifi particle size of less than 0.044 mm or the Zierungsmittel (s) that or the different half of the material a particle size voü smaller can (can) fulfill gifts, but primarily has a value of 0.074 mm, is generally avoided, to soften the particulate starting material as this is not necessary to achieve optimal results teriaUs and to lower the temperatures, which are necessary and generally only cost unnecessarily, in which the active particulate is the main game. More precisely, it does not become an ingredient can be pressed or briquetted, 45 additional result achieved, but only increases this to raw moldings with for further processing the processing costs and can this to Formund the subsequent end use after the body, which lead to undesirable levels Coking to form sufficient strength. Are "dusty".

The non-calci- Before adding the plasticizer should not be used as the starting material

Nated raw coke is preferably produced by "delaying the particles at a temperature above about coking" by adding a heavy petroleum- 149 ° C, suitably between about 160 ° C and hydrocarbon to a volatile content of about 260 ° C and preferably between about 171 ° C Substances, excluding water, from about 8 to 20 ° / o 232 ° C., but below the temperature at which, and preferably from 11 to 10%, coking takes place. The rob coke that can be used according to the invention to melt or bake the particles together can be generally conditioned. According to FIG. 1, the heating takes place from the residue of the thermal cracking of the particles to the desired temperature in the we or coking of petroleum hydrocarbons, mainly in a (hot) inert gas stream, for example cracked asphalt, distillation asphalt, coal tar, in a conveying pipe 8 after the Teilchei pitch, wood tar pitch and the like. Exist. As mentioned, however, through a chute 7, a weight conveyor 7 , is a particularly useful and preferred 60 and a shut-off valve 7 b have passed. Di raw coke a petroleum coke obtained in a delay coking system required for the inclusion heating system. If the petroleum coke has a volatile content of more than about 20% of the air-gas mixture supplied by the combustion of the m a durci, it can be supplied in a chamber 9 under controlled conditions, the gas contained in a chamber 9 which local overheating is to be avoided, 65 mentioned particles are then in a cyclc in order to reduce its content of volatile nenabscheider 11 from the hot gases separated substances to a value within the specified The desired conditioning temperature, at which areas are heated, which in comparatively, however no merging occurs, can be done in any way

can be achieved over a long period of time, depending on the speed of work or the one available standing equipments in a short or long period of time. The particles can also be in the Grinder 5 either fully or partially heated or in various other ways provided that an inert atmosphere is maintained or an inert gas system is provided is to avoid excessive oxidation, which is generally necessary for fusibility the particles and the strength of the final product is detrimental.

The cyclone separator 11 expediently has a high separation efficiency of more than about 95%. The separated solids are conveyed to a mixer 17, where they are with the plasticizer are mixed while trapping the exhaust gases and the rest ! 'one-piece substances are diverted from the cyclone separator 11 to another location. For example they can be fed back into the process via a second cyclone separator 12 with an efficiency of 50% (for the separation the remaining finely divided substances from the exhaust gases). Part of the remaining finely divided substances from Cyclone separator 12 is then fed to the mixer 17, while another part together with the recirculated exhaust gases is returned to the combustion chamber 9. Part of that from the cyclone separator 12 incoming gases is used to control the temperature of the heating gases to the combustion chamber 9 returned, while the excess gas is discharged from the cyclone separator 12 to the outside air. All fine particles contained in the exhaust gases discharged to the outside air can be burned or after are collected in a bag filter chamber after cooling.

The heated particles from the cyclone separator 11 and some of the particles from the cyclone separator 12, as mentioned, typically become a continuous mixer 17, such as one Hammer mill or a continuously operating rotor mill. From FIG. 1 shows that the particles entering the mixer 17 are heated. The violets are mixed in the mixer 17 mixed with a plasticizer supplied from a container 13 (for the plasticizer), whose temperature in the container is kept at such a value that it is a sufficiently low Has viscosity without, however, boiling or decomposing. Either the container can or immediately the plasticizer located in this are heated, which for example can be done by means of an electrical heating device 14 or by means of hot oil or steam. One Dosing pump 15 can control the quantity ratio of the conveyed to the mixer 17 and with plasticizer to be mixed with the heated particles within a range of about 1 to 8, and preferably about 2 to 6 weight percent based on the weight of the in the mixer 17 entering particulate material. This proportion of the plasticizer leaves also print out in parts per hundred parts of the particulate matter. In the one leading to the mixer Plasticizer delivery lines are preferred additional heating devices 16 are provided, with the help of which the temperature of the plasticizer can be raised rapidly to the approximate value of the particulate material temperature. The Heated plasticizers can expediently be sprayed onto the particles in mixer 17. Typically, the mixer 17 is also made, for example, by burning natural or Natural gas heated in a chamber 18 and discharge of the heated gas to a heating jacket 19 or heated so that the mixture of particulate coal, particulate petroleum coke and plasticizer is kept at the temperature desired for pressing or briquetting. This "elevated temperature" is at least about 149 ° C, but is below the fusion temperature the carbonaceous solid prior to mixing it with the plasticizer. The plasticizer and particulate material are preferably used within a short time Time span of, for example, about 0.5 to 10 minutes.

• o quickly mixed together while they are still at an elevated temperature from above about 149 ° C, during which time the mixture melts or becomes plastic. The mixture is then poured or for example

»5 pressed with the help of a briquette press 20 before it turns into a non-plastic one through either time-dependent or temperature-related overheating State is shifted. The dwell time during which the mixture is at its maximum before pressing Temperature is maintained is generally limited to a maximum of about 5 minutes. (Typically the material flows continuously through the mixer and becomes part of the total residence time for the complete mechanical mixing required; the remainder of the residence time is for the implementation or fusion between the plasticizer, the raw coke and the Coal required, this reaction taking place in the mixer 17 and also in a hopper 20 a, in which practically inert or oxidation-free conditions are maintained.)

During the molding or pressing process, the pressure applied can vary depending on the temperature of the Particles, the composition of the mixture to be processed, the type of applied Press or the relevant molding process, etc. can be varied.

The raw moldings formed typically have an apparent density between about 0.85 and about 1.25 g / cm ³ and a porosity of about 8 to 37%. After the pressing, the hot, raw molded bodies are transferred, for example by means of a conveyor belt 21, which typically also runs in an inert or non-oxidizing atmosphere, to a coking plant 22, where they gradually, but fairly quickly, for example in 8 hours or less, become practically inert Atmosphere in such a way, for example to a temperature of 538 to 1093 ° C, heated that their content of volatile substances is considerably reduced compared to the raw state.

The procedure described is the preferred embodiment of the invention Procedure. On the other hand, the particulate starting material can be heated first be mixed with the plasticizer instead to be heated separately prior to mixing with the plasticizer. The whole mixture will

7 8

then heated relatively quickly, whereby the plasticizer is neither the plasticizer nor the active decorating agent during the heating with the particulate materials during the grouting Raw material connects. The process to act as the sole binder, so This heating can expediently with simultaneous that the plasticizer before the molding process Mixing all materials as well as during the conveying 5 actually as plasticizer and less than tion of the substances to the pressing device. Binders act. The plasticizers can be used during the heating process, however, the mixture becomes part one during the coking process Temperature of at least about 149 ° C, either or largely converted into carbon but below the fusing temperature of the, so that they then also act as a binder Particles of coal and / or petroleum coke have an effect.

warms, whereupon the softened, fused or other possible and obvious process-plastic mixture briquetted or deviations consist in the particulate being pressed while it is still on a temperature starting material ^1. , namely either the active temperature from above about 149 ^C C and / or the inert material, separated from the plasticizer before it loses its plastic state. The plasticizing agents use methods other than the dwell time during which the final particle heating is to be heated, for example in a blown material and the plasticizing agent in a batch process, in a mill, in an existing mixture before pressing on a Höchst mixer or in a fluidized bed, etc., and then at temperature, is generally limited to a maximum of the plasticizer to the heated particles for -5 minutes. Obviously, with this »0 is added. The particulate starting material-modified process, the residence time at maximum materials, can also be initially separated and heated to sub-temperature practically the same as at the previously different temperatures, before the procedure described. However, since in the latter no conditioning is mixed with one another and with the plasticizer at elevated temperatures. In this case, the inert maturation can be carried out; in the case of the heating material, a long-active material is typically heated to a higher temperature than the step, as can be seen in general. The more plasticizing time than heating the softened agent can be heated separately, or a mixture in the former procedure requires part or all of its heat from or applied to the softened mixture on the preheated particles.
Bring maximum temperature. The briquetting and 30 The following examples are intended to explain the coking step corresponds to the scope of the invention,
speaking stages in the former procedure. It

It is essential that the temperature of the softened example 1
Particle mixture in all embodiments of the

Process according to the invention at least about 35 50 parts of bituminous coal with a content of 149 ⁰ C reached, otherwise the briquetting of volatile substances of 26.1% and 50 parts Peschwert and the strength of the coked briquettes trol coke with a content of volatiles is deficient. The applied maximum temperatures 13.5 ⁰ O, which were stored in separate triches according to the figure, as well as the dwell times at maximum temperature tern 1 and 2, were variable with the help of are variable and must be set separately for each controlled conveyor in the specified quantity end composition type ratios mixed together The material become. For any given composition, the mixture had a humidity of about 5% and must, however, have a precise control of the time and it was dried in the drum dryer 4 using temperature conditions, since other temperatures of about 10 min the mixture used in each case was not exposed to ^{45 121 ° C.} The dried mixture sufficient for a satisfactory briquetting was then transferred to a grinding plant, as it softens or overheats or is heated too long and is used in, for example, pulverized coal burners, a non-plastic one that cannot be pressed for pressing and then a satisfactory one with additional mixing State is shifted. Particle size of essentially smaller than the main object of the described plastifi- 50 ground 1.65 mm. A sieve 6 was used to ensure that the decorating agent consists in its actual plasticizer - larger material particles at the point of entry into the decorating effect and less in their effect as subsequent processing stages of the process for "binding agent". They are mainly used as a preventive.

The largest part of the heating of the particles at lower pressures and temperatures for forming the desired temperature was made possible by inclusion or pressing, as would otherwise be the case with heating in an inert gas flow in the conveyor pipe ί for the production of solid raw bodies it is possible. performed after the ground and mixture · The plasticizer, in conjunction with th particles the chute 7, the Gewichtsföreinem inert material, such as anthracite, have passed when heated to those Ta and the final valve 7 & \ ⁷ erpreßtemperatur and during compression in itself is not 60 The weight conveyor Ta was used for more precisely cohesive briquette. Likewise, the control of the Maactive Teflchenstoffe entering into the conveying pipe 8 results solely in the processing of the amount of material. In the present embodiment, in this way, ie by heating and playing, the conveyor Ta was set in such a way that eggs, also cores of coherent bodies, press 2118 kg ± 3% of particulate matter per hour. Only in connection with the plasticizing 65 to the conveyor pipe 8 delivered. Although the conveying means results in the active particulate material at tube 8 being drawn horizontally in the figure, such heating and processing can be inclined at will and even vertically arranged shaped bodies. For this reason they can be net so that the particles move downwards

2726

1 771

ίο

The conveying pipe 8 in this case had a diameter of about 61 cm and a length of about 6.4 m Provided. The combustion chamber 9 was designed to deliver an amount of heat of 744 kW, 507 kW of this amount of heat from the combustion of 0.821 m ³ / min. of natural gas in 8.21 m ³ / min air from the air-gas mixer 10 and 237 kW through the recirculation and / or combustion of the hot exhaust gases and of finely divided material from a cyclone separator 12. The non-oxidizing gas exiting from the combustion chamber 9 had an exit temperature of about 427 ° C. and flowed at an amount of 225 m ^s / min. out. This throughput corresponded to a linear velocity of the gases in the conveying pipe 8 of about 15 m sec they had a temperature of about 204 ° C. after the gases had been separated off in the cyclone separator 11. As noted, while high heating rates are preferred for maximum production output, a convenient length of time, both short and long, or a time best suited to process speeds or equipment available, may be used to prepare the particulate feedstock before mixing with the plasticizer to heat to the desired, non-sintering temperature. In addition, the heating of the inclusion is also not decisive, rather the particles can also be heated either completely or partially in the grinder 5 or in various other ways, for example in a fluidized bed.

The cyclone separator 11 used is designed in such a way that it has a high separation efficiency of more than about 95%, for example about 97%, for the size of the particles to be processed. The separated solids are then in a 97% of 2108 kg / Hrs., Ie about 2040 kg / h, corresponding amount transferred to the mixer 17, in which they are mixed with the plasticizer, while the exhaust gases and the remaining trapped fine particles in an amount of about 63.5 kg / h. be discharged from the cyclone 11 to another location. In the method shown in the figure and described in the present exemplary embodiment, these substances were used to a large extent by having them in a throughput of about 159.3 nWMin. for example were returned to the process via the second cyclone separator 12; The cyclone separator 12 had an efficiency of about 50% in separating the remaining fine-particle material from the exhaust gases. About half of the remaining fine-particle material obtained by the cyclone separator 12, ie about 31.8 kg / hour, was transferred to the mixer 17, while another part of about 26.3 kg / hour. was returned to the combustion chamber 9 together with the recirculated exhaust gases. Another, even smaller proportion of around 5.44 kg / hour. was destroyed by incineration or recovered after cooling in a bag filter chamber. Typically, a slide 12 ft is provided to limit the proportion of the finely divided material treated in this way and for the appropriate dimensioning of the proportion of the finely divided material returned to the combustion chamber 9. The shut-off valves 11a and 12 o, which emanate from the cyclone separators 11 and 12, allow solids to enter the mixer and prevent a gas flow into the mixer, the amount supplied to the mixer being controlled by the weight conveyor la.

As mentioned, the heated particles are transferred from the cyclone separator 11 and a small proportion of the material from the cyclone separator 12 to a mixer 17, where they are mixed with the solidifying agent supplied from the plasticizing agent container 13; the plasticizer had a temperature in the container 13, d ^; e was sufficient to make it sufficiently viscous, but not so high that it boiled or decomposed. The container and / or there; Plasticizers located therein were heated or heated by means of a heating device 14. In the present embodiment, the plasticizing agent consisted of so-called "thermal tar" the following properties:

Specific weight at

20/20 ° C 1.02

Conradson carbon. 8.0 weight percent

Ash content 0.005%

Sulfur content 0.97%

Distillation (760 mm Hg)
Volume percentage temperature (° C)

Initial boiling point 254

5 292

10 316

20 333

30 344

40 360

50 376

60 393

70., 417

80 457

90 505

93 527 EndpuE

95
100

The viscosity of this thermal tar, measured
Saybolt Universal seconds at 99 ° C was 95.
A metering pump 15 was used for control

27 26 \ 7 #; - ~ ⁽ «■ ^

Proportion of the quantity of the plasticizing agent introduced into the mixer 17 to be mixed with the heated particles. This proportion preferably varies between about 2 and 6 parts by weight per 100 parts of the particulate material entering the mixer 17 or between about 41.6 and 125 l / hour. In the present case, 5 parts or 5 percent by weight of thermal tar were used. Additional heating devices 16 were provided in the plasticizer supply lines for rapidly increasing the temperature of the plasticizer from about 149 ° C. to the temperature of the particles, which is about 204 ° C. and which is also the temperature desired for briquetting. These additional heating devices were needed because it is not advantageous to heat the plasticizer to the temperature (s) for too long before mixing it with the heated particulate material. The heated plasticizer, which in the meantime has a lower viscosity, can expediently be sprayed onto the particles in the mixer 17. The mixer is typically also heated by hot gases, for example from the combustion of natural gas in a chamber 18, for example about 0.023 m ³ / min. Natural gas in 0.25 nvVmin. Air supply an amount of heat of 15 kW, originate and introduced into a heating jacket 19 so that the mixture consisting of the particulate material and the plasticizer is maintained at the temperature desired for briquetting while the products of combustion are discharged from the chimney. The plasticizer and particulate material were then rapidly mixed in mixer 17, their maximum residence time (in mixer) being about 15 minutes, and preferably about 10 minutes, and then in a twin-roll briquette press 20 at a pressure of about 1970 kg / cm ² and a temperature of about 204 ° C, before the mixture formed was nonplastic. The hot, raw moldings were then added in an amount of about 2040 kg / hour. transferred with the aid of the conveyor belt 21 to a coker 22, in which they were gradually heated to a maximum temperature of 982 ° C. within 6 hours in an inert atmosphere.

The briquettes obtained had a pillow or block shape with a length of 76 mm, a width of 50.8 mm and a width of 50.8 mm maximum 38 mm thickness. The moldings which can be produced according to the invention can, however, also be different; Have shapes and be, for example, semi-cylindrical, tubular or toroidal, etc., what of the necessity or convenience of the porosity of the packed bed of the furnace in which they are

should be used depends. These modified forms can also be used, about the rapid evaporation of volatiles during the coking step and thus to enable this process step to be carried out quickly and, at the same time, the formation of Minimize bubbles, cracks or chips, etc. during coking. In general, however, the raw bodies according to the invention are dimensioned so that at least one of their Dimensions does not exceed approximately 50.8 mm.

In the present case, 50 parts of petroleum coke, 50 parts of coal and 5 parts of plasticizer were used, each based on weight.
The following table I shows the effects

kung different process parameters of the method according to the invention on the properties of obtained coke moldings. The same coal and the same petroleum coke were used in each case processed and the same roller pressure applied as in Example 1, while those given in Table I. different types of plasticizer and proportions can be used. In all examples the coking time was 6 hours, with the heating being uniform over this period of time was carried out to a final temperature of 961 ° C.

Table I.

example money
(Weight Petroleum coke
(Weight Plasticizers
(Parts per 100 parts Mixture-
temperature Modified
Drum test
(Weight pro Apparent
density percent) percent) Coal and petroleum coke) ( ⁰ C) cent + 25.4 mm) 2 50 50 5.3 - coal tar 154 72.1 1.12 3 50 50 5.3 - coal tar 174 73.9 1.14 4th 50 50 5.3 - coal tar 176 79.2 1.12 5 50 50 5.3 - coal tar 178 72.9 1.15 6th 50 50 5.3 - coal tar 205 86.8 1.20 7th 50 50 5.3 - coal tar 228 62.2 1.19 8th 50 50 2.7 - thermal tar 179 63.2 1.10 9 25th 75 5.3 - coal tar 171 80.8 1.33 10 25th 75 5.3 - thermal tar 180 81.6 1.28 11th 25th 75 2.5 - thermal tar 182 71.7 1.26 12th 25th 75 7.5 - coal tar 177 82.3 1.39 13th 25th 75 7.5 - coal tar 178 84.2 1.33 14th 75 * 25th 5.3 - coal tar 193 61.3 1.13 15th 75 * 25th 5.3 - coal tar 179 64.7 1.16 16 75 * 25th 5.3 - thermal tar 191 60.1 1.11 17th 75 * 25th 2.7 - coal tar 208 66.5 1.12

Bituminous coal, degassed to a volatile matter content of about 20%.

In Examples 1 through 17, regular sized coal and petroleum coke particles were formed used. "Regularly sized" particles of the following sieve analysis:

Area size money Petroleum coke over 3.2mm 0.00 0.00 3.2 to 2.0 mm 1.04 0.42 2.0 to 0.84 mm 15.22 11.07 0.84 to 0.42 mm 34.96 34.54 0.42 to 0.149 mm 26.62 27.59 below 0.149 mm 22.70 25.27

15th

The "mixture temperature" means the temperature of the mixture immediately before briquetting. The die was kept in a heated state for molding. The modified drum test corresponds to a standard drum test, but with the difference that the former is a lower test Batch was used, which makes the implementation conditions for the test more difficult and lower Results than those obtained in the norm test. The properties of thermal tar are has already been described. The coal tar used had the following properties:

Specific density, at 25/25 ° C ... 1.20
Benzene insolubles, weight percent 6% viscosity at 25 ° C 900 cps

Distillation (D-20)

up to 270 ° C 2.65%

270 to 360 ° C 13.60%

above 360 ° C 83.75%

Further experiments were carried out using conditions similar to those described in Table I. carried out, although coal is one with a high content of volatile substances (50% and more) was used; furthermore, this coal was not partially degassed before use. There were achieved favorable results.

The plasticizer should not evaporate significantly at atmospheric pressure or below be substantially thermally decomposable at a temperature of about 254 ° C; this temperature is considerable above the temperature at which in general the merging effect of the plasticizer with the raw coke and coal occurs. Substances suitable as plasticizers are coal tar, coal tar fractions, coal tar pitch, certain high-boiling hydrocarbon oils and those resulting from the cracking of petroleum distillates Residues such as thermal tar, petroleum pitch, wood tar pitch, anthracene oil, heavy wood tar oils and pitches, heavy lignite oils and pitches. Phenanthrene and the like, heavy petroleum hydrocarbon residue and asphalts, both cracked and distilled, can also be used as Plasticizers are used.

The selection of the particular plasticizer will depend on a number of factors. for example of the material or materials with which it is to be fused, its cost, etc. Any plasticizer can be used that is partially compatible with the Raw coke and the coal used fuse together, but not all plasticizers are accurate equivalent to. Aromatic hydrocarbons are preferred. The oxygen and nitrogen derivatives of aromatic hydrocarbons are also useful, but the hydrocarbons inferior. The plasticizer should not contain any significant proportions of substances which decompose with the formation of strongly oxidizing decomposition products. Cycloparaffinic ones can be used Hydrocarbons or their derivatives, for example the furfural extract of heavy ones Lubricating oils. In many cases, mixtures of hydrocarbons and their derivatives can be advantageous can be applied.

Of course, there will be a certain amount of volatile hydrocarbons in the coking process and other pyrolysis by-products of the plasticizer obtained, yet the most beneficial plasticizers are those that are made in large quantities Extent can be converted into coke. In the event of excessive formation of vapors and gases, the The porosity of the coke bodies is unacceptably increased. In view of the small amount of plasticizer used, which is in no case above about 8%, and there a certain porosity of the manufactured Moldings are desirable, this generally poses no problem. Materials with high sulfur content are usually undesirable.

The ground coal and petroleum coke as well as the plasticizer can, if this appears appropriate, be premixed at room temperature, in particular when the plasticizer is in the form of finely divided solids. Likewise, the normally liquid plasticizers can be mixed in the cold state with the coal and petroleum coke. Alternatively, mixing at elevated temperatures can be done by a fairly uniform mixture of coal, petroleum coke and plasticizer to a temperature of above about 149 ° C, and typically from about 160 to ^260c C, preferably is heated from 171 to 232 ° C while the mixing is carried out in a suitable device in such a way that the mixing and softening or fusing occur simultaneously. The correct time-temperature factor for this fusing treatment is quite critical and will vary depending on the volatile content of the coal and petroleum coke, as well as the particular plasticizer used and its viscosity. In any case, the softened particles should not be heated for too long and / or at too high a temperature prior to compression, as it is possible that such treatment will render the softened particles "non-plastic" and thus create difficulties in forming the Leading raw body or providing raw body of insufficient strength. These time-temperature conditions or residence times at maximum temperature can easily be determined for any given, described mixture on the basis of the guidelines explained and using the compressibility of the softened particles and the properties of the fired briquettes as criteria. The fusion treatment should preferably be in non-oxidizing

38 each vei stäi vei

sor never ou be mi au rei m d £ ar

a: K a F ii ν tt f

Atmosphere take place, in particular in the duly
or according to the moment in which the first at
soaked particles of their maximum temperature approaching 254 ° C.

or achieve them. D ₃₅ Applying mechanical pressure or that

In certain cases the mixing can be done with about 5 compressing of the softened mixture from Petroibis 93 ° C heated raw materials take place, but coke and coal can take place in various ways below a temperature at which this follows, for example, preferably by means of a roller fusing effect is initiated or full briquetting, extrusion, injection molding is progressed by means of constantly, whereupon the further- a piston press or by molding. Processing at higher temperatures follows. io The in the context of the procedure according to the Erfin-Wie mentioned, the fusion treatment must be suitable for coal or petroleum coke carefully controlled in such a way that they have to be after pressing or briquetting does not progress too far. This control can have such properties that it can be used in all stages usually take place via the temperature, although the coking process only has a low plasticity the time factor also plays an important role. 15 and have no fluidity. If the coal When heating a mixture of plasticizing coke or petroleum coke too high a content medium, coal and petroleum coke possesses volatiles during mixing or the softened up a temperature above the specified mixture tends to melt and flow before a rich or above that for the relevant ge. Decomposition of the decomposable components of the Mixing the desired maximum temperature runs through a raw molding has taken place, seek the the mixture initially has a pasty state and from the inside of the molded body to the outside thereof then changes in its properties leading tiny channels through which the gas and becomes too dry for extrusion and such-shaped decomposition products come out to one with being plugged, for example, after a continuous rolling process, which results in processing difficult briquetting processes difficult to press. With coking skills as well as the formation of large In other words, the softened mixture of pores and coked moldings should be deficient Coal and petroleum coke themselves give a lubricating effect strength. When producing the moldings on the briquetting molds. With certain made of materials with the previously mentioned self-plasticizers can achieve this over-treatment and according to the explained invention take place in the specified temperature range, 30 processes, however, no such material flow occurs if the treatment period is too long and and the canals remain small and all over For example, more than 5 min. Or even less coking moldings distributed away, so that the amounts to. As mentioned, the critical one-gas changes quickly and without the formation of large pores or full of the time and temperature relationship in the channels to be able to escape. Merger step depending on the 35 case within the scope of the procedure according to the Er-Me and the type of plasticization used, a charcoal with a volatile content medium and also depending on the substance content of more than about 20% and up to volatile substances as well as of the particle size of about 45% and in such an amount can be used Throat and petroleum coke. In general, it is supposed that the coal and petroleum coke should melt The mixture typically formed in the case of the invention has a volatile content Fine carbon and greater than about 20 percent by weight used in the process Petroleum coke particles due to their large surface area, it is necessary to place this coal on any, which and their small diameter very light. A person skilled in the art to degas manner, so that the

If the fused mixture has a volatile content or the gas content of the Has reached the point at which the mixture obtained is easily 45 ° / o at most, If the coal is partially degassed, it becomes an overweight not only difficult to briquette by means of rollers moderate agglomeration or agglomeration of the or extrusion, but also leads to form- leads to charcoal, it can be partially crushed and bruised, which show defective areas or voids when brought to an acceptable particle size, urd during or after the coking process 50 whereupon they are used as raw material in the inventive get lower strength. If a proper procedure can be used, m sch too far advanced in the merging step - All materials in the briquetting or

steps, it is possible in some cases to add a small amount of plasticizer to a mixture to be compressed, heated to essentially the same temperature, thereby restoring its briquetting or extrusion properties due to the various components. However, if they are influenced differently. If, for example, the amount of additionally added plasticizing material, such as anthracite, is slightly too large, the coked mold can be turned, this is typically only heated to the body due to the increased volume at the steaming temperature, while on the other hand, the must be driven off, poor 60 the coal and petroleum coke, which are mixed with the plastin strength and the undesired extent of the ornamental agent, develop a fusion-increased porosity. In addition, this will be subject to effect. The time and / or the tempo shrinkage of the coked bodies increases. The temperature during which the particles should also be kept underheating at this heat fusion temperature or at which they are half the temperature at which the plasma is heated, apart from the fact that the particles already decompose or essentially - said they would distill out of the mixture to a certain extent due to various other factors. Petroleum coke begins with a volatile Swr content; However, this occurs in most of the cases of 8 or 9% is related only to the amount

common amounts of coal are used. Obviously change with different mixtures of the type listed below also the time and Temperature conditions; these changes lie

but of course within the scope of the invention. For example, those in table Π compiled starting materials are processed.

Table Π

Parts Petroleum coke Bituminous coal Gas content Plasticizers PeUe Petroleum coke and coal)
Art 90 Teüe 45 (TeUe to 100 1
Parts (to 100 parts) Thermal tar a) 90 10 20th 6.0 Coal tar 70 10 23 6.0 Coal tar c) 50 30th 40 * 5.3 Thermal tar 50 50 17th 2.7 Coal tar pitch e) 30th 50 23 5.3 Coal tar f) 30th 70 26 * 5.3 Thermal tar G) 20th 70 30 * 2.7 Coal tar H) 20th 80 25 * 1.5 Coal tar pitch i) 20th 80 45 * 3 Thermal tar j) 10 80 37 * 5.3 Coal tar k) 90 3 Gas content
( ⁰ Zo) 13th 13th 12th 20th 9 10 14th 15th 11th 9 15th

* In the case of mixtures d, g, h, i, j, and k, the bitumen coal was partially degassed (thus the gas content of the coal-petroleum coke mixture does not exceed a value of about 20 ° / o) before it is mixed with the petroleum coke and after the method according to the invention was treated. In all cases the particulate material became during the fusion heating step as long and / or as high (also within the temperature range above) heated, that the desired softening and melting was caused, but not for so long and / or at such high temperatures that the resulting fusion is nichiplastic would.

The forming device 20 or the rollers of the briquetting machine can be at any temperature and for example the same temperature as the particles, a higher temperature, Have room temperature or a temperature between these ranges, etc. The briquetting rollers can be water-, oil- or otherwise cooled. Must before briquetting the heated solids are protected from undesired oxidation by atmospheric air, since this would be detrimental to the strength of the end product. Obviously, there is a presence excess air also increases the risk of ignition and burning. Therefore, an inert gas atmosphere be provided.

The pressure applied during pressing changes depending on the temperature of the softened particulate material to be deformed, the particular composition, the type of press used or the molding process concerned, etc. In a piston press, this pressure is between about 35.2 and about 1050 kg / cm ² , with lower pressures being used at higher temperatures and vice versa. For a roller press, the pressure (P) is typically between about 281 and about

6330 kg / cm * if P = ~ (A = total area of the

pressurized pockets along the line of contact between the rollers; F = pressure exerted on the rollers of the press). For example, mixing temperatures of 149 to 177 ° C and pressures of 70.3 to 141 kg / cm ² in a piston press can lead to poor strength of the raw and / or the sintered molded body, while temperatures of about 177 to 232 ° C and pressures of 35 , 2 kg / cm ² can provide moldings with good strength. Typically, only such a high pressure should be applied that a raw molded body with a porosity of at least 8%> is obtained, while on the other hand at least such a high pressure should be applied that a raw molded body with a porosity of at most 37% is obtained will. In other words, when the porosity of the molded article formed under 8 ⁰ O or above 37 ° / o or otherwise is not within a desired, satisfactory range, the applied pressure can be reduced or increased accordingly, until the porosity of the obtained crude moldings the desired Value reached. Preference is given to raw moldings with a porosity of about 15 to 30 ^° C.

A roller press is preferred for mass production. When using such a device is the "compression time", d. H. the time during which those to be deformed fused Particles are actually under pressure or during which pressure is actually exerted, usually less than 2 seconds and typically less than 1 second. Of course, however molding devices other than those mentioned above can also be used.

In the case of piston presses, pressures below 176 kg / cm ² are usually used, since higher pressures only mean a waste of energy. In the case of many carbon-containing mixtures or compositions processed according to the invention, especially those with a high gas content, the briquettes or moldings at pressures above about 246 kg / cm ² increasingly contain defective areas (voids), specifically after they have been coked. When piston press therefore generally be avoided pressures above about 28.1 kg / cm ^ä, unless substantial amounts of "inert materials" to be processed mixture to-

19 20

have been set or the processing to be processed.

mix has a low gas content; in such process steps can be compressed In cases, the use of higher pressures can be advantageous. H. much faster than be liable. Roller presses employ higher pressures than those commonly used with by-product coke. 5 oven procedure required period of 18 to

The raw moldings should have a minimum porosity of 24 hours, for example by having a sity of about 8%, so that as little as possible - without deterioration in the product quality - internal difficulties arise during pressing and coking within a maximum of 8 hours. can be heated to a resulting and rapid coking temperature of about 538-1093 ° C. If the porosity of the molded body is the or until a gas content of the product of 5% is too low and a rapid coking of this or less is achieved. Coking periods of moldings are sought, the escape - of 3 to 6 hours are typical. Of course, volatile substances condense after opening the shaped body, even if used for longer periods of time than 8 hours, so that coke is used for metallurgical processes, but this is generally disadvantageous.
ren of unsuitable size and strength is obtained. 15 During the treatment in the hot tasting

The porosity of the molded bodies produced is of course not subject to any re-softening or temperature to which the fused particles stick together because they are "fused" and too warm, or to the temperature at which the fused particles stick together, of course, even by changing the temperature Production of the separate individual moldings, pressed, raw moldings used composition are influenced, whereby a solid, coherent effect. As mentioned, the porosity of the raw manure within the raw moldings should be at most 37 ⁰ Zo. When higher was brought. For this reason, the bond is porosity, the moldings are either too little solid between the particles in the individual moldings or, after coking, they are very good for the pre-coking and the provided intended use has too low an apparent coke density, typically superior Fe density. The apparent density of the coked shape. For certain compositions and underbody it is generally about 1.0 to 1.5 g / cm ³ . In certain circumstances, however, there can be a tendency for the density of the raw moldings should be between about 0.85 and 1.25 g / cm ^{3 of} the briquettes sticking together during processing, with self-coking. In this case, the less dense shaped bodies can be subjected to a short or limited surface area higher and the denser shaped bodies to less oxidation, so that they have higher porosity. solidify and re-soften during the

After pressing the fused or coking is prevented.

softened particles are formed raw The raw moldings can be

Moldings are preferably coked practically immediately and without a coking device, in which a substantial cooling coked. If the temperature is practically inert or non-oxidizing atmosphere door the molded body can be maintained between pressing and. To achieve the best The coking device 22 is so likely to result for the formation of cracks and laid or is the operation of this device Voids in the moldings larger than in the 40 regulated so that the raw moldings under a case, when the moldings are immediately and without substantial flawless regulation to the desired finite Cooling to be coked. Coking temperature can be heated.

In the preferred mode of operation, wherein said When the desired final temperature of about C particles with a heated is 800 'prior to mixing and the raw molded body has a temperature plasticizer are heated separately, perma- 45 of 204 ^c C have when selected from the Formvorert Working cycle of heating the particles in direction 20 exit and into the coker 22 aetv> a 149 to 260 ° C, mixing the particles with the step, their heating takes place from 204 to S00 ^: C plasticizer, pressing the melted - preferably with very precisely regulated Green particles, while they are still at a temperature of no more than 400 ^c C / hour, temperature of about 149 to 260 ° C, ie with 50 to a temperature of between about 500 and only little or none Cooling before the 650 ° C and afterwards of no more than about the molding process, and transferring the moldings in 500 ° C'h. To the final temperature of 800 ° ^C, the coker not long it is longer than about 10 minutes. During lower heating rates becoming more typical of these phases of the process, none are used to any significant extent until the raw moldings allow a significant "bump" in the working cycle. Reach the critical temperature or until they are permanently warmed up carbonaceous particles or which are "solidified", typically with a temperature-deformed, masses to be processed are kept at a very temperature of 600 to 700 ° C, whereupon a somewhat even movement, with any higher heating rate until the desired substantial build-up is avoided. »Bumps« or final temperature can be applied. The pre- "damming" can, however, in a possible heating process described above, is preferable to a previous preheating step in which the hot which the particles on a predetermined, similarly lower temperature of about 93 ° C temperature difference, for example from 200 to 200 ° C, or exposed to 800 ° C during the subsequent fermentation. Preferably, comments will occur without this increasing the temperature of the molded bodies practically linearly within a given or significant effect on the quality of the product or on the failure-free quality of the manufactured product with a heating rate of not

more than 10 ° C has in each minute during the initial cooling zones also may be used as well for cooling both the Ver-heating time, which is not more than 400 Koken ⁰ C per hour; Should be made and but not more than Optionally, the cooling in a geetwa 13 ⁰ C per minute during a period of time, separated apparatus include heating. The coke moldings which have cooled down during which the moldings by no more than 5 days can then be stored in a store at about 500 ° C / hour. are to be heated, stored through containers, immediately dispatched or immediately in leads, instead of the moldings used, for example, a cupola, a blast furnace or the like. To heat them for 1 hour at 500 ° C, they are then.

For 1 more hour in a zone at 600 ° C to In general, coking temperatures are from

transfer etc. io at least about 538 ° C required while higher

Controlled temperature gradients, the lower temperatures of, for example, about 800 to 960 ° C

are preferred as those given above and by way of example for obtaining optimal results

wise a temperature increase of 300 ° C / hour. or the. Temperatures above 960 ° C, for example

8 ° C / min. not exceed and at those at up to about 1093 ⁰ C, can also be used

For example, a heating rate of 15 will be used, but are generally for delivery

3 ° C / min. is applied, are even more typical of an industrially satisfactory product

games for the generally required in the inventive game.

koken applied temperature gradient. The content of volatile substances or the gas within the ranges described above is the content of the petroleum coke and coal types that are selected and applied heating-up according to the invention are used so speeds also depend on the density, the len, is made according to ASTM method No. D 271-48, Porosity, size, shape and content of modified for peat and lignite, determines and closes volatile substances of the raw form to be processed - the water content. According to this procedure, body off. a relatively small amount of petroleum coke or coal, for example

Rotary cookers, wave cookers and walkways are heated to approx. 510 ° C for 5 to 10 minutes. the run of the shaped body movement through the coker weight difference of the sample before and after the Eralhnählich higher temperature zones in which warmth represents the "gas content" of the tested material practically inert atmosphere maintained rials. As mentioned, have when the invention can, are advantageously suitable for petroleum coke used in accordance with the method the described warming. 30 preferably not just a prescribed gas

After heating the molded body to the content or content of volatile substances, but rather

the desired temperature they are usually in a hard coke agglomerate or "grain",

inert atmosphere gradually to a temperature when it is

cooled from about 104 ⁰ C or below. One can be heated, however, instead of a 1-g sample

Uniform device that uses both heating and 5 g.

In addition 1 Biatt drawings

Claims (6)

Patent claims: 1. A process for the production of shaped coke bodies from a mixture of carbonaceous substances Material and a relatively small amount of a plasticizer in which the The mixture is preheated, then briquetted under pressure and at elevated temperature and finally the briquettes obtained are coked, characterized in that 1. First a mixture of 15 to 85 parts of baking coal with a content of at least 15 Vo of volatile components, 85 to 15 parts of uncalcined petroleum coke with a content of volatile components, with the exception of water, of 8 to 20%, which by Coking a difficult-to-liquefy hydrocarbon was produced _ao , and, based on the weight of the coal and petroleum coke, 1 to 8, preferably 2 to 6, parts of a plasticizer, which at a temperature below 254 ° C practically neither evaporate _a5 bar nor is thermally decomposable, with the proviso that the average total volatile content of coal and petroleum coke does not exceed 20%, that 2. then the plasticizer at least partially with the coal and the Petroleum coke is fused by leaving the mixture in one for no more than 15 minutes practically inert atmosphere to a temperature of at least 149 ° C and at most 260 ° C, d. H. to a temperature below the sintering temperature both the coal and petroleum coke before mixing with the plasticizer, is heated that 3. then the mixture, which is still in the plastic state and at a temperature between 149 and 260 ° C., in a practically inert atmosphere at a pressure above 35.2 kg / cm ² to form molded bodies with an apparent density of at least 0.85 g / cm ^s and a porosity of at most 37% is pressed, and that 4. Finally, the obtained molded articles are carbonized in a substantially inert atmosphere at a uniform rate of heating at a temperature of 538-1093 ⁰ C. 2. The method according to claim 1, characterized in that the mixture to be compressed an inert material in amounts up to 25 parts per 100 parts of that of coal, raw coke and inert Material added to existing mixture and the amount of plasticizer added each to the 100 (weight) parts of the mixture of coal, raw coke and inert material is related. 3. The method according to claim 1, characterized in that the mixture in process stage 2 prior to pressing in process stage 3 is kept at a temperature between 160 to 260 ° C for a maximum of 5 minutes. 4. The method according to claim 1, characterized in that that the coal and / or the petroleum coke prior to mixing with the plasticizer are heated in process stage 1 in a known manner. 5. The method according to claim 4, characterized in that the plasticizer before the mixing with the coal and the petroleum coke in process stage 1 is heated. 6. The method according to claim 4, characterized in that the coal and / or the petroleum coke heated with entrainment in a stream of inert gas and prior to mixing with the plasticizer are or will be separated from the inert gas stream.