DE1771160A1 - Process for the production of metallurgical shaped coke bodies - Google Patents

Description

The invention relates to a novel method of manufacture of coke, which is suitable for use in cupola and blast furnaces as well as for other metallurgical processes.

The object of the invention is to provide a method of making coke of practically uniform size and strength, with all of the coca lending itself to metallurgical use, as opposed to normally coke produced in a by-product furnace which is characterized by a significant proportion of undersized material.

Another aim of the invention is to produce coke with precisely controllable porosity properties and density, which, moreover, is only very low Should have ash content. Such types of coke are suitable as reducing agents for the phosphorus and calcium

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carbide induction and as a carbonaceous aggregate for the production of Soderberg anodes or pre-sintered anodes for the aluminum industry.

This coke should be able to be produced in a much shorter time than is the case for the production of coke conventional by-product coke oven processes, which typically take periods of about 18-24 days. require, is required. The coke production was practically continuous and less manpower worked and maintenance costs than the by-product coke oven process, which can be referred to as a "multiple batch process".

In a preferred embodiment, the inventive fle Process in the production of metallurgical coke from two active, particulate, carbonaceous Main ingredients, namely coal and uncalcined Raw coke made by coking a heavy, liquefiable Hydrocarbon to a content of volatile substances, excluding water, of about θ - 20 {< has been produced, for example Hohpetrolkoke, eowie from a plasticizer for one or both of these substances. The mixture can also contain smaller amounts of up to about 25% by weight, based on the entire particle size

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mixed, inert, calibrated during the coking process Substances that do not essentially fuse together are added, for example anthracite, coke breeze, calcined Petroleum coke or poorly fusing or oxidized crude petroleum coke or also in the following use ores to be reduced in the coke. In less preferred embodiments of the invention, the final obtained coke temporarily also from raw uncalcined Coke as the only starting particulate matter plus a plasticizer for this or from raw or partially degassed bitumen coal as the only active one particulate starting material in conjunction with a Plasticizers are produced for this. In general, however, the invention is preferably carried out in such a way that as the starting particulate active material a mixture of coal and raw uncalcined coke is used, 85 to 15 parts per 100 smell parts dos raw uncalcined coke and 15 to 85 parts coal omitted. A very important feature of the invention consists in the use of the plasticizer. who can perform various tasks, but primarily to soften the particulate Starting materials and for lowering temperatures serve, in which the active particulate main ingredients can be compressed or briquetted to

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Raw pony body with for further processing and the subsequent use of the earth after carbonation or Coking to form sufficient strength.

All raw coke used is preferably uncalcined raw coke produced by "delayed coking" by adding a heavy petroleum hydrocarbon a content of volatile substances, excluding water, from about θ - 20fC and preferably from 11-16) 1 coked will. Preferably, this material should be able to be used later in connection with the examination of the salary of volatile substances, and have a volatile substance content of at least about 10 #, especially when uncalcined raw coke is used as the only active particulate source material. Using this material mixed with coal can have a volatile content of up to 8%.

The coal has a volatile content of about 15 - 4-5 ^, with the coal being those of the low, medium and high levels of volatile substances. Palis the coal a salary of volatiles greater than about 20ji and than sole or major active particulate

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Starting material is used, it must be the starting material forming coal before use in the process according to the invention on to be described in more detail Way to be subjected to an initial or previous partial degassing.

It has been shown that the aforementioned objects and advantages can be achieved with methods as described in the schematic representation of Pig. 1 or in Pig's block diagrams. Figures 2 and 3 are illustrated.

According to Pig. 1, the particulate starting materials are typically stored in separate hoppers 1, 2 and 3 and are mixed in the desired proportions by means of controlled conveyors. If necessary can use the materials in these hoppers drained or partially dried. Palis the material is not dry enough, ea or the mixture is first introduced into a drum dryer 4 before it is introduced into a grinding system 5. In the grinding plant 5, the starting materials or the mixture are crushed, ground or crushed and this under additional mixing brought to a typical particle size at which practically 1OOj £ of the material one size of less than 3.2 mm, provided the particles do not

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already have such a size. Of course However, the particle size can also be coarser or finer than the specified. For limiting or setting A sieve 6 can be provided for the size of the good particles processed in the following preliminary steps. Particle grinding to exceptionally small particle sizes, for example 100J6 smaller are all 0.044mm (325 mesh) or even 50JG smaller are than 0.074 mm (200 mesh), is generally avoided since this is not necessary for optimal results and is unnecessarily expensive is. More precisely, this does not produce any additional result, but only increases the processing costs and this can lead to molded articles which are undesirably "dusty".

Prior to the addition of the plasticizer, the particles are subjected to a conditioning that at a temperature above about 149 ⁰ C, typically between about 160 ⁰ C and about 26O ⁰ C and preferably awicchen about 171 ° G and 232 ⁰ C, but below the temperature at which the particles easily fuse or agglomerate. According to Pig. 1, the main part of the heating of the particles to the ßcwlmsehte temperature by inclusion heating in an Irertpanntron, leg for example

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take place in a conveyor pipe 8 _f after the particles have passed through a chute 7 _f, a weight conveyor 7a and a closure valve 7b. The heat required for the Einsehluß heating system is supplied by the combustion of the gas contained in an air-gas mixture supplied by a mixer 10 in a chamber 9. The heated particles are then separated from the HeiSgaeen in a cyclone tank or separator 11. The desired conditioning temperature, at which, however, no fusion occurs, can be reached in any length of time, and depending on the speed at which the process is carried out or the equipment available, in a short or longer period of time. The particles can also be heated in the grinding plant 5 either fully or partially or in various other ways, provided that an inert atmosphere is maintained or an inert gas system is provided in order to avoid excessive oxidation, which is generally responsible for the fusibility of the particles and the strength of the end product is detrimental.

The cyclone separator 11 typically has one high separation efficiency of more than about 95 ^. The separated solids become a miller

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promoted, where they are mixed with the plasticizer, while the exhaust gases and the remaining trapped particulate matter are discharged from the cyclone separator 11 to another location. For example, they can be fed back into the process via a second cyclone separator 12, which typically has an efficiency of 50% in separating the residual fine particles from the exhaust gases. A part of the residual particulate matter from the separator 12 is then fed to the mixer 17, while another part is returned to the combustion chamber 9 together with the recirculated exhaust gases. Part of the oasis coming from the cyclone separator 12 is returned to the combustion chamber 9 to ensure temperature control of the heating gases, while the excess gas is diverted from the cyclone separator 12 to the outside air. All particulate matter contained in the exhaust gases discharged to the outside air can be incinerated or, after cooling, recovered in a bag filter chamber (baghouse).

The heated particles from the cyclone separator 11 3, as well as some of the particles from the cyclone separator 12, as mentioned, typically on a continuous basis working mixer 17, such as a beater mill or a continuously operating rotor mill, transferred. the end

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Pig. 1 it can be seen that those entering the mixer 17 Particles are heated. The particles are delivered in the mixer 17 with one from a plasticizer container 13 Plasticizer mixed, the temperature of which is kept in the container at such a value that it is a sufficient has a low viscosity, but without boiling or decompose. Either the container or directly the plasticizer located in it be heated, for example by means of a clektrisehen heating device 14 or by means of hot oil or steam can be done. A metering pump 15 can be used to control the Ratio of the quantity of the plasticizer conveyed to the mixer 17 and to be mixed with the heated particles within a range of about 1-8, and preferably about 2-6 wt .- ^ based on the weight of the in the Mixer 17 of incoming particulate matter. This proportion of the plasticizer can also be used express in parts per hundred parts (pph) of particulate matter. In the plasticizer delivery lines leading to the mixer Additional heating devices 16 are preferably provided, with the aid of which the temperature of the plasticizer can be raised rapidly to the approximate value of the particulate material temperature. The heated plasticizer can expediently be sprayed onto the particles in the mixer 17. Typically the mixer 17 is also

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if, for example, heated or heated by burning natural or natural gas in a chamber 18 and discharging the heated gas to a heating jacket 19 so that the particle-plasticizer mixture is kept at the temperature desired for pressing or briquetting. This "elevated temperature" amounts to at least about 149 ⁰ C, but below the Yerschmclzungstemperatur of the carbonaceous solid prior to mixing the same with the plasticizer. The plasticizer and the particulate material are preferably quickly mixed with one another within a short period of time, for example about 0.5-10 min, while they are still at an elevated temperature of above about 149 ° C., during which time the mixture fuses or becomes plastic . The mixture is then poured or, for example, pre-pressed with the aid of a briquette press 20, before it is brought into a non-plastic state by either time-dependent or temperature-dependent overheating. The residence time during which the mixture consisting of the particles and the plasticizer is kept at the maximum temperature before pressing is generally limited to a maximum of about 5 minutes. (Typically, the material flows continuously through the mixer and part of the total residence time is required for the complete implementation of the mechanical mixing zone; the

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Remainder of the dwell time for the implementation or fusion between the plasticizer and the raw coke and / or the raw coal necessary, this conversion in the mixer 17 and also takes place in a hopper 20a, in which practically inert "b ^ w. Oxidation-free conditions been sustained.)

In the molding or compression process, the pressure applied can be varied depending on the temperature of the particles to be compressed, the composition of the mixture to be prepared, the type of press used or the molding process concerned, etc.

The green moldings formed typically have an apparent density between about 0.85 and about 1.25 g / cm 'and a porosity of about 8-37 «6. After this The hot, raw moldings are pre-pressed, for example by means of a conveyor belt 21, which is typically also in an inert or non-oxidizing atmosphere runs, transferred to a coking plant 22, where it gradually, but fairly quickly, for example in eight hours or less, in a practically inert atmosphere in such a way, for example to a temperature of 538 - 1093 C, Throw heated compared to that of their volatile matter content dom its raw state is considerably reduced.

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The procedure described above is do the preferred embodiment of the invention Procedure; this procedure is for you in the Bloekdiagramra illustrated in FIG. Of course, however, they are also within the scope of the invention Changes and modifications to the procedure described above. Such a modified procedure is on the block diagram of Pig. 3 illustrates where the particulate starting materials prior to Heating must be mixed with the plasticizer first, rather than separately heated prior to mixing with the plasticizer be su. The whole mixture is then heated comparatively quickly, the plasticizer during this Heating connects with the particulate starting materials. This heating can be expedient at the same time Mixing of all materials as well as taking place during the conveyance of the substances to the pressing device. While the heating process is the mixture to a temperature of at least about 149 ° C, but below the merging temperature of the particles of the fundamental Coal and / or coke materials lies, heated, whereupon the softened, fused or plasticized Mixture is briquetted or pressed while it is still at a temperature of above about H9 ° C and before it loses its plastic state. the

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Residence time during which the mixture consisting of the particulate material and the plasticizer before the Pressing is at maximum temperature is generally limited to a maximum of 5 minutes. Obviously In this modified process, the residence time at maximum temperature is practically the same as in the process according to Pig. 2. However, since no conditioning is carried out at an elevated temperature in this case, the heating step evidently generally a longer period of time than when heating the softened mixture according to Pig. 2 required or applied to bring the softened mixture to maximum temperature. Of the The briquetting and coking steps are then carried out in the same way as in the Pig pail. 2 carried out. It It is essential that the temperature of the softened particle mixture in all embodiments of the invention reached at least about 149 ° C, otherwise the briquetting is made more difficult and the strength of the coked Briquettes is deficient. The maximum temperatures used and the dwell times at the maximum temperature are variable and must be set separately for each type of composition to be pressed. With everyone given composition, however, there must be precise control of the time and temperature conditions Otherwise the mixture used will not change

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sufficient for satisfactory briquetting softened or overheated or heated too long and turned into a non-plastic, dissatisfying one for promising State is shifted.

The main task of the plasticizers described is in their actual softening effect and less in their effect as a "binder". They are mainly used as processing aids as they facilitate the application lower pressures and temperatures for molding or Allow pressing than would otherwise be possible for the production of solid blanks. The Weichenaacher ergrfc in connection with an inert substance such as anthracite, when heated to the crimping temperature and when crimping not in itself a cohesive briquette. Likewise, the particulate active materials alone yield upon processing in this way, i.e. by heating and packing, too no cohesive body. Only in connection with the plasticizer does the active particulate material result or if the particulate materials are heated and processed in this way, they result in coherent shaped bodies. the end For this reason, neither the plasticizer nor the active particle chemicals are able to act during the process of processing sole binding agent to act, so that the plasticizer the Formvori ^ nfr actually air plasticizer and less

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act as binders. The plasticizers can, however are partially or largely converted into carbon during the coking process, 30 that they then also act as binders.

Other possible and obvious process deviations are to heat the partial starting material or the particulate starting materials, either the active or the inert material, separately from the plasticizer by methods other than inclusion heating, for example in a batch process, in a mill, in a mixer or in a fluidized bed, etc., and then adding the plasticizer to the heated particles. The particulate starting materials can also be initially separated and heated to different temperatures before they are mixed with one another and with the plasticizer. In this case, the inert material can typically be heated to a higher temperature than the active material. The plasticizer may be getrennterwärmt or part 3einer heat or its overall Y refer entire heat from the preheated particles. Other possible process modifications are obvious to the person skilled in the art.

The invention is set out below for better understanding explained using examples.

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Example 1

50 parts of bitiunenhal term coal with a volatile content of 26.1J ^ and 50 parts of crude petroleum coke with a volatile content of 13.50, which exactly Fig. 1 were stored in separate funnels 1 and 2, were controlled with the help of Conveyors mixed with one another in the specified proportions. The material mixture contained about YFO moisture and was dried in the drum dryer 4 by 10 min * exposed to a temperature was about exposed from about 121 ⁰ C. The dried mixture was then transferred to a grinding plant, such as that used for pulverized coal burners, and ground there, with additional mixing, to such a particle size that practically 1ΟΟ $ ί of the mixture was a sieve with a mesh size of about 1.6 T mm ( 10 mesh Tyler sieve scale or about less than 1/8 inch) matched. A sieve 6 served to prevent the larger particles of material from entering the subsequent processing stages of the process.

Most of the heating of the particles to the desired temperature was carried out by inclusion heating in a stream of inert gas in the conveying pipe 8 after the ground and mixed particles had passed through the chute 7 »

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the weight conveyor 7a and the cutoff valve 7b pass through. The weight conveyor 7a was used to precisely control the amount of material entering the conveyor pipe 8. In the present embodiment, the conveyor 7a was set so that it delivered 2118 kg + "% of particulate matter per hour to the conveyor pipe 8. Although the conveyor pipe 8 is drawn horizontally in FIG. 1, it can be at any inclination and even be arranged vertically The conveying pipe 8 in this case had a diameter of about 61 cm and a length of about 6.4 nt in the Luft-Grae mixture supplied by the mixer 10. The combustion chamber 9 was designed to provide a heat quantity of 2.54 million BTU / hour, with 1.73 million BTU / hour of this heat quantity being provided by the Combustion of 0.821 m / min (29

• z

Standard cubic feet per minute) of natural gas in 8.21 nr / min (290 SCFM) air from the air-gas mixer 10 and 0.81 million BTU / hour. by recirculation and / or incineration of the hot exhaust gases and fines from the "fines" cyclone separator 12. The gas emerging from the combustion chamber 9 non-oxidizing gas had a Auntrittstemperatur of about 427 ⁰ C and poured into a

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Amount of 225 m ⁵ / min (7950 cubic peet per minute). This throughput corresponded to a linear velocity of the gases in the conveying pipe 8 of about 15 m / s. The particles were conveyed into this gas stream and had the conveying pipe a durchechnittliche residence time of less than 1 s, during which they were heated to a temperature such that they had a temperature of about 204- ⁰ C after the separation of the gases in Zyklonenabeeheider. 11 Although, as mentioned, high heating rates are preferred for maximum production efficiency, an appropriate period of time, both short and long, or a period best suited to process speeds or the equipment available, can be used, vat that heating particulate starting material to the desired non-fusing temperature prior to mixing with the plasticizer. In addition, the heating of the enclosure 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 typical cyclone heather 11 used is designed to that he is for the mi processing particle size a high separation efficiency of more alo about

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955 *, for example about 97 #. The separated pesticides are then transferred in an amount corresponding to 97J * τοη 2108 kg / hour, ie about 2040 kg / hour an amount of about 63.5 kg / hour TCM cyclone separator 11 can be discharged to another location. The one in Pig. 1 and described in the present exemplary embodiment, these substances were used to a large extent in that they were returned to the process at a flow rate of around 159.3 m / min (5610 CPM), for example via a second cyclone separator 12, which is typically a Efficiency of about 506 in the separation of the Eest fine particles from the exhaust gases. About half of the residual fine particles obtained by the cyclone separator 12, ie about 31.8 kg / hour. » was transferred to mixer 17 while another portion of about 26.3 kg / hr. was returned to the combustion chamber 9 together with the recirculated exhaust gases. Another, even smaller proportion of about 5.44 kg / hour. was destroyed by incineration or, after cooling, rewrote in a bag filter canister. Typically, a damper or slide 12b is used to limit the proportion of particulate matter treated in this way and for appropriate dimensioning

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the portion of the particulate matter returned to the combustion chamber 9 is provided. The outgoing from the Zykloncnabseheidern 11 and 12 shut-off valves 11a and 12a allow entry of solids into the mixer and prevent a flow of gas therein, wherein the supply amount to the mixer effectively by the weight of conveyor 7a is controlled.

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 plasticizer supplied from the plasticizer container 13, which was at a temperature in the container that was sufficient for it to be sufficient to make it viscous, which on the other hand was not so high that it boiled or decomposed. This container and / ^or the plasticizer located in it were heated or heated by means of a heating device H. In the present embodiment, the plasticizer also consisted of so-called "thermal tar" with the following properties:

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1771160 •
Specific weight at 20 / 2O ⁰ C 1.02 Conradson carbon 8.0 wt .-? 6 A3che content o, 00556 Sulfur content O.97 # Distillation (760 mm Hk) Volume. {$>) Temperature ( ⁰ C) Initial boiling point 254 5 • 292 10 316 20th 333 30th 344 40 360 50 376 60 393 70 417 80 457 90 505 93 527 endpoint 95 100

The viscosity of this thermal tar, measured in Saybolt-Univereal seconds at 99 ° C, was 95

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A metering tape 15 was used to control the proportion of the amount introduced into the mixer 17 with the heated one. Particles of plasticizer to be mixed. This proportion preferably varies between approximately 2 and 6 parts by weight per 100 parts of the particulate material entering the mixer 17 or between approximately 41.6 and 125 l / hour. In the present exemplary embodiment, 5 parts or 5% by weight of thermal tar were used. In the softener supply lines additional heaters 16 were provided for the rapid increase in the temperature of the plasticizer is from about 149 ° C to about 204 ⁰ C euf amount Teraperatunrert ends of the particles, which also represents the desired temperature for briquetting. These additional heating devices are used for the reason that it is not advantageous to heat the softener at this temperature for too long before mixing it with the heated particulate material. The heated plasticizer, which now has reduced viscosity, can expediently be sprayed onto the particles in the mixer 17. The mixer is typically also heated by hot elements, for example from the combustion of natural gas in a chamber 18, where for example about 0.023 m ^ / min (0.8 SCPM) natural gas in 0.25 mVmin (8.8 SCM) air an amount of heat from 51 170 BTü / hour supply, originate and introduced into a heating jacket 19

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I? :

so that the aue of the particulate material and the The mixture consisting of plasticizers is kept at the temperature desired for pressing or briquetting while the combustion products are discharged from the heating jacket to the forge. The plasticizer and the particle material were then quickly mixed together in mixer 17, their maximum residence time being about 15 min and is preferably about 10 minutes, and were then in a twin-roll briquette press 20 at one pressure of about 1970 kg / cm at a temperature of about 204 ° C pressed before the mixture formed became nonplastic. The hot, raw moldings were then made in an amount of about 2040 kg / hour. with the help of Conveyor belt 21 transferred to a coker 22, in which they gradually within 6 hours. In an inert atmosphere heated to a maximum temperature of 962 ° C.

The briquettes produced had a pillow or block shape with a length of 76 mm, a width of 50.8 mm and a maximum thickness of 38 mm. The raw bodies produced according to the invention can, however, also have other shapes and, for example, be semi-cylindrical, tubular or toroidal, etc., which is of the notYrenaiskeit orter expediency of the porosity of the Packing bed of the oven in which they are used should, depends. You can also use these modified forms

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be resorted to to the rapid evaporation of volatile substances during the coking step and thus a quick implementation of this process step and at the same time the formation of bubbles, puffs or chips, etc. during coking reduce to a minimum. In general, however, the raw bodies according to the invention are dimensioned so that for at least one of its dimensions does not exceed about 50.8 mm.

In the example described above, 50 parts of high petroleum coke, 50 parts of coal and 5 parts of soft maize were used, each based on weight. Typically and preferably, the active materials used comprise a mixture of coal and raw coke which contains 15 - B5f> a charcoal capable of coking and correspondingly 85 - 15j6 raw coke, preferably raw petroleum coke. According to the Pig. 2 and 3, small amounts of inert substances can be added to these active basic substances.

The examples listed in Table I below
illustrate the effect of some predecessors of the process according to the invention on the properties of the coked moldings obtained. The same coal and raw petroleum coke were processed.

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and the same rolling pressure was applied as in Example 1, while the different types of plasticizer and proportions indicated in Table I were used. In all examples, the coking time was 6 hours, the heating taking place uniformly to a final temperature of 961 ^° C. within this period of time.

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Table I.

(O 00 CD

«Ο

money coke Plasticizer (parts per Gemi Solltem (Weight-96) (Wt. -96) 100 parts coal and temperature At, ST) i el 50 50 Coke) ( ⁰ C) 2 50 50 5.3 - coal tar 154 3 50 50 5.3 - coal tar 174 4th 50 50 5.3 - coal tar 176 .5 50 50 5.3 - coal tar 178 6th 50 50 5.3 - coal tar 205 7th 50 50 5.3 - coal tar 228 8th 25th 75 2.7 - thermal tar 179 9 25th 75 ■ 5.3 - coal tar 171 10 25th 75 5.3 - thermal tar 180 11 25th 75 2.5 - thermal tar 182 12th 25th 75 7.5 - Cabbage tar 177 13th 0 . 100 7.5 - coal gate 178 14th 0 100 2.7 - coal tar 225 15th 0 100 5.3 - coal tar 188 16 0 100 5.3 - Cabbage Cr 223 17th 75 * 25th 7.5 - Cabbage tar 204 18th 75 * 25th 5.3 - coal tar 193 19th 75 * 25th 5.3 - coal tar 179 20th 75 » 25th 5.3 - thermal tar 191 21 100 * 0 2.7 - coal tar 208 22 · 100 * O 5.3 - Cabbage Cr 171 23 100 * 0 2.7 - coal tar 190 24 100 ** 0 2.7 - thermal tar 195 25th 5.0 - coal tar 267

modified

Drum test Apparent

(Wt .- ^ + 25.4 mm) density

72.1 1.12 73.9 1.14 79.2 1.12 72.9 1.15 86.8 1.20 62.2 1.19 63.2 1.10 80.8 1.33 81.6 1.28 71.7 1.26 82.3 1.39 84.2 1.33 60.2 1.40 56.2 1.42 56.7 1.44 52.6 1.43 61.3 1.13 64.7 1.16 60.1 1.11% 66.5 1.12 * 59.6 1.09 ' 55.4 1.06 53.2 1.01 57.8 0.90

• Bitumen coal, degassed to a volatile matter content of about 20 ?. ** Mixture of 90? $ Bitumen, cntpast to volatile matter content of 20 $, and 1OfS anthracite.

In the examples described above, as well as in Example 1, regular size carbon and Coke materials used. "Regularly sized" material is characterized by the following screen mesh analyzes s enval e t

Mesh size 3.2 ram 2 , 0 mn money Petroleum coke above 3.2 - O f 84 nn & 0.00 0.00 2.0 - O , 42 mm 1.04 0.42 0.84 - 0 , 149 am 15.22 11.07 0.42 - η 34.96 34.54 0.149 m 26.62 27.59 under 22.70 25.27

The "normal temperature ¹¹ " means the temperature of the mixture immediately before briquetting. The Yerpreßfona was typically kept in the heated state for molding. The modified drum test corresponds to a standard drum test, the only difference being that a smaller batch was used in the first cm the conditions for carrying out the test were made more difficult and results were lower than those obtained with the Horm-Iest. The properties of the thermal tar have already been described. The coal tar used had the following properties:

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Coal gate - properties

Specific density, at 25/25 ⁰ C 1.20, Benaol-Insoluble, wt-96 6 #

Viscosity at 25 C 900 cp

Distillation (D-20)

bi3 to 270 ⁰ C 2.65 #

270-36O ⁰ C. 13.6096

Radical or about 36O ⁰ C "83

Further experiments were carried out as described in Table I using similar conditions, but the raw petroleum coke replaced with calcined petroleum coke, the plasticizer omitted or as coal such a high content en volatiles in proportions of 5Oj6 and more of the mixture was used this coal had not been partially degassed prior to use. In all of these cases unsatisfactory results were obtained.

As mentioned, the method according to the invention can be used using of uncalcined raw coke as the only active particulate starting material has been carried out; if this type of coke is used alone, the coke possesses

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a volatile content of at least about 105 ^ and up to about 2O? 6, preferably in the range of about 11 - 16 #, with the exception of the existing Wasier. The said Raw coke can be used as a fusible residue from thermal cracking or coking of petroleum-hydrocarbons, Cracked asphalt, distilled asphalt, cabbage ent eerpech, Wood tar pitch and the like. Can be obtained. As mentioned, however, a particularly useful and preferred raw coke is raw petroleum coke obtained in a delay coking plant. The process according to the invention can also be carried out using raw coal or partially degassed coal as the only active, particulate feedstock so long as the content of the coal of volatile substances does not exceed about 2OfS. The usage from raw coke alone or from coal with the corresponding volatile content alone is in the examples given in Table I. As can be seen from the drum tests, mixtures result from Coal and raw coke have higher values and are therefore preferred for the process according to the invention.

Only those can use the method according to the invention Raw types of coke are used that have a content of volatile substances in the range of about 8 - 20J $ b2w. from 10-2056 if Bie is the only particulate active material

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are used, or which are degassed in a separate process step, 30 that the contents of volatile substances are in this range and preferably in the range of about 11-16) 6. Cokes with a volatile content of more than about 20 ^ _1, not including water, generally experience difficulties in the coking step due to excessive fusibility. Raw cokes with a volatile content of $ 10 or less when used without charcoal present difficulties in that they do not allow for fusion with the plasticizer. Raw cokes with a low sulfur content are also preferred.

If the raw coke has a volatile content of more than about 20) ί, it can be under controlled Conditions in which local overheating should be avoided is, in order to reduce its content of volatile substances to a value within the specified ranges be heated, which can be done at comparatively low temperatures of around 260 - 558 ° C. Here proceed carefully so that no oxidation occurs and the content of volatile substances does not drop to a value is reduced below the specified ranges.

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The plasticizer should neither evaporate significantly at atmospheric pressure nor below a temperature of about 254 ° C substantially thermally decomposable eeinj these The temperature is considerably higher than the temperature at which the amalgamation effect of the Plasticizer occurs with the raw coke and / or the coal. Substances suitable as plasticizers are coal tar, Coal tar fractions, coal tar pitch, certain high boiling points Hydrocarbon oils and residues resulting from the cracking of petroleum distillates, such as Thormalteor, Petrolpech, Wood tar pitch, aritoracen oil, heavy wood tar oils and pitch, heavy lignite oils and pitches, phenanthrene and the like .. Heavy petroleum hydrocarbon residues and Asphalts, both cracked and distilled, can also be used as plasticizers.

The choice of a plasticizer, which can also be referred to as a softener or fusing agent, depends on a number of factors, for example on the material or materials with which it is to be fused, its cost, etc. Any plasticizer can be used which is partially compatible with the Raw coke and / or the coal used melts, but not all plasticizers are exactly the same. Preferred are aromatic hydrocarbons. The oxygen and

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Oxygen derivatives of aromatic hydrocarbons Bind also usable, but inferior to hydrocarbons »The plasticizer should not be essential Contain proportions of substances that decompose with the delivery of strongly oxidizing decomposition products. Eyeloparaffinic hydrocarbons are useful or their derivatives, for example the furfural extract of heavy lubricating oils. In many cases, mixtures of hydrocarbons and their derivatives can be advantageous can be applied.

As mentioned, the plasticizer should preferably be at one Temperatures well below about 254 3 are not subject to evaporation or decomposition. Of course During the coking process, a certain amount of volatile hydrocarbons and other by-products of the pyrolysis of the plasticizer, but the most beneficial plasticizers are those that are in large Extent can be converted into coke. With excessive formation of vapors and gases, the porosity of the coke bodies becomes unacceptably increased. In view of the small amount of plasticizer used, which in no case above about 8 «£, and a certain porosity is created there Molded body is desirable, dien in general no problem. Materials with a high sulfur content

109883/0494

BATH ORIGINAL

contents are generally undesirable because they are more metallurgical High sulfur coke is often rejected by consumers.

The ground coal and / or the raw coke and the plasticizer can, if this appears expedient, be premixed at room temperature, and especially when the plasticizer is in finely divided pesticide form. Likewise, the normally liquid plasticizers can be mixed with the coal and / or the coke in the cold state. Optionally,-this can be done mixing at elevated temperatures by the coal or coke or a fairly uniform mixture of carbon and / or raw coke and plasticizer to a temperature of above about 149 ° C and typically from about 160 - 26O ⁰ C, preferably from 171-232 ⁰ C is heated, while the mixing is carried out in a suitable device in such a way that the mixing and Erwsehen bsw. Merging take place at the same time. The correct time-temperature factor for this blending treatment is quite critical and varies depending on the volatile content of the coal and / or the raw coke and the leveling agent used and its viscosity. In any case, the softened particles should not be too long and / or not too long before pressing

109883/0494 - 34 -

BATH ORIGINAL

high temperature, since it is possible that such a treatment makes the softened particles "non-plastic ¹¹ and thus leads to difficulties in the shaping of the green bodies or gives green bodies of insufficient strength. These time-temperature conditions or residence times at maximum temperature can be easily determined for any given mixture described on the basis of the guidelines explained and using the compressibility of the softened particles and the properties of the fired briquettes as criteria after the moment at which the softened particles approach or reach their maximum temperature.

In certain cases, the mixing can with about 38 - 93 ⁰ C held heated raw material, but below a temperature at which the Verschmclzungewirkung is initiated or is fully advanced, whereupon dio processing at higher temperatures followed.

As mentioned, the fusion treatment must be carried out carefully be controlled in such a way that they do not go too far

109883/0494 "' ^y} ~

BATH ORIGINAL

advances. This control can usually be done using the temperature, although also the time factor plays an important role. When heating a mixture of a plasticizer and coal and / or raw coke during mixing at a temperature above the specified range or above that for the subject Mixture at the desired maximum temperature, the mixture first passes through a paste-like state and changes afterwards in its properties and becomes too dry for extrusion and thus for example according to a continuous roller briquetting process difficult to pre-press. In other words, the softened mixture of coal and / or raw coke should itself be one Ensure the lubricating effect on the briquetting molds. at Certain plasticizers can cause this over-treatment in the specified Temperature range take place if the treatment time is too long and, for example, more than 5 min or less. As mentioned, the critical influence of the time and temperature ratio changes in the merging step depending on the amount and the type of plasticizer used and also depending on the content of volatile substances and on the particle size of the coal and / or the raw coke. In general, they typically merge with one another in accordance with the invention Yerfehren used fine coal and / or

1Q9883 / CU94 ~ ³⁶ "

BATHROOM ORIGlNAt

Raw coke particles due to their large surface and very light due to their small diameter.

When the fused mixture is passed beyond a point at which it is easy or strangprese- ver preesbar and pourable, it is not only difficult to extrude or briquetting means of rollers, but also leads to moldings which exhibit flaws or cavities and may have lower strength during or after the coking process. If a mixture has progressed too far in the fusing step, it is in some cases possible to add a small amount of plasticizer and thereby restore its briquette or extrusion properties. However, if the amount of the additional plasticizer added is too large, the coked bodies may develop poor strength and, to an undesirable extent, increased porosity due to the increased volume of vapors which must be expelled. In addition, this increases the shrinkage of the coked bodies. The fusion temperature should also be below the temperature at which the plasticizer begins to decompose or to a substantial extent begin to separate out of the mixture; With most of the plasticizers used according to the invention, however, this does not occur until Erroichcn at the earliest

109883/0494 " ³⁷ "

BAD ORfGfNAL

Temperature of about 254 ° C.

The application of mechanical pressure or the pressing of the softened mixture of coca and / or coal can be done in many different ways, for example preferably by roller briquetting, extrusion, Injection molding by means of a piston press or by molding. '

The softened types of coal or raw coke that can be used in the process according to the invention must, after pressing or briquetting, have such properties that they have little plasticity and no flowability in all stages of the coking process. If the coal or coke has too high a volatile content or the softened mixture tends to melt and flow before the decomposable components of the raw moldings have decomposed, the tiny channels leading from the inside of the moldings to the outside seek to Via which the decomposition vapors escape, they become clogged, which results in processing difficulties during coking and the formation of large pores and coked moldings with insufficient strength. Eei production of the moldings aue materials with the properties mentioned above and the explained methods according to the invention

109883/0494 - 38 -

BAP ¹

However, no such material flow occurs and the steam escape channels remain small and distributed over the entire molded body to be coked, so that the gases are able to escape quickly and without producing large pores or channels.

If, in the process according to the invention, a coal with a volatile content of more than about 20% and up to about 45 $ is to be used and in such an amount that the mixture formed from the coal and the petroleum coke has a volatile content would have more than about 20 wt. · 4> , it is necessary to partially degas this coal in any manner known to the person skilled in the art, so that the volatile matter content or the gas content of the mixture obtained is at most about 20ji. If this partial degassing of the coal leads to excessive agglomeration or balling of the coal, it can be partially crushed and brought to an acceptable particle size, whereupon it can be used as a raw material in the process according to the invention.

All materials in the mixture to be briquetted or compressed are generally based on essentially heats the same temperature, making the different

109883 / 0A9A " ³⁹ "

BATH ORIGINAL

If, for example, a practically inert material such as anthracite is used, this is typically only heated to working temperature, while on the other hand the coal and / or the raw petroleum coke, which are mixed with the plasticizer, is subjected to a melting effect The time and / or the temperature during which the particles are held in this heating stage or to which they are heated depend on various other factors in addition to those already mentioned. consists of raw petroleum coke, ie contains no coal and no inert material, and has a gas content of about $ 12, the ratios are different than when it is, for example, 10056 raw petroleum coke with a gas content of 15J & or 18 # or if the particulate material is too 50? S consists of crude petroleum coke and $ 50 from coal, etc. When using vo In addition, raw petroleum coke with a volatile substance or gas content of 8 or 9 ^ is not used on its own, but is typically used in conjunction with considerable amounts of coal. Obviously, in the case of coal compositions of the type listed below, the time and temperature conditions also change; these changes are of course within the

109883/0494 " ⁴ °"

ι * ■ ■

The scope of the invention. For example, the starting materials listed in Table II can be worked up.

- 41 -

1Q9883 / 0A9A

BATH ORIGINAL

1098 a) • petroleum coke Gas content • Table II Gas content OO
co ^) Parts 13th Bituminous coal "ν.
O _? ) '100 13th Parts - co
* «- 100 13th - r) 100 13th
13th
13 - - 45
20th H) 100
90
90 12th - 23 BAD ORIC 70 20th 10
10 4O ⁺ so 9
10 30th 17th
23 I) so
30th H 50 26 ⁺ T "0 30th 15th 50
70 3O ⁺ "■) 20th 11 70 25 ⁺ O) 20th 9 80 45 ⁺ ■ n) ? 0 15th 80 37 ⁺ 10 _ 80 37 ⁺ _ 90 100

Plasticizers

uf 10Q parts of coal;

Parts (qgf 100 parts)

7.0

6.0 6.0 5.3 2.7 5.3 5.3 2.7 1.5

5.3

Asphalt anthracene oil

Thermal tar

Petroleum pitch Thermalteer ^Kohlcnteer] coal tar Thermalteer coal coal tar coal tar Thermalteer Kohlent EERP ech Thermalteer Kohlent e he Thermalteer ". *

With the mixtures h, k, 1, η, η. ο and ρ became the Bituminous coal partially degassed (so that the gas content of the Coal-petroleum coke mixture does not have a value of about £ 20 exceeds) before it is mixed with the petroleum coke and treated according to the method of the invention. In all cases the particulate matter was during the Interleaving-heating step within the previously specified tent spans bo long and / or on a so high (also within the previously mentioned temperature ranges lying) temperature warmed that the desired softening and icing was caused, but not for so long and / or at such high temperatures, that the resulting fusion became non-plastic.

The molding device 20 or the rollers of the. Briquetting machines can be at any temperature and for example, the same temperature as the particles, a higher temperature, room temperature, or one between them Areas have lying temperature, etc. The briquetting orphans can be water, oil or in some other way be chilled. Before briquetting, they must be warmed up Pest substances from undesired oxidation by atmospheric air must be protected as this would be detrimental to the strength of the end product. Obviously, the Presence of excess air also carries the risk of a Igniting and burning. An inert gas atmosphere can therefore be provided.

The pressure applied during pressing changes depending on the temperature of the softened clay to be molded Partial materialo, the respective composition, the other

109883/0494 - 43 -

BATH ORIGINAL

applied press type or the relevant molding process, etc. In a piston press, this pressure is between about 35 »2 and about 1050 kg / cm, with lower pressures being used at higher temperatures and vice versa. In a roller press, the pressure (P) is typically between about 281 and about 6330 kg / cm when 3? = T (A η total area of the pockets under pressure along the line of contact between the rollers; F = pressure exerted on the rollers of the press). For example, mixed ^{temperatures of H9 - 177 0} C and pressures of 70.3 - H1 kg / cm in a piston press can lead to insufficient strength of the raw and / or the sintered molded body, while temperatures of about 177 - 232 ⁰ C and pressures of 35 » 2 kg / cra moldings can provide good strength. Typically, only so high a pressure should be applied "that a green molded article with a porosity of at least» SjC is obtained, while on the other hand at least such a high pressure should be applied that a raw molded article with a porosity of at most 37 # is obtained. In other words, if the porosity of the formed shaped body is below 8 # or above 37 ^ or otherwise not within a desired, satisfactory range, the pressure applied can be reduced or increased accordingly until the porosity of the resulting green shaped body is the desired value -

101813/0494

BATH ORiGINAL.

enough. Preference is given to raw moldings with a porosity from about 15-3Oj6.

A roller press is preferred for size production. When using such a device, the "Verpreeezeit" is i.e. the time during which the deformed, reproached particles actually undergo Or during which pressure is actually exerted, usually less than 2 β and typically shorter than 1 s. Of course, molding devices other than those mentioned above can also be used can be applied.

In the pail of ram presses, prints of applied below 176 kg / cm, since higher pressures only one Mean waste of energy. According to the invention for many processed carbonaceous mixtures or compositions, in particular those with a high gas content, the briquettes or moldings are obtained at pressures of above about 24-6 kg / cm increasingly defective Places (voids), specifically after coking the same. In piston presses are therefore generally Avoid prints greater than about 28.1 kg / cm unless otherwise substantial amounts of "inerts" to be processed Mixture has been added or that to be processed

109883/04 Qi

ORIGINAL

Mixture has a low gas content; in such cases it may be advantageous to use higher pressures. In roller presses, higher pressures are used.

The raw moldings should have a minimum porosity of about B $ so that the least possible difficulties arise during pressing and coking and the coking can be carried out quickly. If the porosity of the molded body is too low and rapid coking of such molded bodies is sought, the escaping residual gases or volatile substances tend to break up the molded body, so that coke is obtained with a size and strength unsuitable for metallurgical processes.

The porosity of the molded bodies produced becomes a matter of course also by changing the temperature to which the fused particles are heated, or affects the composition used for the production of the hollow moldings. As mentioned, the The porosity of the raw moldings is at most 37 ^. If the porosity is higher, the moldings are either closed not very firm or, after coking, they appear to be too low for the intended use Density «, the apparent density of the coked moldings

109963/0494 -46-

BATH ORIGINAL

Style·,.

is generally around 1.0-1.5 g / cm ³ . The density of the raw moldings should be between about 0.85 and g / cm, the less dense moldings of course having a higher porosity and the denser moldings a less high porosity.

After pre-pressing the fused or softened Particles, the raw fora bodies formed are preferably coked practically immediately and without substantial cooling. If the temperature of the molded body can drop too much between the pressing and the coking, the The likelihood of the formation of cracks and voids in the shaped bodies is greater than in the case when the shaped body cokes immediately and without significant cooling will.

The particles 26O ⁰ C, mixing with the plasticizer, pre-pressing of the fused particles, while - in the preferred mode of operation, wherein the particles are initially heated separately before de "mixing with a erwäret en plasticizer, the duty cycle lasts of heating the particles to about 149 they are still at a temperature of about 149-260 ° C., ie with little or no cooling before the molding process, and the molded bodies are not transferred into the coker for longer than approximately

100883/04 «* -47-

BATH ORIGINAL

10 min. During these phases of the process, no significant "shocks" are permitted in the work cycle. The heated carbon-containing parts or the deformed masses to be processed are kept in very even motion, avoiding any significant build-up. Dams "can, however, in a possibly preceding Yorerwarming step, in which the particles to a predetermined, comparatively lower temperature of about 93 ⁰ C

be brought, or in the subsequent Yerkokungsstufe occur without this having a significant or significant effect on the quality of the product manufactured or has the trouble-free procedure.

If the above-described procedural steps are strictly observed, the pressed molded bodies can be coked "quickly", that is to say much faster than in the time usually required for the coke oven process of 18-24 hours, by "for example without deterioration of the product quality within a period of up to 8 hours to a Tenporatur of about 538 -. heats 1093 ⁰ C warden or bi3 is a gas content of the product of 5r> or less achieved Yerkokungszeitspannen of 3-6 hours are typical course also longer periods of time than...

109883/0494 -'M-

BATH ORIQINAL

θ h are. applied, but is diee generally disadvantageous.

During the treatment in the hot coking plant -22 , the raw moldings are generally not subject to any re-softening or sticking together, since they have been "fused" and molded into separate individual moldings, producing a firm, self-hanging bond within the raw moldings. Aue this reason, the bonding between the particles in the individual shaped bodies is very good and have the coked molded articles produced typically superior strength. in certain compositions and in certain circumstances, however, a tendency for a tacking together of the briquettes may be made while dos Verkokons. in this case, the briquettes are subjected to a short or limited surface oxidation, so that they solidify and a re-softening during the coking is prevented.

The raw moldings can be coked in a coking device, in which a practically inert or non-oxidizing atmosphere can be maintained. For best Ergebnis3e ^v eats the Yerkokunge device 22 is so designed and the Arbeiteweiee

109883/0404 -49-

BAD ORlGiNAl.

This device is regulated so that the raw moldings can be heated to the desired end coking temperature with proper regulation. When the desired final temperature is about 800 ° 0 and the raw molded bodies have a temperature of 204 ⁰ C, if eie emerge from the forming device 20 and entering the coker 22, its heating takes place from 204 ⁰ C to 800 ⁰ C, preferably with very accurate controlled heating speed of nfht more than 400 ° C / hour. up to a temperature of between about 500 ° and 65O ⁰ C and then of not more than about 500 ° C / hr. to the final temperature of 800 C. Lower heating rates are typically applied until the raw molded body has a critical temperature is reached or until they are "solidified" permanent, typically at a temperature from 600 to 700 ⁰ C, followed by a slightly higher Aufheizgepchwindigkeit to the desired final temperature can be applied. Heating method described above Da3 is preferable to a heating method, wherein the hot molded articles are, for example, exposed to a harsh or wide temperature difference of 200 ⁰ C to 800 ⁰ C immediately. In addition, the temperature of the shaped bodies is preferably increased in a practically linear manner within a predetermined period of time. This means that the heating is fairly uniform with a heating rate of no longer ale

109863/0404 - 50 -

BATH ¹

1O ⁰ C in every minute during the initial heating time, which should not ^{include more than 40O 0} C heating per hour, and of no more than about. 13 ⁰ C per minute during the period of time during which clic moldings are not to be ^{heated by more than about 500 0} C per hour, instead of heating the moldings for one hour at 500 ⁰ C, for example, and then heating them for a further hour long to move into a zone with 600 ⁰ C etc.

Controlled temperature gradients that are lower than those specified above and, for example, cino temperature increase of 300 C per hour bsw. Not exceed 8 ⁰ C per minute and in which, for example, a Angev Srwärmungsgeschwindigkeit of 3 ⁰ C per minute / andt is, are still more typical examples of the generally used in accordance with the invention on coking temperature gradient. The heating rates selected and used within the ranges described above also depend on the density, the porosity, the size, the shape and the volatile content of the raw moldings to be processed below.

Rotary stoves, fur stoves and walkways with in the course of the Shaped body movement gradually higher through the coker

100883/0494 - 51 -

BATH

Temperature suns in which a practically inert atmosphere can be maintained, are advantageously quiet for the heating described above.

After heating the molded body to the desired temperature · Ttm they are gradually cooled usually in an inert atmosphere to a temperature of about 104 ⁰ C or less. A uniform device, which has both heating and cooling zones, can be used both for coking and for cooling; Alternatively, the cooling can also take place in a separate device. The cooled shaped coke bodies, which can be referred to as "porcelain coke ¹¹ ", can then be stored in a product shaft, dispatched immediately or used directly in a cupola furnace, a blast furnace or the like.

In general, coking temperatures of at least about 538 ⁰ C are required, while higher temperatures of for example about 800-960 ⁰ C for optimum results, are preferred. Temperatures of about 96O ⁰ C, for example up to about 1093 ⁰ C, can also be applied, but are not, in general, for the supply of an industrially satisfactory product required.

109883 / CU94 - 52-

BATH ORIGINAL

Iks ,,, "- ■

1771180

The content of volatile substances or the gas content of the raw coke and coal types, which are used in the method according to the invention, is determined according to ASTM method No. D271-48, modified for peat and lignite, and excludes the water content. Gemäfl this method is about 5-10 heats a comparatively small sample of raw coke or coal minutes at about 510 ⁰ C. The difference in weight of the sample before and after the Srwftrmen represents the "gas content ¹¹ dos tested material. As noted, have the Rohkok33orten used in erfindungsgemäSen method preferably not only a prescribed gas content bsw. Volatiles content zwiechen about 8 and 2O # and preferably? ! w ± rule about 11 and 16Ji when used in conjunction Rait coal or of at least 1OjC when used alone, but also form a hard coke agglomerate or "grain", if it has been heated by said dom ASTM method, wherein _t 1edoch instead of a 1 g sample, a sample of 5 g is used. The latter property is important when the raw coke is used as the only active, particulate ingredient.

- 53 -

109883/049 /, BADOfWWt

Claims (1)

Claims 1. A process for the production of metallurgical coke moldings, characterized in that first a mixture of 15-85 parts of fusible coal particles with a volatile content or gas content of at least about 15 # »85-15 parts of particles of raw, uncalcined coke made by coking a heavy liquefiable hydrocarbon to a volatile matter content of about 8-2Oj6, with the exception of water, and about 1-8 parts of a plasticizer based on the weight of the coal and raw coke particles, of, is at a temperature below about 254 ⁰ C do not significantly vaporized still substantially thermally decomposable wherein the average gas content of the coal and Rohkoksteilchen about not exceed together 2Oj6 that then the plasticizer is at least partially fused with the coal and Rohkoksteilchen 'wherein the coal and coke particles in a mechanical pressure pl Aestical material can be converted by the substances forming the mixture in a practically inert gas system 109883/0494 - 54 - BATH ORIGINAL a temperature of at least about 149 ° C, but below the fusion temperature of the particles of coal and coke base materials are heated, that then the heated, softened, still in a plastic state and at a temperature of above about 14-9 ⁰ C located Mixture is compacted in a practically inert atmosphere under a pressure of above stvra 35.2 kg / cm, with raw moldings with an apparent density of at least 0.85 g / cm and a porosity of at most 37 # are formed, and that finally the moldings be coked in a practically inert atmosphere with uniform Aufheizgeschirmdigkcit to a temperature of about 538 - 1093 ° C. 2. Process for the production of metallurgical coke moldings, characterized in that initially a mixture of 100 parts of fusible coal particles with a Content of volatile substances or gas content of airido-Btens about 15 # and at most about 20 ^ 3 and 1 to 8 Parts, based on the weight of the Kohlcteilchen, a plasticizer is produced, which is not significantly evaporable below a temperature of about 254 ° C is still substantially thermally decomposable that the plasticizer is then at least partially fused with the coal, with a below created! maohani 109883/0494 BATH ORIGINAL see pressure plastic material is made by the substances forming the mixture in a practically inert atmosphere to a temperature of at least around K9 ° C, but below the insolation temperature the particles of the coal base materials would be heated, that afterwards the heated, softened mixture, while it is still plastic and at a temperature of located above about 149 ° C, compacted under a pressure of above about 35.2 kg / cm, throws being raw Shaped body formed with an apparent density of about 0.85 g / ca and a porosity of at most 37 # and finally the moldings come in handy inert atmosphere with a constant heating rate to a temperature of approx. 538 - 1093 C. be coked. 3. Process eur production of metallurgical coke porous bodies, characterized in that first a mixture of 100 parts of raw, uncalcined coke particles, which by coking a "heavy liquefiable hydrocarbon" to a content of volatile substances, excluding water, of about 10-20 ° C. is produced were, and about 1 to 8 parts by weight of the bezogen- Kokst eil chen, a "plasticizer is prepared, which is below a temperature of about 254 ⁰ C. 161113/0494 - 56 - BAD ORIGINAL · ^ 1771180 Neither practically vaporizable nor essentially thermally replaceable, so that afterwards the plasticizer fcumindeet is partially fused with the coke particles, the coke particles being converted into a material which, under applied mechanical pressure, eats flat, while the substances forming the mixture become practically inert Atmosphere to a temperature of at least about 149 ⁰ C, but below the Versohaeleung temperature of the particles of the coke base material, so that the heated, softened mixture then in a practically inert atmosphere, while it is still in the plastic state and at a temperature above about 149 ⁰ C, is compressed under a "pressure of above about 35" 2 kg / cm, with raw moldings with an apparent density of at least 0.85 g / cm * and a porosity of at most Wf * are formed, and that finally, the shaped body in an inert atmosphere substantially uniform AufheiEgeschwindigkeit to about 53β - 1093 ⁰ C verk be oct, 4. The method according to claim 1, characterized in that the practically the same amounts in the compacting mixture used on coal and raw coke. 109883/0494 BATH ORIGINAL 5. The method according to claim 1, 2, 3 or 4 _1, characterized in that the coal and / or Hohkokteile are heated prior to mixing with the plasticizer. 6. The method according to claim 5, characterized in that the "plasticizer before mixing with the charcoal and Raw coke is heated. 7. The method according to claim 5, characterized in that ^ the coal and / or raw coca particles by means of inclusion heating the particles are heated in an inert gas stream and that the heated particles prior to mixing be separated from the inert gas stream with the plasticizer. 8. The method according to claim 1 or 3, characterized in that the raw, uncalcined coke iet a raw petroleum coke obtained in a delay overcoker, 9. The method according to any one of the preceding claims, characterized in that the coal and raw coke particles all have a particle size below about 3.2 µm. 109883 / Q494 BATH ORIGINAL 10. The method according to any one of the preceding claims, characterized characterized in that the molded body sehnoll and jn be coked for a maximum of 8 hours. 11. The method according to any one of the preceding claims, characterized in that the mixture to be compressed, an inert material is added in amounts of up to 25 parts per 100 parts of the outside of the coal and / or the raw coke and the inert mixture existing mixture. . 12. The method according to any one of the preceding claims, characterized marked that in the mixture to be compressed 2 to 6 parts of plasticizer are used. 13. The method naoh one of the preceding claims, that as
known by the fact that / Woichmacher thermal tar (thermal tar) is used * A method according to any one of the preceding claims, by that the mixture "is including partially heated» Verschraolaen maximum at about 160 ° to 260 ⁰ C, and that the Geniech is held in front of the compacting at most about 5 minutes at this maximum temperature. 109883/0494 - '- BATH ORIGINAL 1 * 5 * Verffiftron for a dor preceding claims _f DA "dtireh in that at least one dimension of the raw molded body fitirüh compacting mm produced a value of about 50» does not exceed 8. 1 & * ancestors according to one of the preceding claims, characterized characterized that daö compaction using a of at most 2 β takes place. 1? «Method according to claim 5« characterized in that the maximum temperature is approximately 171 and approximately 232 ⁰ C » IS »method according to one of the preceding claims, characterized Gelennzeiehnet that the compaction by means of a roller labeling process is carried out. 19. The method according to claim 2, characterized in that the raw mixture to be compacted, unkaleiniertor Koke, the volatiles s by coking of a heavy liquefiable KohlenwÄßSerstoffs to a content, excluding water, of about 8 - 20 $ mirde prepared, ir a.! close is from bi3 zn to 15 parts per 100 parts of carbon!. 109883/0434 BATH - 60 - 20. Ancestors according to claim 3, characterized in that the mixture to be compressed meltable coal with a volatile content of at least about 1556 in an amount of bin πυ 15 parts per 100 parts of the raw, unkalziniortcn Eolcnes is added, and daft the average The volatile content of the raw coke particles and coal combined does not exceed about $ 20. 109883/0494 BAD ORlGlNiAL