BE510545A - - Google Patents

Description

       

    <Desc / Clms Page number 1>
 



  PROCESS FOR DETERMINING THE COMPOSITION AND COKEFIING PROPERTIES OF A COAL, AS WELL AS THE COMPOSITION OF THE LOAD. TO BE INTRODUCED IN A
COAL CARBONIZATION PLANT.



   The present invention relates to a process for determining the composition of the feed to be introduced into a carbonization plant in order to obtain, in this plant and under good explosive conditions, the same coke - a standard coke already obtained in that plant. here and under good operating conditions, from a charcoal or from a known mixture of charcoals, carbonized at the rate of carbonization imposed by the quantities of products to be supplied by the satilation in a given time. Little is known about the components of coal and their respective molecular structure, as well as the chemism and mechanism of carbonization and coking.



   Consequently, none of the many empirical methods of examining coals, recommended and applied to date in laboratories, with a view to determining the coking properties of coals or mixtures (possibly including carbonaceous substances other than fossil coals). - les) ensured scientific mastery of industrial coking, so that from its inception, the coke manufacturing industry has remained largely empirical in character.



   In the absence of appropriate scientific criteria, the methods for determining the coking properties of coals, among others the psmmaeric, dilatometric, viscometric, penetrometric, posoimetric processes have benefited or still benefit from a wave which is not related to their real value.



   In all areas of use of coals and mainly in the coal upgrading industries, such as carbonization, hydrogenation, gezation, separation of petrophic elements from coals, extraction of coals by solvents , etc ..... the gaps in scientific knowledge relating to charcoal as well as the absence of appropriate methods for determining the composition of charcoal and their coking properties constitute a very serious handicap.

  <Desc / Clms Page number 2>

   rieuxo
The empiricism currently of rule in the manufacture of coke leads to the industrial production of cokb, whose characteristics,

   in particular the rate of calibration stability, the rate of swelling and foaming, the rate of cracking, the texture. As well as the rate of carbonization pressure and the rate of exothermicity of the coal or of the mixture of coals treated, may be subject to variations which adversely affect the economic results of the operation of the coal plant. carbonization and on the efficiency rate of the use of coke in the consuming appliances for which it is intended.



   The various means which have been proposed to guide the technician in the choice of a new mixture which is suitable for obtaining, in coking plants for example, a good metallurgical coke without degradation of the heating walls and without great difficulty of discharge always lead to the adoption of a tower with crushed and mixed coals in which large quantities of coals to be coked are stored. The mixtures thus formed must be able to be introduced into certain furnaces of a battery, the other furnaces of which are supplied with another mixture. In these mixtures, a high proportion of coal called “coke-type coal” always enters.



   This way of finding the composition of a suitable new mixture is very expensive and often very time consuming because of the unforeseen results which are most often obtained from mixtures which are expected to be good. It also happens that when a mixture has been found with which one is satisfied, the necessary supplies are no longer available for the industrial feeding of the whole installation.



   The object of the present invention is to provide means, based on the chemism and on the mechanism of coking, which make it possible to determine quickly and inexpensively the constitution of self-coking mixtures of coals from all types of coals. fossils, i.e. both from non-self-coking coals and from self-coking coals
This process makes it possible, in coking plants for example, to industrially and permanently produce excellent metallurgical coke under economical operating conditions. It is based solely on data which can be deduced from the in vitro carbonization in the laboratory of small quantities of coals or mixtures of coals
Those data,

   most of which are not known to coking specialists, will first be exposed and defined. The same will apply for the "in vitro" carbonization test referred to in this specification. ,
The presentation of these data and the "in virtr carbonization test" will be facilitated by the attached figures which are diagrams relating to this presentation.



   . FIG. 1 represents the law of heating followed during an "in virtro" carbonization corresponding to an industrial carbonization carried out in a modern battery of silica coke ovens with an average width of about 450 millimeters and working at a load cooking rate corresponding to the nominal capacity of the battery.



   Figures 2 to 16 show the variation of different properties of "in vitro" carbonized coals, as a function of the ratio of fixed carbon content to carbon content of these coals.



   FIG. 17 is a differential graph of the evolution of permanent gases during the "in vitro" carbonization test of a particular coal, the differential volumes having been measured from minute to minute.

  <Desc / Clms Page number 3>

 
Figures 18 and 19 show the variation in properties of certain fossil coals as a function of the same ratio as that envisaged in Figures 2 to 16.



   FIG. 20 represents the variation of the unit asphaltic material value as a function of the unit humic carbon value.



   Figures 21 to 32 are differential graphs of the evolution of permanent gases during the "in vitro" carbonization test of different types of coal, this "in vitro" carbonization having been carried out according to the law of heating. shown in Figure 1 and the differential volumes having been measured 15 in 15 minutes.



   Figure 33 is a graph to aid in determining the composition of the mixture of two coals to produce standard co-ke.
The application of the process according to the invention presupposes that the desired coke, hereinafter referred to as "standard coke", has already been produced in the carbonization plant, and that from a known carbon of a known mixture of coals which we can no longer ensure non-existence.



   This known mixture of coals is industrially carbonized in a wet state, for example containing 5 to 10% water, and the firing rate is carried out so as to obtain the standard coke. While the cooking rate is being carried out in this way, the operation of the battery is carefully monitored and the draft and the pressure at the barrel are adjusted so that the fumes coming out of the chimney are not black. This ensures that no tars are burnt and that, consequently, complete carbonization is carried out without apparent loss of volatile products from the coal.



  It is known by analysis of the coal gas produced that any internal combustion of gas is avoided.



   The debensolated gas produced is measured. It should be noted that the debenzolated coal gas to be taken into account is pure coal gas, that is to say the gas supplied by the battery minus the gas to air coming from 1. • action on hot air coke or fumes which may have entered the carbonization chambers as a result of improperly adjusted differential pressures. In the basic industrial test the differential pressures at the coil should be set so that the industrial coal gas contains 5-7% nitrogen by volume.

   Knowing the nitrogen content of industrial coal gas makes it possible to calculate the volume of gas in the air which has mixed with the gas resulting from the carbonization of coal.



   When we know the volume at 0 C and 760 mmo of mercury of pure coal gas debenzolated from carbonization, we measure its specific weight at 0 C and under a pressure of 760 millimeters of mercuryo We deduce the weight of gas from pure debenzolated coal obtained per tonne of wet coal.

   To obtain the weight of gas per tonne of dry coal, it suffices to consider letpodsge the water contained in the treated coal (in: general treated coal -! Contains 5 to 10% water)
A small quantity p of the same carbon but in the dry state is then carbonized in the laboratory. This carbonization is carried out in an apparatus making it possible to obtain, after having made all the necessary corrections to take account of the spaces. death of the equipment and of the temperatures to which the gaseous carbonization products are subjected; a measurement accuracy such as the sum of the weights of the groups of products (coke, tar, benzols:

  , ammonia, reaction water, permanent gases) after multiplication by!, 000ka reaches 1,000 kg (to within 2 - 3 kg} ,.



   P
The carbonization operation in the laboratory must be carried out (by adjusting the heating mode and the cracking rate) in such a way that the weight of debenzolated coal gas obtained per tonne of dry coal corresponds to the weight of Pure debenzolated coal gas obtained per ton of the same dry coal which has been carbonized in the wet state in the battery, the firing rate and setting of which were those described above.

  <Desc / Clms Page number 4>

 that with a tube comprising two heating sections, it is possible to easily carry out the carbonization operation in the laboratory,
It was thus determined, for a given industrial installation,

   the conditions under which the carbonization must be carried out in the laboratory so that it can serve as a reference in the case where it is proposed to carbonize a coal or a mixture of coals of another composition, in this same industrial installation.



     It is the carbonization in the laboratory carried out under these special conditions that is called in this report "in-vitoro carbonization.
In FIG. 1, the duration of the cooking in the laboratory apparatus is represented on the abscissa. This duration is expressed in minutes. The ordinate shows the temperatures in degrees centigrade reached outside the carbonization tube of this device.



   The broken line 2 represents the heating law of this device. This law must be respected for all "in vitro" carbonizations which will be discussed later. It can be seen that with this "in vitro" carbonization the temperature goes from 300 ° C. to 900 ° C. in two hours.



   Let us now explain the concepts, for the most part unknown to specialists, which are necessary for understanding the process according to the invention.



   Lignin is the parent substance of all fossil coals.



  The lignin molecule is made up of C, O, H, S and N. These elements are chemically linked in a nucleus of very strongly polycyclic aromatic chemical structure and in branches of this nucleus.



   The branches are partially acyclic and partially heterocyclic in chemical structure. The heterocyclic portion of the branches includes naphthenic, aromatic, polycyclic, aromatic and highly polycyclic chemical structures approximating the lignin core structure.



   In this specification, only the C, 0 and H elements of the lignin nuclei and the branches of the nuclei are considered.



  The elements S and N can be neglected and are in order to facilitate the exposition.
The nuclei of the lignin molecule are hereinafter referred to as "graphite nuclei." Branches of the nuclei of lignin molecules are hereinafter referred to as "human materials".



   The carbonification of lignin is a succession of spontaneous reactions which, through thermal action (temperature) and spontaneous chemical action (autooxidation), give up thermally and chemically more stable carbon combinations. This evolution tends towards graphite, which is a thermally and chemically very stable form of carbon.



   The graphite molecule has a very strongly polycyclic aromatic chemical structure.



   The carbonaceous chemical combinations considered in this specification are classified in the following order of increasing thermal and chemical stability: - compounds of 09 0 and H, of acyclic chemical structure - compounds of C and H, of acyclic chemical structure - compounds of C, 0 and H, naphthenic chemical structure - compounds of C and H, naphthenic chemical structure - compounds of C, 0 and H, aromatic chemical structure

  <Desc / Clms Page number 5>

 compounds of C and H, of: aromatic chemical structure.



   - compounds of C, 0 and H, of polycyclic aromatic chemical structure - compounds of C and H, of polycyclic aromatic chemical structure - compounds of C, 0 and H, of strongly or very strongly aromatic chemical structure polycyclic - compounds of C and H of aromatic chemical structure, strongly or very strongly polycyclic - compounds of 0, 'of aromatic structure very strongly polycyclic (graphite).



   The graphite form of carbon is never reached in fossil coals or in semi-cokes or cokes.



   The carbonification of lignin begins with the auto-oxidation of humic matter with an acyclic structure. This exothermic reaction eliminates H20 and CO. ) reganant in the environment o This is in fact a stationary equilibrium independent of the concentration factor, given the length of geological time o
Auto-oxidation of acyclic humic materials, abandons materials of acyclic structure no longer containing oxygen
In this specification, carbonaceous substances.

   free of oxygen and derived, by auto-oxidation, humic materials are designated by the expression "asphaltic materials". In the order of increasing thermal and chemical stabilities, that is to say in, 1? structure order acyclic, aromatic naphthenic, polycyclic aromatic ,. highly polycyclic aromatic, the auto-oxidation of humic materials continues, leaving in the same order asphaltic materials of corresponding structure respectively and therefore increasingly thermally stable.



   Finally, the woody graphitic seeds undergo auto-oxidation, leaving asphaltic graphitic seeds no longer containing oxygen.
During carbonification and depending on the temperature of the medium, asphaltic materials are thermally decomposed, mainly eliminating CH4
As the elimination of CH4 progresses, the asphaltic residue of thermal decomposition evolves towards a thermally more stable chemical structure, therefore in the direction: acyclic, naphthenic, aromatic, polycyclic aromatic :, strongly aromatic polycyclic.



   At a given temperature of the medium, the speed of ato-oxidation of humic substances of all chemical structures is greater than the speed of thermal decomposition of asphaltic substances which derive from them. Likewise, at a given temperature of the medium, the rate of self-oxidation of the ligneous graphitic seeds is greater than the thermal decomposition rate of the asphaltic graphitic seeds which derive therefrom.
In this specification, the chemical structure evolution of asphalt materials and asphalt graphite seeds is referred to as "graphite evolution".
We deduce from the chemism of carbonification, that at the time of carbonification, lignin undergoes the following modifications
1)

   Weight reduction at variable speed depending on the carbonification rate;

  <Desc / Clms Page number 6>

 
2) Increasing carbon content at variable rate according to the carbonification rate;
3) Decreasing oxygen content, at variable rate according to the carbonification rate;
4) Decreasing hydrogen content, variable rate depending on the carbonification rate. The variation in the hydrogen content is much less than that of the C and 02 contents given that the hydrogen is mainly eliminated in the form of H20 and CH4, the H2 contents of which are relatively low compared to the 02 contents and C respectively.



   5) Decreasing content of humic matter, at variable rate depending on the carbonification rate;
6) Decreasing content of asphaltic materials with variable appearance depending on the carbonification rate;
7) Increasing content of woody graphitic seeds, at variable rate according to the carbonification rate;

   
8) Increasing content of asphalt graphitic seeds, at variable rate depending on the carbonification rate
Fossil coals, in a neutral and non-oxidizing environment, are thermally stable at temperatures not exceeding those to which they were exposed during their fofmationo
If the fossil coals are heated, in the absence of air and under atmospheric pressure, to a temperature higher than that which corresponds to the state of perfect thermochemical equilibrium which they have reached during geological temperatures, the The carbonification chemism described above continues, but at a much brighter overall pace than in carbonification. The operation of heating fossil coals, in the absence of air and under the absolute pressure of an atmosphere,

   commonly referred to as "caronization". differs from carbonification, mainly a) by the use of temperatures higher than those which acted in carbonification; b) by the absence of pressures greater than an absolute atmosphere; c) by a greater speed of elevation of the. temperature; d) by the absence of any state of stationary equilibrium; e) by the variation of the equilibrium rate reached at any time during the operation as a function of 1% of the composition of the coal and of the carbonization conditions; f) by the importance acquired in carbonization, the reactions strongly accelerated by the rise in temperature and which, therefore., manifest themselves infinitely less in carbonification, for example, the reactions between water vapor and the carbonaceous substances present.



   The "volatile matter" value of a charcoal expresses the weight loss it undergoes during carbonization under determined operating conditions. The result of the operation is calculated, by calculation, to be dry charcoal, ash-free
The coke yield of the coal under given carbonization conditions is therefore 100% of the weight of coal treated minus the percentage of volatiles. For a given coal, the "volatile matter" value is all the lower and the coke yield all the higher the higher the rate of thermo-chemical equilibrium reached during carbonization.



   The "in vitro" carbonization test of a charcoal can be carried out in such a way that

  <Desc / Clms Page number 7>

 (a) coke yield, comprising the solid products resulting from the thermal decomposition of volatile products generated during the carbonization of coal; b) the coke yield not including the solid products resulting from the thermal decomposition of the volatile products generated during the carbonization of the coal.



     It is the value b) which is designated by the term Cf. In the present specification. By associating Cf, which is a variable dependent on the carbonization conditions, with the carbon content C, which is a variable independent of the carbonization conditions, in the C / Cf expression of the coals, indications emerge, for example , with regard to the variations in behavior of different types of fossil charcoals, carbonized under identical operating conditions (for example "in vitr" carbonization at high temperature).



   The shape of the variation in the C, O 2 and H2 contents of the coals in the whole series of fossil coals is shown in Figures 2, 3 and 4, as a function of the C value of the coals. This last will
C is plotted on the abscissa while the percentage respectively in C, 02 and H2 is plotted on the ordinate,
All fossil coal contains, in proportions which vary according to the rate of carbonification; humic materials, asphaltic materials, woody graphitic seeds and asphaltic graphitic seeds defined above The thermal and chemical stabilizers of these four products are increasing from one product to the next.

   The petrographic elements of the coals, that is to say durain, vitrain and charcoal correspond respectively to humic matters, to asphthalic matters and to graphitic seeds in a more or less concentrated and more or less evolved state,
Clairain is to be considered as a mixture of durain and vi train. In carbonification, the weight loss of the coals is mainly undergone by humic and asphaltic substances which are chemically and thermally much less salty than the ligneous and asphaltic graphitic seeds.



   Examination of Figures 2 3 and 4 reveals that the C, 02 and H2 contents of fossil charcoals as a function of the C value of these vary very little for the values of the C ratio comprised between- Cf tre 1.175 and 1 , 0950
Cf We deduce that, during the carbonification period during which the decrease in the weight of the coals corresponds to a variation of the ratio e from 1.175 to 1.095, all the spontaneous carbonification reactions defined above are above s' perform at speeds, uniform for each of them, while from the highest values of the ratio C of the fossil coals up to the value 1.175 and from Cf then the value 1.095 to the lowest values of the fossil coals,

   spontaneous carbonification reactions take place at varying rates for each reaction.



   The completion rates of each of the carbonification reactions are in the range of the C values of the carbons from 1.175 to
CF 1.095 uniform for each reaction but different from one reaction to another depending on the chemism of the carbonification defined above.



   These rates correspond to a) decreases in the concentrations of the coals of humic and asphaltic substances, The first decrease takes place at a uniform rate different from the speed one flame and the second decrease; b) an increase, at a uniform rate, in the concentration of charcoal in woody graphitic seeds;

  <Desc / Clms Page number 8>

 c) an increase, at a uniform rate, in the concentration of carbon asphalt graphitic seeds; d) a graphitic evolution at a constant rate for each of the chemical structures of the asphaltic materials present.

   The rate of graphite evolution for each of these chemical structures is obviously different from the rate of evolution of the other; e) a constant rate auto-oxidation of each of the chemical structures of the bernic materials present. The rate of the auto-oxidation of each of these chemical structures is obviously different from that of the auto-oxidation of the other. f) a respectively constant shift between the different forms of chemical structure of the humic and asphaltic materials present; g) a constant overall rate of auto-oxidation of humic matter; h) a constant overall rate of thermal decomposition of asphaltic materials; i) a constant difference between the speeds g) and h);

   j) a con- stantly higher concentration of asphaltic materials than the concentration of humic materials. k) a constant difference between the concentration of coals in asphaltic matter and their concentration in humic matter;
1) a constant rate auto-oxidation of the ligneous graphitic seeds; m) a thermal decomposition at constant rate of asphaltic grapintic seeds.



   This state of equilibrium persists until the moment when the humus of the chemically least stable structures in the C region
Cf 1.175 to 1.095 disappear one after the other in the order of increasing chemical stability and where; therefore, the corresponding asphaltic materials become increasingly rich in structures with a high rate of graphitic evolution. Consequently, the rate of formation of asphalt graphitic seeds increases and becomes preponderant over the rate of formation of asphaltic substances in the region of the Ç values included.
See between 1.095 and lower values.



   In the region of the highest C values of the fossil carbons up to the value 1.175, the carbonification reactions result in the equilibrium state described above for the region of the C ratio values included. between 1.175 and 1.0950
Cf
If we start from lignin, formed of little evolved woody graphitic germs and humic matter containing in high proportion the humic structures chemically stable rm ins, carbonification, by auto-oxidation of humic matter, leads, in the first stages from carbonification to completely decomposing asphaltic materials.



  The concentration of woody graphitic germs, the self-oxidation of which progresses at a much slower rate than that of humic matter, increases in the residual woody matter as the asphaltic matter is destroyed by thermal decomposition. derived from the least chemically stable human structures.



   As soon as the asphaltic materials derived from the humic materials are thermally stable enough to resist complete thermal decomposition at the temperature of the medium.

  <Desc / Clms Page number 9>

 siduary is enriched with asphaltic materials, Due to the greater thermal stability and graphitic evolution of asphaltic materials as their thermal decomposition progresses, the concentration of residual woody material in asphaltic materials increases in relation to the concentration of humic matter, while the concentration of woody graphitic germs increases as a result of the continual decrease in the sum of residual asphaltic matter + residual humic matter,

   at a much faster rate than the decrease in the concentration of woody graphitic seeds as a result of their auto-oxidation,
This development leads from lignin to lignite, brilliant lignite and dry flaming coals. In the latter, the concentration of humic matter is still greater than their concentration of asphaltic matter. But as evolution continues, the shift between the asphaltic and humic chemical structures increases so that the concentration of humic matter in the coals decreases more rapidly than the concentration of asphaltic matter,

   The concentration of woody graphitic seeds increases continuously as a result of the continual decrease in the sum of the concentrations of asphaltic matter + humic matter,
From the value C¯. Equal to approximately 1.300, the shift between
Cf the humic and asphaltic chemical structures decrease, so that the respective concentrations of asphaltic matter and humic matter come closer.



   Around the value C = 1.205, there is equality of the concentrations. Cf trations in humic matter and in asphaltic matter, In region C between 1.205 and 1.175, the concentrations in humic matter Cf and in asphaltic matter gradually deviate until reaching the values which correspond to the state of equilibrium described for the values of C com-
Cf taken between 1.175 and 1.0950
The composition, chemical structure, thermal and chemical stabilities of humic and asphaltic materials therefore vary constantly throughout the series of fossil coals from dry flaming coals to anthracite coals.



   In the region between the highest values of the ratio C of the fossil coals and the value Ç = 1.175, the materials as-
Cf Cf phaltics formed will give rise to increasingly high proportions of asphaltic materials of composition, structure, physical and chemical properties, approaching those of the asphaltic materials present in C coals between 1.175 and 1.0950
Cf
On the other hand, in the region between the value C = 1.095
Cf and the lower C values, the asphaltic materials of the coals
Cf will contain increasingly lower proportions of asphaltic materials similar in composition, structure, physical and chemical properties to those of the region where the C value is between 1.175 and 1.0950
Cf
In carbonification,

   the equilibrium rate of all possible spontaneous reactions for the prevailing temperature and pressure is always 100% and the respective concentrations of the reactants do not play a role in the equilibrium
In carbonification the auto-oxidation of humic matter only eliminates H20 and C020 Thermal decomposition of asphaltic materials mainly eliminates CH4 Auto-oxidation of woody graphitic seeds

  <Desc / Clms Page number 10>

 eliminates H20 Thermal decomposition of asphalt graphitic seeds eliminates CH4
On the other hand, in carbonization, all the factors influencing the equilibrium rate of the possible reactions must be considered.

   Among these factors are the respective concentrations in the coal of reacting substances under given carbonization conditions.



   The differences already mentioned between carbonification and carbonization have as a consequence, among others., That in carbonization: a) the auto-oxidation of humic substances eliminates from the environment, in addition to H20 and CO2, a whole series of oxygenated substances which are mainly found in tar;

   b) the water vapor produced by the auto-oxidation of humic matter engages, in proportions determined at any time by the reaction conditions of the moment, in reactions of equilibrium with the carbonaceous substances present c) the Asphaltic substances in coal supply, by thermal decomposition, in addition to CH4, a whole series of non-oxygenated carbonaceous substances, which are gaseous and liquid at room temperature, a large proportion of which is found in the tar;

   d) the auto-oxidation of the ligneous graphitic seeds, eliminating water vapor, is much more intense and more extensive than in carbonification and, because of the higher temperature in carbonization, the gas reactivons at water here acquire an importance that they cannot reach in carbonification; e) the thermal decomposition of asphaltic graphitic seeds eliminates, in addition to CH4 from C2H2, the latter partially transforming into C6H6 under the influence of temperature (in carbonization at high temperature for example) and of the catalyzing action of coke .



   In FIGS. 5 to 16, the values of the ratio C relating to the high temperature carbonization of coals, Cf carried out under strictly identical conditions, have been plotted on the abscissa. The ordinates of these figures represent; - for figures 5 and 6, kilogs of reaction water respectively per tonne of ash-free dry coal and per 100 klogs of volatile matter, these being equal to 1000 - Cf), - for the figure 7, normal and homologous cubic meters of methane per tonne of dry coal, - for figures 8 and 9, kilogs of "benzols" respectively per tonne of dry coal free of ash and per 100 kg of volatile matter ( 1000 - Ci)

   (the word "benzols" designates the hydrocarbons which can be extracted from the gas by washing with heavy tar oil for example)., - for FIGS. 10 and 11, kilogs of asphalt graphitic seeds deriving from the cracking of volatile materials, respectively by ton of dry coal free of ash, and per kilogs of volatiles (1000 - Cf) - for figures 12 and 13, kilogs of tar respectively per ton of dry coal free of ash and per 100 kilogs of ma - volatiles (1000 - Cf), - for figure 1, percent of fixed carbon (Cf0 - for figure 15, percent of volatile matter (100 - ci), - for figure 16, percent of the difference 100 - (Ci + asphaltic graphitic seeds deriving from the cracking of volatile materials).



   It can be seen that in carbonization, the equilibrium phenomena respond to

  <Desc / Clms Page number 11>

 to the law of variation of the concentration of reacting substances but that this law becomes more complicated as a result of variations in the chemical structure of the reacting substances and that the influence of variations in chemical structure is clearly more marked in the regions of coals at - C) 1.175 and at C <1.095 than in the region of coals with a C value compriCī Cf Cf pe between 1.175 and 1.0950
According to one characteristic of the present invention, the concentrations of the coals in humic materials, in asphaltic materials and in graphitic seeds are established in units which are immutable in composition,

   in chemical structure and in charring behavior across the whole series of fossil coals. The concentrations thus established are quantitatively comparable across the whole series of fossil coals, but by using these concentration data in applications such as carbonization and coking, it is suitable, mainly, for coals whose C value 1.175 and for those whose C value 10.095 to consider 'Cf' Cf the consequences resulting from the simultaneous variation of the concentration and chemical structure of the substances considered.
Choice of units;

   
During the carbonization of coal at high temperature, the following phenomena take place in chronological order a) auto-oxidation of humic matter. b) thermal decomposition of asphaltic materials c) auto-oxidation of woody graphitic seeds d) thermal decomposition of asphaltic graphitic seeds.



   If, during the "in vitro" carbonization test, an appropriate heating law is applied to a sufficiently thin layer of carbon, the differential curve of the evolution of permanent gases as a function of time, hereinafter called profile carbonization, shows a fairly clear separation between; primary carbonization (phenomena a) and b) above) and secondary carbonization (phenomena c) and d) above) '.



   In Fig. 17, curves 3 and 4 represent the carbonization profiles of a particular coal during primary carbonization and during secondary carbonization, respectively. On the x-axis, we plotted the "in vitro" carbonization times in minutes and on the y-axis the differences in the volumes of the permanent gases expressed in cubic centimeters. those of gas at 20 C, under a pressure of 764 millimeters of mercury, saturated with water vapor and released per minute for 20 grams of the aforementioned particular dry coal
It follows from Figure 17, that we can afford to neglect the interference of primary and secondary carbonization towards the end of primary carbonization,

   .whereby the primary carbonization of a coal is reduced to:
1) auto-oxidation of humic matter
2) thermal decomposition of asphaltic materials
3) the liberation of current and potential asphaltic graphitic germs and asphaltic germs from coal. All of the graphite seeds constitute the semi-coke.



   During secondary carbonization, semi-coke turns into coke ,,
During secondary carbonization, the graphitic evolution of the graphitic seeds from which the semi-coke is formed continues under the action of the rise in temperature and the auto-oxidation of the granules.

  <Desc / Clms Page number 12>

 woody phitics. This development leads by contraction to an increase in density of the material accentuating its cracking as a result of the contraction of the semi-coke, The number of benzene rings joined in the mol-
 EMI12.1
 The semi-coke cell becomes larger and larger as the graphite development continues.



   It is from the data of the elementary composition and the primary carbonization that the composition of the coals according to the present invention is determined.



   The least evolved fossil coal, for example a dry flaming coal coming from a layer mined in the open air, contains asphaltic materials and asphaltic graphitic seeds but the sum of the concentrations of which is less than for all the fossil coals. more advanced. Its concentration of woody graphitic seeds is lower and its concentration of humic matter higher than those of all the more evolved fossil coals.



   By determining the composition of fossil coals in relation to the least evolved coal, the concentration of asphaltic matter of the more evolved coals does not express the total concentration but rather the difference between the total concentration and the concentration of asphaltic matter of the most evolved coal. less evolved.



   By determining the concentration of the coals, not in current woody graphitic seeds and asphaltic graphitic seeds, but by the sum of g woody graphitic seeds plus current asphaltic graphitic seeds plus potential asphaltic graphitic seeds (this sum corresponds to semi-coke), we obtains a data of more value in carbonization and in coking than the concentration of coals in woody graphitic seeds and in current asphaltic graphitic seeds.



   By choosing, according to the present invention, as units of expression for the composition of the fossil charcoals, a highly humic charcoal.
 EMI12.2
 little evolved, a suitable asphaltic material and a semi-coke which each have an unchanging composition, chemical structure and carbonization behavior through the whole series of fossil coals, the expression of the composition of the coals is made in value unit humic coal, in asphaltic matter value; unit and in unit semi-coke value, the total of which varies according to the carbonification rate of the coals and the difference between the semi-coke yield of the current and potential asphaltic materials of the coal and the immutable semi-shell yields of the selected unit humic coal and unit asphaltic material.



   These three unit materials are defined as follows
As unit humic charcoal, a flaming dry charcoal with a high oxygen content is chosen, the carbonization of which is carried out "in vitro" and the oxygen content of which is determined. One chooses, for example, as humic charcoal '' unit a charcoal of which the coke yield "in vitro", without
 EMI12.3
 semi-graphite, thermal decomposition of raw materials, is 52.46% and the oxygen content is 25.75%. These contents relate to dry coal free of ash.



   As the unitary asphaltic material, a natural grindable asphalt is chosen, the properties of which are close to those of the asphaltic materials of coals and which, therefore, has an appropriate decomposition curve.
 EMI12.4
 thermal sition and is free of oxygen. This asphalt is carbonized "in vitro".



  One chooses, for example, as an asphaltic material a hard grindable asphalt which softens at 110 G9 which melts at QC1 C, which produces abundant gases and vapors at 47p G which hardens at 500P C, which does not contain any acid. oxygen and which, on "in vitro" carbonization gives rise to 20% 3semi-coke. The absence of oxygen and the yield of semi-noke are considered to be ash-free solids.

  <Desc / Clms Page number 13>

 
 EMI13.1
 



  As unitary semi-coke, one chooses ur qTmÀ = eoke at 606 G, the composition of which corresponds to the i6ßenne composition of at least 20 semi-cokes at 600 C of different types of 0., ne 'E / Î z found that the volatile materials which emanate from the unit semicoke between 600 ° C and 900 ° C represent approximately 5% of the weight of the unit semicoke and that the oxygen it contains weighs approximately 2.5%. % of the weight of the unit semi-coke. The proportions ..exist for .11 dry semi-coke free of ash .., ..1, '..: Unit humic carbon contains humic substances,
 EMI13.2
 asphaltic materials, woody graphitic seeds and asphaltic graphitic seeds.



   During carbonization, the humic materials of the unit humic carbon form more or less fusible gases, vapors and asphaltic materials.



   During carbonization, '' the asphaltic materials present in the unit humic carbon and those formed from the human materials
 EMI13.3
 mics of unit humic charcoal form gases, vapors .., and semi-coke .. '' All of the semi-coke supplied by the carbonization of the coal.
 EMI13.4
 Unit humic carbon includes the iemi @ cpke, arising from graphitic germs present in the unit humic carbon, and the semi-coke formed during the carbonization of the unit humic carbon from the asphalt materials.
 EMI13.5
 ticks it contains and those 'which have formed' a. from the humic materials contained in the unit humic carbon.

   '
During "in vitro" carbonization, unit humic carbon gives, since Cf = 524.6 kg per tonne:
 EMI13.6
 6 kg + 26.23 kg '. $ 5,509 3'kg of semi-coke per tonne (the 26.23 kg correspond to the 5%' of volatile matter which is released
 EMI13.7
 unit semi-coke between 6000 G-. and 9000 C) ....



   Humic Coal Primary Volatiles Unit = 10,000 kg 550; 83 kg = 449.17 kg per tonne. '
Oxygen in primary volatiles of unit humic carbon:
 EMI13.8
 257.5 kg - (550.83 kg x 0.025) = 257.5 kg - 1} 7 kg = 243.73 kgo A 1 kg of primary volatile oxygen corresponds 'therefore 1 3' =, 19g4 kg of volatile matter, primary.



  243'973 J.eres eS, prJlIlaJ.reso A 1 kg of primary volatiles corresponds to 550.83 kg 1,226'kg'de ', semi-coke' 447? -'- <. '. ,,. ,.



  To express the composition of any charcoal in unit humic charcoal, unitary sphaltic matter, unit semi-coke values, we start from the results of elemental analysis of the coal and from the results of: its: - "in vitro" carbonization. To 'avoid having' to carry out the elemental analysis of charcoal, its elemental composition can also be calculated from the results of "in vitro" carbonization.



   Indeed, it results from the chemism of carbonization that the compositions of the tars of carbonization at high temperature and those of the carbonization shells at high temperature tend towards identical compositions whatever the composition of the coal. charred.

   The compositions of the high temperature carbonization tars of all types of coal
 EMI13.9
 good approximate autawt p.us' 7. e tilae of 1 Other than the'proportion of. low temperature tar which they contain ost weaker o However, the methods of carbonization Iliri vitro "as they are defined above as-

  <Desc / Clms Page number 14>

 As much as possible, there was no low temperature carbonization tar in the high temperature carbonization tar provided by the "in vitro" carbonization test of any coal. The compositions of the cokes (free of ash) from "in vitro" carbonization of all types of coals can be assumed to be practically identical.



   Knowing the carbon, hydrogen and oxygen contents of tar and carbonization coke "in vitro", the elemental composition of coal can be easily calculated, with sufficient precision for the needs of practice, from the data provided. by the "in vitro" carbonization test.

   These data are the coke obtained by carbonization, the semi-graphite obtained by thermal decomposition of the primary volatiles, the tar, the benzols, the ammonia, the water of reaction, the, weight of permanent gases, the volume of permanent gases, saturated with water vapor, at 0 C and 760 mm Hg and the volume composition% of permanent gases CO2, CmHn 02 CO H2 CH4 N2
In the calculation of the elementary composition of coal, ben zols are considered to be benzene (C6H6) Heavy hydrocarbons (CmHn) of permanent gases are considered to be composed of half of ethylene (C2H4) and half of acetylene (C2H2)
Knowing the coke yield "in vitro",

   (ash-free coal and coke without thermal decomposition semi-graphite of primary volatiles) and the oxygen content (on dry ash-free coal) of any coal, is calculated according to the example given. -after, the values; unit humic carbon, unitary asphaltic materials and unit semi-coke.



   EXAMPLE
Coke yield Cf "in vitro" of the coal 1781 kg per tonne.



   Oxygen content of coal 51.2 kg per tonne.



  820.05 kg unit semi-coke value 781 kg + 781x1005 = 781 + 39.5
Primary volatiles: 1,000 kg - 820.05 kg = 179.95 kg
Primary volatile oxygen (of humic origin): 51.2 kg - (820.05 x 0.025) kg = 51.2 kg - 20.5 kg = 30.7 kg corresponding to 30.7 kg x 1.84 = 56 , 48 kg of primary humic volatiles.



   These correspond to 56.48 kg x 1.226 = 69.24 kg of semi-coke
Unit humic charcoal value 56.48 kg 69.24 kg = 125.72 kg
Asphaltic primary volatiles 179.95 kg - 56.48 kg = 123.47 kg
Since the semi-coke yield of the unit asphaltics is 20%, the unit asphaltics value is
123.47 kgx5 = 154.33 kg
Unit humic carbon values,

   Unit asphaltic materials and unit semi-coke are expressed in this way in immutable units across the whole series of different types of fossil coals and mixtures of these coals and thus provide quantitative data for comparison of the compositions of the different coals. fossils and mixtures of these coals in these three unit substances as well as the quantitative data essential for the study and calculation of the constitution of the mixtures with a view to the industrial production of standard coke.



   In figure 18, the abscissas represent values of the ratio C for part of the series of fossil carbons while the ordinates Cf

  <Desc / Clms Page number 15>

 represent kilogs. Lines 5, 6 and 7 represent, for these coals, the variation, as a function of the C values, respectively of the coal value
Cf unit humic, the unit asphaltic materials value and the unit semi-coke value.,
In figure 19, the abscissas are the same as in figure 18 but the ordinates correspond to the values of the unit asphalt materials ratio for the fossil coals studied.

   The unitary asphalt limestone gne 8 therefore represents the variations of this ratio as a function of the ratio Ç
Cf
In figure 20, line 9 represents, for the whole series of fossil coals, the variation of the unit asphaltic matter value as a function of the unit humic carbon value.

   The abscissas express kilogs of unit humic coal and the ordinates express kilogs of unit asphaltic materials.
Figures 21 to 32 represent the "carbonization profiles" of different types of fossil coals (gas volumes of 15 in 15 minutes)
FIG. 21 represents the "in vitro" carbonization profile of an antracitous type charcoal; FIG. 22 that of a semi-fatty type charcoal; FIG. 23, that of a three-quarter-fat type coal, FIG. 24 that of a coke type coal with high carbonization pressure; Fig. 25, that of a typical low carbonization pressure coking coal;

   Figures 26, 27 and 28, those of three coals each of a type intermediate between the low carbonization pressure coke type and the gas type; FIG. 29 that of a gas type coal ..; Figures 30 and 31, those of two flaming fat type coals; figure 32 that of a flaming dry type coal
The "in vitro" carbonization profiles shown in Figures 21 to 32 illustrate, for the main types of fossil coals, the different periods of carbonization and their relative importance in the volume production of permanent gases during carbonization of each of the types of coals considered.



   Among the three constituents of coal, the asphaltic material is the only more or less fusible o Its fusibility varies due to the carbonification rate of the charcoals o The plastic melting of certain types of so-called au-to-coking coals is determined by the fusibility of the asphaltic materials which 'they contain? The phenomenon generally designated by the expression "plastic melting - of the coals" is better defined by the expression "asphaltic melting - of the carbons".
The possible formation, at a given moment of carbonization, of a coherent semi-coke from pulverulent carbon is due to the binding of the graphitic seeds contained in the latter by the graphitic seeds deriving from the thermal decomposition of asphaltic materials. ,
In a load of charcoal,

   the zone where the welding of the graphitic seeds takes place, that is to say the zone of birth of the coherent semi-coke, temporarily offers a great resistance to the passage of gases and vapors o This zone is called here- after "screen zone".



  This zone exists in the carbonizing coal charge for as long as the formation of coherent semi-coke lasts and it progresses from the heating wall towards the core of the mass of coal to be coked, leaving behind a-, mass which has become - ¯, as a result of the graphite evolution, permeable to gases and vapors which are at a temperature higher than that at which this zone was formed. The permeability behind the screen zone arises from the cracking of the semi-coke by contraction.



   The asphaltic fusion of coal brings about a reconciliation of the graphitic germs, This reconciliation is accentuated as the asphaltic material is decomposed and it provides knotty graphitic germs.

  <Desc / Clms Page number 16>

 ticks to the mass in treatment At the time of the birth of the semi-coke, an asphaltic liquid -phase may remain and, therefore, be enclosed in the cells of the skeleton of the nascent semi-coke
The possible formation of coherent semi-coke from a carbonaceous substance takes place at a temperature that is all the lower as the concentration of graphitic seeds in the carbonization medium is greater; this concentration depends on the composition of the substance. carbonaceous, the rate of compression it undergoes during carbonization, among others,

   due to the carbonization pressure or the pressure to which it was subjected before carbonization o
In the case of carbonization of carbonaceous substances in the calibrated state, the asphaltic melting during caristion is not always necessary for the formation of a coherent semi-coke, just as it may not be. necessary if the carbonaceous substance is subjected to strong compression before carbonization
In Figures 1, and 21 to 32, there is also shown -four vertical lines designated by 10, 11, 12 and 13. These lines pass through the abscissa points corresponding to 15, 30, 45 and 60 minutes respectively. They serve roughly as a limit for five successive periods of carbonization.



  The set of the first four corresponds to primary carbonization while the fifth period corresponds to secondary carbonization. During these five periods, the following phenomena take place Period 1. This period is represented between the ordinate axis and the vertical line 100 During this period, the start of auto-oxidation and thermal decomposition of humic materials and the fusion of fusible asphalt materials.



   Period 2 This period is represented between vertical lines 10 and 11 During this period, the maximum auto-oxidation and thermal decomposition of humic materials takes place as well as the onset and development of pyrolysis of asphaltic materials o C ' It is during the second period of primary carbonization that the possible reactions between the products of auto-oxidation of humic materials, molten asphalt materials and the products of thermal decomposition of asphalt materials and graphitic seeds reach a maximum intensity during primary carbonization. In particular, it is then that the reactions between the water vapor and all the carbonaceous substances present are the most intense.



   Period 3 This period is represented between the vertical lines 11 and 12 During this period, the pyrolysis of asphalt materials reaches its maximum intensity o It can be seen that the "in vitro" carbonization profiles 14 of the self-coking coals shown in Figures 24, 25, 26, 27, 28, 29 and 30 show a peak at the end of the third period of primary carbonization. This peak corresponds to the maximum intensity of the pyrolysis of asphaltic materials. This pyrolysis gives rise to the formation of a large quantity of methane, In other words, it corresponds to a preponderance of methane in all the gases given off during this period. This is the reason why it is called hereinafter "methane peak".



   The viscosity of a portion of the slice of the filler which may be in asphalt melt increases as the pyrolysis of the asphaltic materials progresses with the increase in temperature. the semi-coke side at the edge of the asphaltic molten slice constitutes the semi-coke mother stock and it is in this that the semi-coke backbone eventually develops, consistent when the concentration of graphitic seeds in the semi-coke mother paste became sufficient to allow the laision between them and the already formed semi-coke.

   The viscosity of the semi-coke mother stock at the time when the semi-coke backbone is formed and the amplitude of the gas phase (gas + vapors) which develops at this time are among the determining factors

  <Desc / Clms Page number 17>

 texture of semi-coke. The layer of incipient semi-coke constitutes the screen zone in the charge of self-coking coals.



   Period 4 This period is represented between vertical lines 12 and 13. During this period, the pyrolysis of asphaltic materials possibly occluded in the cells of the semicoke skeleton takes place. Contraction and cracking of the screen zone continues as a result of the pyrolysis of the semi-coke which begins immediately after its anaissanco This is the final period of thermolysis of asphaltic materials and primary carbonization. At the end of this period, the possibly coherent semi-coke is completely formed and already partially cracked.



   Period 5 This period is shown to the right of the line
 EMI17.1
 vertical 130 During this period, the graphitic evolution of the semi-coke continues, accompanied by a contraction of the mass. Cracking of the semi-coke is accentuated if the semi-coke was coherent at the time of its formation. The graphitic development reaches a maximum intensity at about 800 C - approximately (820 C outside the carbonization tube of the gas analyzer.
 EMI17.2
 Sai "in vitrai!) The graphitic evolution during the secondary carbonization is accompanied by the presence of a high proportion of hydrogen in the mixture of permanent gases formed during this period.

   The volume of
 EMI17.3
 these fall sharply and quickly after the maximum intensity of the pyrolysis of the semi-cokeo. For this reason the peak of the "in vitro" carbonization profile which precedes this drop is hereinafter called the "hydrogen peak";
The characteristics of coke such as rate of size stability, rate of swelling and foaming, rate of cracking, texture, bulk density, specific reactivity as well as the charring pressure of the filler are influenced not only by the composition of the load but also by factors independent of this composition.



   These include, among others, the heating method, the temperature of the carbonization regime, the dimensions of the container
 EMI17.4
 in which the carbonization takes place, the geometric shape of this receptacle, the water content of the coal., the particle size of this goose the uniformity rate of the size distribution of the coal in the charge, the compression rate of the coal , the method of loading the charcoal into the receptacle in the
 EMI17.5
 What is the carbonization effect? These factors influence the rate of carbonization and, for example,
 EMI17.6
 therefore,

   on the thermochemical equilibrium rate reached at any time during the operations on the intensity of the swelling work at the time of the birth of the semi-coke on the intensity of the contraction and cracking work of semi-coke during secondary carbonization and on pressure.-carbonization.



   For example, for the same carbonization regime temperature in a circular prismatic retort and in a rectangular prismatic coke oven, the width of which is equal to the diameter of the retort considered not only the average carbonization rate is greater
 EMI17.7
 in the retort than in the coke oven, but the acceleration in the rate at which all successive periods of carbonization are accomplished as the carbonization operation progresses in the charge, is considerably greater for the prismatic retort. circular than for the rectangular prismatic coke oven.



   The increase in the rate of carbonization, and hence the resulting decrease in the rate of thermochemical equilibrium reached at any time during primary carbonization, can increase the proportion of meltable asphaltic material contained in the coal which arrives at the semi-coke mother stock stage. From this head, certain coals
 EMI17.8
 non-self-coking at a given carbonization rate become self-coking at a more rapid rate (carbonization.

  <Desc / Clms Page number 18>

 



   Variations in the rate of carbonization in a charge of carbonizing coal, as the operation progresses, are among the causes which determine the variations in coke characteristics (e.g. the rate of cracking and the rate of swelling and foaming) in
 EMI18.1
 different planes of a pri1B1Jiàtiq1leo charge For example, the coke salmon resulting from charring in a rectangular prismatic coke oven contains the least blistered and cracked coke in the regions closest to the heating walls of the furnace while the The most bloated (possibly the coke froth) and the most cracked coke are in the regions closest to the longitudinal mid-vertical plane of the salmon.



   Despite the greater amplitude of the crevices in the coke salmon in the vicinity of the heating walls of the oven, the large caliber pieces in the loose coke always show a greater proportion of pieces of which one of the planes presents the bumpy appearance of a cauliflower, only pieces without cauliflower face, which proves that the rate of cracking
 EMI18.2
 tion of the coke near the heating walls is less than inside the salmon
In industrial practice in the manufacture of coke, the independent factors of the composition and molecular structure of the char-
 EMI18.3
 good are the carbonization plant,

   the imposed carbonization rate resulting from the quantities of products to be supplied by the carbonization plant at a given time and the treatment and handling of the coal prior to carbonization.



   It results from the chemism and mechanism of carbonization and
 EMI18.4
 coking that the differences in quantity, composition and molecular structure of the three constituents: humic materials, asphaltic materials and graphitic seeds in the different types of fossil coals
 EMI18.5
 and the mixtures of these carbon coals entailed differences in the characteristics of the coke, which they produce industrially in a given oven, at a given firing rate, the other characteristics of the charcoal or mixture
 EMI18.6
 such as the water content, the particle size and the degree of size distribution uniformity, the spatial density of the load in the oven, expressed as dry matter, being assumed to be identical.



   The rate of swelling and defoaming of semi-coke or coke is determined: by the viscosity of the semi-coke mother stock immediately
 EMI18.7
 before the formation of the semi-coke backbone; by the amplitude and the intensity of the ewoaatzon of the gas phase (mainly asphaltic) at the time of the formation of the semi-coke skeleton, by the carbonization pressure at the time of the formation of the semi-coke skeleton - The viscosity of the semi-coke mother stock at the time of forming
 EMI18.8
 tion of the semi ... coke skeleton is determined; by the quantity and the fusibility of the asphaltic materials, by the quantity of solids present in the zone of birth of the semi-coke.



   The amount and fusibility of asphaltic materials in the semi-coke mother-paste depend mainly on the amount and fu- sibility of the fusible asphaltic materials present in the coal or the mixture of coals relative to the amount of humic dobby. that this carbon or mixture contains and from the moment of primary carbonization when the semi-coke mother-paste stage is situated, the latter being reached immediately before the moment when the binding of the graphitic seeds takes place in the pre-coke phase.
 EMI18.9
 sence, that is to say where the first zone (screen zone) of the coherent semi-coke develops.The quantity of graphitic seeds present in the pulp - mother-of semi-coke is therefore little different from that which constitutes the emerging semicoke in the screen zone,

   
 EMI18.10
 The amplitude of the gas phase at the time of the birth of the semi-coke is substantially proportional to that indicated by the height of the methane tip of the "in vitro" carbonization profile of the coal or of the mixture of coals, while the intensity of the evolution of this phase

  <Desc / Clms Page number 19>

 zeuse (permanent gases + vapors) depends on the position of the birth zone of the semi-coke skeleton (screen zone) in the charge, a position which determines the rate of acceleration of the carbonization speed with respect to at the rate of carbonization in the other planes of the charge. The carbonization pressure, which varies with the variation in the rate of carbonization, varies from load plane to load plane.

   It is greater doubt that the rate of swelling and foaming of the incipient semi-coke is higher and the rate of contraction and cracking of the semi-coke or coke is lower. The rate of contraction and cracking of semi- coke or coke is determined by the average rate of graphite evolution of the graphitic seeds which make up the nascent semi-coke (the graphitic seeds resulting from the thermolysis of asphaltic materials during the char - primary improvements are always of very small caliber because they are formed at a very brisk pace and at a relatively low temperature) and by the rate of secondary carbonization.



   This latter speed is variable from one plane to another of a carbonization charge.



   As a gum for primary carbonization, it accelerates as the secondary carbonization progresses in the charge.



   The size stability of coke is determined by three factors: swelling and foaming rate, contraction and cracking rate and carbonization pressure rate, and it is doubtful that the value of the first two factors is lower and that the the value of the third factor is higher.



   The texture of coke is determined by the rate of swelling and foaming and the pressure of carbonization.



   The specific reactivity of coke is determined by the rate of graphitic evolution, by the texture and by the nature of the surfaces of the cells.



   The rate of exothermicity of the coal or the mixture of coals is determined by the difference between the heat energy released by the exothermic reactions and that absorbed by the endothermic reactions of carbonization.
The quantity of heat energy to be supplied for the carbonization of a given weight of a coal or of a mixture of coals is all the greater as the rate of exothermicity of the coal or of the mixture of coals is greater. low.



   The thermolysis of humic substances and woody graphitic seeds is accompanied, among other things, by the production of water vapor
This is involved, among other things, in endothermic reactions of gas to water. The composition of this water gas depends at any time during carbonization on the equilibrium factors which determine the composition of the water gas. These gas-to-water reactions, which form part of the carbonization reactions, can, for example, for coals with a low carbonization rate, therefore rich in humic matter and, consequently, in oxygen, considerably reduce the rate of carbonization. exothermicity of all the carbonization reactions and, therefore, the carbonization of such coals requires a high expenditure of heat energy.



   Humic substances, asphaltic substances and graphitic seeds are groups of substances. Each of these groups comprises a very large number of substances of very different composition, molecular structure, chemical vulnerability and thermal stability.



   According to the chemism of carbonification, the asphaltic substances contained in the coals are formed by the deoxygenation of humic substances, while the asphaltic graphitic seeds of the coals are formed by the thermal decomposition of the substances.

  <Desc / Clms Page number 20>

 asphaltic.



   The oxygen contained in the woody graphitic seeds is energetically bound to them, since temperatures of more than 600 C are required to actively decompose the woody graphitic seeds.



   Oxygen binding in humic materials is rather weak as demonstrated by the concentration of oxygenates in the volatile products of the onset of thermal decomposition of humic materials in poorly evolved charcoals.



   In the formation of the coherent semi-coke during carbonization, it is the fusible asphaltic substances which ensure the asphaltic melting of the coal.



   It is of little importance from the point of view of coking that these fusible asphaltic substances exist in the coal in the free state or chemically combined, for example, in the form of branches of more or less graphitically evolved graphitic nuclei. The same is the case for humic substances.



   Humic materials generate asphaltic materials which may possibly melt during carbonization, depending on the rate of carbonification of the coal and their concentration in the coal.



   Asphaltic substances generate graphi- tic germs during carbonization depending on the carbonization rate of the coal and their concentration in the coalo
Therefore, if by means of extraction of the coals by means of sufficiently selective solvents one achieves the quantitative separation and the exact dosage of humic substances, asphaltic substances and graphitic seeds contained in the coals, the the results of these analytical methods would not be fully efficient in the control of coking;

  ,
On the other hand, any method of classifying coals according to their order of carbonification rate, starting from the semi-coke or coke yields which they accuse when carbonization is carried out, is marred by errors, sometimes significant, mainly for coals. little evolved because of the importance which can acquire, during the carbonization of these coals, the reactions of gas with water.



   The implementation of the process according to the invention which will be described later requires knowledge of the concentration of coals in humic materials, asphaltic materials and graphitic seeds, as well as knowledge of the behavior of these three constituents of the carbon or mixtures of coals during carbonization, both when the coal is carbonized in isolation and when it is carbonized in admixture with other coals or with carbonaceous materials other than fossil coals.



   The method according to the invention for determining the unit humus, unit asphaltic and semi-coke values of the different types of coals in the whole series of fossil coals meets the requirements cited above and mixtures of coals. possibly containing carbonaceous substances other than fossil coals o
In the series of different types of fossil coals, namely 1) flaming dry type, 2) flaming fat type, 3) fat gas type, 4) coke type with low carbonization pressure, 5) coke type with high carbonization pressure - sation, 6) type 3/4 fat, 7) type 1/2 fat Sypopathon types 1, 7 and 8 are characterized by a high value of the ratio:

   unit semi-coke unit asphaltic materials
These are the coals my auto-cokfiats

  <Desc / Clms Page number 21>

 
The types of self-coking coals, i.e. types 2, 3, 4 and 5 show values of the unit semi-coke ratio asphaltic unit asphaltics which increase in the order of type 2 to type 5.



   Type 6 coals lie between types 5 and 7 and their coking properties are sometimes strongly influenced by the rate of carbonization ;, The same is true of the coking properties of certain type 1 coals which are at the limit between types 1 and 2 coals.



   Due to their low concentration in non-self-coking charcoal types 1, 7 and 8, the poorly or non-fusible asphaltic materials contained in the charcoals quickly and strongly dissociate during carbonization so that asphaltic melting does not occur. or insufficiently to ensure the binding in coherent semi-coke of the graphitic seeds present.



   The coals of types 2, 3 4 and 5 all show the phenomenon of asphaltic melting during carbonization o Humic materials, asphaltic materials and graphitic seeds contained in the coals of types 3 4 and 5, in the most evolved coals of the type 2 and the less developed type 6, are largely additive. On the other hand, humic substances, asphaltic substances and graphitic seeds of coals of types 1, 7 and 8 have very different compositions and chemical structures from those of the components of coals of types 3, 4 and 5. , the components of coals of types 1, 7 and 8 do not behave additively with the components of coals of types 3, 4 and 5 in carbon mixtures.



   The differences in composition and chemical structure between the components of the different types of carbon are necessarily the greatest for humic and asphaltic materials and much less for woody and asphaltic graphitic seeds, due to thermal stability and strength. much greater chemical stability for graphtics than for humic and asphaltic materials
Concept of the overall rate of swelling and foaming of semi-coke.



   According to the chemism and the mechanism of the coking. the materials present in the semi-coke mother-paste of self-coking coals or self-coking mixtures of coals, at the time of the birth of the semi-coke, are the residual fusible asphalt materials of the disso - ciation and the chemical action which preceded the semicoke mother-pulp stage; graphitic seeds present in the coal and those which have been formed from asphaltic materials until the moment when the semi-coke mother-pulp stage is reached.



   The proportion of meltable asphaltic materials which arrive at the semi-coke mother-pulp stage and their own fusibility in this stage are all the greater as the unit asphaltic materials value of the coal or of the carbon mixture is greater, than the value unit humus charcoal is smaller and the temperature is lower at the time of birth. sem-coke
The viscosity of the semi-coke mother stock immediately before the birth of the semi-coke is determined by the quantity and inherent meltability of the asphaltic materials in the semi-coke mother stock, by the quantity of solids (graphitic seeds + ashes) in the semicoke mother paste and by the temperature at which the semicoke birth takes place.



   The viscosity of the semi-coke mother paste is lower the greater the quantity and inherent meltability of the asphaltic materials in the semi-coke mother paste, the greater the quantity of solids in the semi-coke mother paste.

  <Desc / Clms Page number 22>

 the semi-coke mother stock is weaker and the birth temperature of the semi-coke is lower.



   The amplitude of the gas phase (gas + vapors) at the time of the birth of the semi-coke is all the greater as the quantity and the inherent fusibility of the fusible asphaltic materials present in the semi-coke mother stock are larger.



   The semi-coke mother-pulp stage and the birth of semi-coke occur for all coals or all self-coking coal mixtures at a given point in the primary carbonization period 3 of the carbonization test. "in vitro", that is, in the region of 4700 C to 5600 C temperatures measured outside the carbonization tube of the "in vitro" carbonization tester.



   The height of the methane tip of the "in vitro" carbonization profiles of the coals indicates the amplitude of a fraction of the gas phase (in particular the permanent gases) during the third period of the primary carbonization.



   Depending on the chemism of the carbonization, the amplitude of production of permanent gases and vapors gradually decreases as the temperature rises during this third period of the primary carbonization.



   The greater the height of the methane tip of the "in vitro" carbonization profile of a coal, the greater was at any time during the third primary carbonization period; the production of gases and vapors.



   The temperature at which, during the third period of the primary carbonization of the "in vitro" carbonization test, the formation of semi-coke from a charcoal to a self-coking mixture occurs. of carbon is all the lower as its "primary volatiles" value is lower.



   Indeed, the study of the different types of auto-coking coals, that is to say types 2, 3, 4 and 5, reveals, if we consider these types in the order in which they are named, that the unit semi-coke value increases regularly, that the unit asphaltic materials value decreases regularly and that the unit humic carbon value decreases regularly.



   For a given value of the carbonization pressure of the coal or of the mixture of coals and for given carbonization methods, the overall rate of swelling and foaming of the semi-coke or of the coke derived from a coal, or from a mixture of self-coking coals, is defined by a relation which expresses:

   - that the overall rate of swelling and foaming is directly proportional to the height of the methane tip of the "in vitro" carbonization profile of the coal or of the mixture of coals considered, - that the overall rate of swelling and foaming is not proportional to the unit semi-coke value of the coal or of the mixture of coals, - that the overall rate of swelling and foaming is inversely proportional to the primary volatiles value of the coal or of the mixture of coals.



   The overall rate of swelling and foaming can be expressed by the methane tip height relationship of the carbonization profile unit semi-coke value x primary volatile matter value
The overall rate of swelling and foaming of the semi-coke can also be expressed by any other relation having the same physical meaning as

  <Desc / Clms Page number 23>

 
Concept of the overall rate of contraction and cracking of semicoke or coke during secondary carbonization.



   The average rate of graphitic evolution of the graphitic seeds from which the semi-coke is formed is ¯determined mainly by the rate of graphitic evolution of the graphitic seeds contained in the carbon or the mixture of carbon
According to the chemism of the carbonification, the rate of graphitic evolution of the graphitic seeds contained in the coals is all the higher as the rate of carbonification of the coal is higher.
In the series of carbon types or self-coking carbon mixtures, the higher the unit semi-coke value, or the higher the coke yield. (Ashless and semi-graphite cracking of the primary volatiles ) "in vitro", is high,

   the higher the graphitic devolution of the graphitic seeds contained in the coals, the less the semi-coke contracts and cracks during secondary carbonization.



   The overall rate of contraction and cracking of semi-coke or coke, of a coal or of a mixture of coals under given carbonization conditions is expressed by the relation Global rate of contraction and cracking of the semi-coke. coke or coke = yield of coke "in vitro" without ash and without semi-grapes of carcking primary volatiles) or by any other relation having the same physical meaning.



   Concept of the global rate of carbonization pressure.



   Under given carbonization conditions, the overall rate of carbonization pressure of a charcoal or a mixture of self-carbonating coals is greater the higher the overall rate of swelling of the semi-shell.



   The overall rate of carbonization pressure of a coal or a mixture of self-coking coals is lower the higher the rate of contraction of the semi-coke. We express the global rate of carbonization pressure of a coal or a mixture of coals under given carbonization conditions by the relation Value overall rate of carbonization pressure = global rate of swelling or by any other relation having the same signifiTs global physical cation contraction.



   The carbonization pressure opposes the free development of the semi-coke skeleton and, consequently, the swelling and foaming of the semi-coke.
Rate of swelling and foaming of semi-coke, rate of contraction and cracking of semi-coke or coke, rate of carbonization pressure are only of physical significance for coals or mixtures of self-coking coals .



   Concept of the overall cokeo size stability rate
Under given carbonization conditions, the overall rate of coke size stability is higher the lower the overall rate of swelling and foaming of the semi-coke, the lower the gobai rate of contraction and cracking. is lower and the overall rate of carbonization pressure is higher o
The overall rate of size stability of coke derived from a charcoal or a mixture of self-coking coals under given carbonizing conditions is expressed by the relation

  <Desc / Clms Page number 24>

 
Overall rate of caliber stability =
Overall rate of carbonization pressure or by
Overall rate of swelling x Overall rate of contraction any other relationship with the same physical meaning.



   Concept of the level of exothermicity of coal or of a mixture of coal.



   It is the difference between the latent heat, at room temperature, of combustion of coal or a mixture of coals and the latent heat, at room temperature, of combustion of the products of the "in vitro" carbonification of the carbon. charcoal or a mixture of coals.



   To avoid having to resort to the use of the bomb calorimeter, we can determine the latent heat of combustion of coals and cokes according to the methods recommended by Lefebvre and Georgiadis (See Chimie et Industrie - Vola 46, n 2 = August 1941).



   The latent heat of combustion of the permanent gases produced during the "in vitro" carbonization test of coals or mixtures of coals is one of the data of this test.
Depending on the chemism of the carbonization and the way in which the "in vitro" carbonization test is carried out, the latent heat of combustion of the tar can be regarded as constant for all the "in vitro" carbonization tars of all types of coals. The latent heat of combustion of benzols produced by the "in vitro" carbonization of coals or mixtures of coals can be considered to be the same for all coals and mixtures of coals. The latent heat of combustion of "in vitro" carbonization tar = 8,500 ko cal / kg.



   The latent heat of combustion of "benzols" of "in vitro" carbonization = 10,000 k.cal / kg.



   With equal exothermicity rate, a given weight of coal or a mixture of coals requires the same expenditure of calorific energy under given carbonization conditions.
According to the present invention, and from the data of the only "in vitro" carbonization test, all the values are therefore determined which clearly determine the characteristics of the coke that a coal or a mixture of coals produced in a given industrial installation, at a given firing rate, and the amount of heat energy that must be expended for the coking of the coal or the mixture considered, for given values of the water contents of the coal or of the mixture of coals, of the thermal efficiency of the battery of ovens and the rate of uniformity of cooking of the loads.



   There is, for example, a battery of modern coke ovens, made of silica, that is to say designed to withstand high operating temperatures and ensure a high rate of carbonization. The loose coke produced by the coking plant should give as high a yield as possible of the best metallurgical coke. It is general experience that charcoal type coke at high carbonization pressure best meets this requirement. However, the carbonization of this type of coal, at high cooking rate, can give rise, because of its too high carbonization pressure at high firing rate, damage to the masonry of the ovens or laborious digging.



   The coking plant working at a high carbonization rate must therefore choose a type of coal or constitute mixtures of coals whose coking properties are as close as possible to the coke type coal at high carbonization pressure but deviate sufficiently from it to avoid damage to heating walls and laborious diversions. This is called working in good operating conditions.

  <Desc / Clms Page number 25>

 



   Thus, by way of example., For a modern coking plant, equipped with silica coke ovens, with an average width of approximately 450 mm and working at a charge firing rate corresponding to the nominal capacity of the battery, the coal or the mixture of coals to be baked in order to permanently produce the highest proportion of metallurgical coke, the best that such a coking plant can produce without having to fear too strong pressures of carbonization and laborious unloading, must permanently acknowledge the characteristics given below, deduced, in accordance with the present invention, from the results of "in vitro" carbonization of the coal or of the mixture of coals providing industrially, under the operating conditions defined more high,

   the standard coke for the coking plant in question
 EMI25.1
 Carbon content o000000oooooaaooooaoooo 87.28%) on carbon Hydrogen content oooaoooooeooooo000000 5.17%) dry Oxygen content 00000.0000.0..0000.0.00 5.71%) free from Sulfur content + nitrogen "00000.00.0 .. .... 1.84%) ash Semi-coke unit value.

   o ......... <, <,? = ¯ 788.76 kg
 EMI25.2
 
 <tb> Value <SEP> humic.charcoal <SEP> unitary <SEP> = <SEP> 153.30 <SEP> kg
 <tb>
 <tb> Value <SEP> materials <SEP> asphaltic <SEP> unitary <SEP> = <SEP> 177.96 <SEP> kg
 <tb>
 Height of the methane tip of the carbonization profile = 1.300 cm3 Value overall rate of contraction and cracking of semi-coke or coke =
1.33 Value of global rate of swelling and foaming of the semi-coke '= 7.80 Value of global rate of carbonization pressure = 5.85 Value of global rate of stability of the size of coke 56.3 Value of exothermicity of the coal or of the mixture of coals 380,000 k.cal / tonne Ash content of the coal or mixture of coals between 6 and 7%
The characteristics defined above are those of coal. or the typical mixture;

   which industrially produces the standard coke for the coking plant in question under the carbonization conditions defined above o These are the basic data for the comparison of the coking properties of the coals and mixtures for the coking plant in question o
Any charcoal or mixture of charcoals giving rise to the same charac- teristics, deduced according to the present invention from the results of "in vitro" carbonization of the charcoal of this typical mixture of coals, produced industrially, under the carbonisation conditions defined above. , the standard doke and requires the same expenditure of heat energy for coking as coal or the typical mixture of coals.



   As is the case for any coal or mixture of coals giving rise to the same unit semi-coke, humic unit coal, unit asphaltic materials and the same height of the methane tip of the "in vitro" carbonization profile as the coal or the typical mixture of coal.



   In fact, for self-coking fossil coals or self-coking mixtures of fossil coals, identical values for the unit semi-coke, for the unit humic coal, for the unit asphaltic material and for the height of the unit. the methane tip of the 'in vitro' carbonization profile imply identical coking properties. The same value for the unit semi-coke implies the same rate of graphite evolution of the graphitic seeds present, therefore, the same rate of contraction and cracking of semi-coke and coke.

   The same value for the unitary asphaltic material associated with the same height of the methane tip of the "in vitro" carbonization profile, signifies the same concentration of materials.

  <Desc / Clms Page number 26>

 asphaltics, the same fusibility of asphaltic materials and the same yield of asphalt graphitic seeds during carbonization.



   The same concentration of current and potential graphitic seeds and the same concentration of asphaltic materials with the same chemical structure and the same meltability result in the same birth temperature of the semi-coke. This results in the same rate of swelling and foaming of the semi-coke.The equality of the rate of swelling and foaming and the rate of contraction and cracking results in the equality of the rate of carbonization pressure and, therefore, the equal rate of cokeo size stability
Unequal concentration, composition and structure of graphitic seeds as well as unequal concentration, composition and structure of current and potential asphaltic materials lead to equality of concentration,

   composition and structure of humic materials and even signify exothermicity of carbonization reactions.



   To constitute the standard mixture from two or more self-coking coals which are available, they are carbonized separately "in vitro" and the semi-coke unit value is established for each of them, the coal value. humic unit, the asphaltic materials-unit value and the height of the methane tip of the carbonization profile.



   By calculation, it is easy to determine the proportions of the charcoal which must be mixed to constitute the mixture showing a unit humic carbon value close to 153.3 and included, for example, between 150 and 155, an asphaltic unit value close to 177.96 and included, for example, between 175 and 1800
The "in vitro" carbonization of the mixture, as has just been indicated, is then carried out and its different characteristics are determined in order to compare them with those of the carbon or of the standard mixture which industrially provides the standard coke.



   If the self-coking coals available are categorized frankly among types 3, 4 and 5, verification by carbonization "in vitro" of the mixture determined by the process according to the invention is not essential. But, as soon as among the Self-coking coals used Some are found to be classified too close to type 6 or too close to type 2, verification by "in vitro" carbonization of the mixture determined according to the invention is necessary.
1 There are two types of self-coking carbon, that is to say that, narbonized "in vitro" in the isolated state, they each give a very coherent coke.



     One, called A to simplify the explanation, is a flaming fatty type coal which has a unit humic carbon value of 227.02 and a unit asphaltic matter value 199.62 The other, called B is a high pressure coke type coal of carbonization, which has a unit humic charcoal value 98,27 and a unit asphaltic material value 158, 200
To easily find the proportion of A and B coals which gives rise to a mixture whose unit humic carbon value is close to 153.30 (value for the standard mixture providing the standard coke in the battery considered) and whose unit asphaltic matter value is close to 177.96 (value for the standard mixture providing the standard coke)

   we can use a graph such as that shown in figure 32 On the x-axis, we plotted the values corresponding to charcoal A and on the y-axis those corresponding to charcoal B We draw on this graph a straight line such that 15 whose equation is x + y = 1000

  <Desc / Clms Page number 27>

 We also draw a line 16 whose equation is 227.02x98.27 y = 150 (value a little less than 153.30) and a line 17 whose Inequation is 227.02 x + 98-, 27 y = 155 (value a little greater than 153.30) Line 15 intersects lines 16 and 17 respectively at points 18 and 19.

   We then draw a line 20 whose equation is 195.62 x + 158.20 y = 175 (value a little less than 177.96)
It can be seen that this last straight line intersects straight line 15 at a point 21 which is more or less coincident with the point of intersection 19 of straight lines 15 and 170 As a result, point 21 can be adopted as the figurative point of the mixture to be made, , This must contain 44% of the carbon A and 56% of the carbon B.



   The "in vitro" carbonized mixture gives a unit humic carbon value of 152.03, a unit asphaltic matter value of 183.40 and a height of the methane tip of the carbonization profile corresponding to 1,300 cubic centimeters.



   If, in the series of self-coking coals in vitro ", that is to say the flaming fat type, the gas fat type, the low carbonization pressure coke type and the high pressure coke type, carbonization, on the one hand, several coals of the same type or of closely related types are available, for example several coals of the flaming fat type and / or of the fatty gas type and, on the other hand, several coals of the coke type at low carbonization pressure and / or of the coke type at high carbonization pressure, the respective different points of the coals of one of the two types are plotted, for example, on the y-axis of the graph,

   the different respective points of the coals of the other type on the abscissa axis of the graph and one thus quickly realizes the possibility of constituting the standard mixture from one coal or from several coals mixed in given proportions of the first type, and one or more coals mixed in given proportions of the second type.



   The results of the “in vitro” carbonization of mixtures calculated, according to the present invention, from the different types of “in vitro” self-coking coals correspond with a sufficient approximation to those of the original mixture and therefore they industrially provide the result. standard coke.



     If the line 20 had not met the line 15 at a point 21 close to one or the other of the points 18 and 19, we would have drawn a line corresponding to Inequation 195.62 x + 158.20 y = 180 ( value a little higher than 177.96) in order to see if the point of intersection of this new line with the line 15 would not have been closer to one or the other of the points 18 and 19 In 1-'affirmative, we could have adopted this point as a figurative point of the mixtureo This line similar to the line 2o has not been represented so that figure 33 remains clearer.



   If we had not found a meeting point of lines 15, and 16 or 15 and 17 close to the point of meeting of lines 15 and 20 or of line 15 with the line similar to line 20 but not shown, this- would have meant that the. two coals envisaged could not by themselves give the standard coke and that it was necessary to add a third component, the necessary characteristics of which are indicated by the graphical study which has just been carried out for the two auto-coals. coking agents available.

   This third component can be a mixture of self-coking charcoal and non-self-coking charcoal or a non-self-coking charcoal (type 1, 6, 7 and 8) or a mixture of several non-self-coking charcoals or a mixture of non-self-coking coal with a carbonated substance other than fossil coals and whether or not derived from fossil coals.



  We then have to solve the problem below.



   If the graphic study of the mixtures of the self-coking coals available reveals that to constitute the standard mixture it would be necessary to be able to have a self-coking coal corresponding to approximately 150 kg. char-

  <Desc / Clms Page number 28>

 good humic unit and about 220 kg of unit asphaltic materials, such a coal can be constituted, for example, by 36.20% of flaming charcoal, 54.30% of lean charcoal (semi-fat) and 9.50 % hard grindable asphalt with a thermal decomposition curve similar to that of the unitary asphalt material.



   This artificial self-coking charcoal has the following characteristics:
 EMI28.1
 
 <tb> - ': Value <SEP> C / Cf <SEP> = <SEP> 1.187
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Value <SEP> semi-coke <SEP> unitary <SEP> = <SEP> 756.94 <SEP> kg
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Value <SEP> coal Humic <SEP> <SEP> unitary <SEP> = <SEP> 153.66 <SEP> kg
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Value <SEP> materials <SEP> asphaltic <SEP> unitary <SEP> = - <SEP> 217.53 <SEP> kgo
 <tb>
 
Height of the methane tip of the "in vitro" carbonization profile = 1230 cubic centimeters.



   If, instead of having coals which are all self-coking, only at least one self-coking coal and at least one non-self-coking coal are available to constitute the new mixture, it is no longer possible to be based, as in the case of only self-coking coals, on the fact that the actual and potential asphaltic materials of the various coals can be added to give rise to an arithmetic mean.



   In fact, the current and potential asphaltic materials of lean coals (anthracite 1/4 fat, 1/2 fat, 3/4 fat) are little or not fusible and do not or hardly arrive at the stage of semi-mother paste. -coke during primary carbonization. This is due to their too low concentration in these types of coals and, consequently, to the high rate of their dissociation during primary carbonization and to their high and variable rate of graphite evolution.



   Current and potential asphaltic materials from dry, non-self-coking "in vitro" flaming coals exhibit a low and variable rate of graphite evolution and are therefore thermally and chemically unstable. They also do not or almost do not reach the stage of semi-coke mother paste due to their low concentration in these types of coals and the action of the pyrolysis products of humic materials on the asphaltic materials during the second. period of primary carbonization.



   However, in the presence, on the one hand, of certain coals of the flambame fatty and fatty gas types, the meltable asphaltic materials of which reach a large proportion of the semi-coke mother-paste stage; or on the other hand, of coals situated at the limit between self-coking coals and non-self-coking “in vitro” coals, the “in vitro” carbonization of mixtures determined from the “in vitro” carbonization data. vitro "of the isolated charcoals, still responds with sufficient approximation to the characteristics of the typical mixture).



   2 By way of example, let us choose two coals A and B, the first of which is self-coking "in vitro" and the second is non-self-coking "in vitro", these two coals also having the following characteristics:
 EMI28.2
 
 <tb> A <SEP> B
 <tb>
 <tb> Value <SEP> bharbon Humic <SEP>
 <tb>
 unitary <tb> <SEP> 212.71 <SEP> 70.02
 <tb>
 <tb>
 <tb> Value <SEP> materials <SEP> asphaltic
 <tb>
 <tb> unitary <SEP> 214.42 <SEP> 119.60
 <tb>
 <tb>
 <tb> Height <SEP> of <SEP> the <SEP> point <SEP> methane
 <tb>
 <tb> from <SEP> profile <SEP> of <SEP> carbonization <SEP> 1.700 <SEP> 1035
 <tb>
 
During carbonization, a high proportion of the fusible asphaltic material of the A coal arrives at the. mother dough stage. semi-coke;

   com

  <Desc / Clms Page number 29>

 thinking in admixture with a non-self-coking charcoal, 1? absence, in the semi-coke mother stock; more or less fusible asphaltic materials derived from nn-self-coking carbon "in vitro" o
The calculation of the mixture of these two coals for the purpose of constituting the typical mixture gives 58% coal A and 42% coal B
The "in vitro" carbonization of this mixture gives the following characteristics:

   
 EMI29.1
 
 <tb> Value <SEP> semi <SEP> coke <SEP> unitary <SEP> = <SEP> 785.92 <SEP> kg
 <tb>
 <tb> Value <SEP> coal Humic <SEP> <SEP> unitary <SEP> = <SEP> 161.78 <SEP> kg
 <tb>
 <tb> Value <SEP> materials <SEP> asphaltic <SEP> unitary <SEP> = <SEP> 176.75 <SEP> kg
 <tb>
 <tb> Height <SEP> of <SEP> the <SEP> point <SEP> methane <SEP> of <SEP> profile <SEP> of <SEP> carbonization <SEP> = <SEP> 1.300 <SEP> cm3
 <tb>
 
These values are sufficiently close to the values of the typical mixture to allow the industrial production of standard coke from the mixture of A and B coals in the calculated proportions.



   The coals intermediate between coke-type coals and gas fatty coals generally do not withstand strong additions of lean non-self-cokefinate coals "in vitro" to constitute the standard mixture.



   As such, the mixtures calculated from the "in vitro" carbonization data for the constitution of the new mixture from these types of carbon generally give "in vitro" values sufficiently close to those of the mixture. type to allow industrial production of the standard coke.



   3 Let us choose two coals A and B, the first of which is self-coking "in vitro" and the second of which is non-self-coking "in vitro", these two coals having, among others, the following characteristics
 EMI29.2
 
 <tb> Ao <SEP> B.
 <tb>
 <tb>
 <tb>



  Value <SEP> coal Humic <SEP>
 <tb>
 unitary <tb> <SEP> 172.40 <SEP> kg <SEP> 83.27 <SEP> kgo
 <tb>
 <tb>
 <tb> Value <SEP> materials <SEP> asphalti-
 <tb>
 <tb> ques <SEP> unitary <SEP> 185.60 <SEP> kg <SEP> 128.3 <SEP> kg
 <tb>
 <tb>
 <tb> Height <SEP> of <SEP> the <SEP> point
 <tb>
 <tb> methane <SEP> of <SEP> profile <SEP> of
 <tb>
 <tb> carbonization <SEP> "in <SEP> vitro " <SEP> 1465 <SEP> cm3 <SEP> 1100 <SEP> cm3
 <tb>
 
The calculation of the mixture of these two coals for the purpose of constituting the typical mixture gives 77% A coal and 23% B coal.



   The carbon B gives "in vitro" a slightly coherent coke so that the meltable asphaltic materials which it contains are not completely devoid of value for the coking. The mixture industrially gives a coke very close to the standard coke.



   In the case where a calculated mixture comprising high proportions of "in vitro" non-alto-coking charcoals does not give, during its "in vitro" carbonization, results sufficiently close to those of the standard mixture, the results of its carbonization "in vitro" provides in all cases the quantitative and qualitative indications necessary for the correction of the calculated mixture. To carry out these corrections, the possible use of all carbonaceous substances, whether or not derived from fossil carbons, should be considered.



   Let us now consider how it is necessary to operate to determine the constitution of the new mixture from coals, none of which is self-coking "in vitr".

  <Desc / Clms Page number 30>

 
The causes of the more or less complete absence of coking properties. charcoals of the anthracite, 1/4 fat, 1/2 fat, 3/4 fat and flamboyant dry types are revealed by the chemism of charring and charring by the mechanism of coking.



   Compared to charcoal or to the mixture of coals which industrially produces the standard coke, anthracite coals, 1/4 fat, 1/2 fat, 3/4 fat have too high a concentration of graphitic seeds, too low a concentration of humic matter , too low a concentration. in asphaltic materials, an excessively high rate of graphite evolution of current and potential asphaltic materials and an excessively low rate of exothermicity of the carbonization reactions.



   The dry flaming coals and a high proportion of the flaming fatty coals have, compared to the coal or mixture of coals which industrially produces the standard coke, a too low concentration of graphitic seeds, a too high concentration of materials. too high a concentration of asphaltic materials, too low a rate of graphitic evolution of current and potential asphaltic materials, too great a chemical vulnerability of current and potential humic and asphaltic materials, and a rate of exothenicity of the carbonization reactions which, as a result of the massive intervention of gas reactions with water during the primary carbonization,

   may be significantly lower for these types of coals than for the coal or the mixture of coals which industrially provides the standard coke.



   We can see from this overview and from the concepts set out in this descriptive document that the most graphitically evolved flamingo coals and the less graphitically evolved 3/4 fat coals together lend themselves to the constitution of the mixture which produces industrially the standard coke.

   But this is no longer the case for flaming coals less evolved graphitically (flaming gras are similar to dry flamingos and flaming dry ones) and lean more evolved coals graphitically approaching anthracite (1/2 fat, 1/4 fat) and the anthracite
The constitution of the mixture which industrially provides the standard co-ke from non-self-coking coals is carried out according to the present invention by adding carbonaceous substances other than fossil coals and deriving or not from fossil coals and the dosage of which in the mixture is determined by the data of the process according to the present invention.



     Three kinds of carbonaceous substances are to be considered:
1) substances with a high concentration of graphitic seeds, including charcoal, semi-coke, coke, with an appropriate fineness of grinding.



   2) substances with a high concentration of humic matter, including lignites, shiny lignites, durains of different types of coals, certain products of the partial oxidation of coals and lignites, oxygenated extracts of different types of coals.



   3) substances with a high concentration of asphaltic materials, among which may be mentioned, natural asphalts with a high level of polycyclic aromatic structure, vitrains of different types of charcoal, non-oxygenated extracts of different types of charcoal, certain carbon products. partial or total hydrogenation of coals or lignites and their derivatives, petroleum pitches.



   In addition, certain substances containing mixtures of humic and asphaltic materials can be considered. Among these materials, mention may be made of low- and high-temperature carbonization tar pitches, clairains of various types of carbon, partially oxidized asphalt.

   The study of these substances and their ability to intervene in the constitution, from non-self-coking coals,

  <Desc / Clms Page number 31>

 of the mixture industrially producing the standard coke, is carried out according to the data resulting from the process according to the present invention, for example, by application of the data provided by the carbonization "in vitro" of a mixture of the carbonaceous material with a carbon of coking properties already studied according to the present invention,
Some of these carbonaceous substances, alone or mixed, will only be suitable after having undergone a treatment to increase thermal and chemical stability, inter alia by heating in 1-shelter of Air, at an appropriate temperature, for example, between 300 and 4000 C,

   possibly in the presence of pressurized water vapor for a longer or shorter time
The control of the graphitic evolution of the asphaltic substances and of the increase in the thermal and chemical stability of the humic and asphaltic substances subjected to this treatment is carried out, according to the process according to the present invention, for example, by data provided by the "in vitro" carbonization of a mixture of the carbonaceous material with a charcoal of coking properties already studied according to the present invention.



   Thus, the re-use of an asphalt which is insufficiently thermally and chemically stable leads to an insufficient height of the methane tip of the carbonization profile for the unit asphaltic material value of the mixture: Example mixture of 30.5% carbon from an intermediate type between flambant sec and flambant gras; 52.0% of lean type coal, 17.5% asphalt with low rate of polycyclic aromatic development. Unit semi-coke value = 707.49 kg Unit humic carbon value = 169.82 kg Unit asphaltic material value = 270.27 kg Height of the methane tip of the "in vitro" carbonization prof.il = 1300 cm3.



   The mixture is self-coking "in vitro" but would come much closer to charcoal types 3, 4 or 5 by the use of a thermally and chemically more stable asphaltic material.



   For carbonization installations such as alumino-silicate cocoa furnaces, gas furnaces with horizontal or inclined chambers, gas furnaces with vertical retorts with intermittent or continuous operation, gas furnaces with horizontal retorts, gas furnaces or coke, the heating methods of which differ in principle from those generally applied in the carbonization industry and, in general, for any given installation of high or low temperature carbonization of coal or mixtures of carbon. coals, the standards of the coal or of the mixture of coals which industrially supplies the standard coke for the installation considered, must be established for each specific case, according to the data of the present invention.



   CLAIMS.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

1 Process for determining the composition of the feed to be introduced into a carbonization installation - 'du coal in order to obtain in this installation and under good operating conditions the same coke as a standard coke already obtained in this and under good operating conditions, from a known coal or from a known mixture of carbonized coal at the carbonization rate imposed by the quantities of products to be supplied by the installation in a given time, characterized in that the known charcoal or the known mixture of coals giving rise industrially to the standard coke is carbonized "in vitro", in that the elemental composition of this coal or of this mixture is determined of coals, in that we <Desc / Clms Page number 32> carbonises "in vitro" under the same conditions, a little evolved coal .. with a high oxygen content (unit humic coal), in that the elemental composition of this coal is determined, in that a natural asphalt is carbonized "in vitro", under the same conditions, grindable hard, oxygen-free, with an appropriate thermal decomposition curve (unit asphaltic material), in that the average oxygen content and the average volatile matter value at 900 C of a sufficient number of semi -cokes obtained at 600 C (unit semi-coke); , in that one determines, from the elemental composition and in vitro carbonization data "of the known coal or the known mixture of coals, its unit humic carbon values, unit asphaltic materials semi-coke, in that the coking properties of the known charcoal or the known mixture of coals are expressed from the data of "in vitro" carbonization, the chemism of the carbonification and the chemism and mechanism of coking, by the overall rate of swelling and foaming the semi-coke; the overall rate of contraction and cracking of the semi-coke and of the coke, the overall rate of carbonization pressure of the known coal or of the known mixture of coals, the overall rate of size stability of the coke, as determined, from the data of "in vitro" carbonization, the exothermicity of the carbonization reactions of known coal or of the known mixture of coals, in that one carbonizes "in vitro" under the same conditions, each of the coals proposed to use in the new mixture, in that we determine the elemental composition of each of these coals, in that we determine for each of them the unit humic carbon, unit asphaltic materials and semi- unit coke, as has been done for known coal or the known mixture of coals, in that the proportions of the various coals in the new mixture are determined from their unit asphaltic material and unit humic carbon values so that the unit asphaltic material and unit humic carbon values of the new mixture correspond to these same values of the known coal or of the known mixture of primitive coals, ', 2. Following method of claim 1, characterized in. that the new mixture, determined in the manner which has just been indicated, is carbonized "in vitro", under the same conditions, in that it is checked whether the characteristics of the new mixture correspond to those of the charcoal or mixture of primitive coals, in that, in the case where the agreement of the characteristics of the new mixture and of the original mixture does not exist in a satisfactory manner, the new mixture is corrected according to the indications given by the results. of its "in vitro" carbonization. 3. - Method according to either of claims 1 and 2, in the case where at least one of the coals intended to constitute the new mixture is a non-self-coking coal, characterized in that the corrects differences between the results of the "in vitro" carbonization of the new mixture determined according to claim 1 or 2 and the results of the "in vitro" carbonization of known coal or of the known mixture of coals, by the introduction into the new mixture of carbonaceous substances other than fossil coals 4. Method according to claim 3, characterized in that the carbonaceous substances of humic character and / or of asphaltic character are subjected to a heat treatment in the presence of water vapor in order to increase their thermal and chemical stability, in that we ensure the control of this treatment by carbonization "in vitro", in that we determine the dosage in the new mixture, of one or more carbonaceous substances other than fossil coals, by the indications for the "in vitro" carbonization of the orientation mixture 5. Process according to Claim 4, characterized in that the "in vitro" carbonization of the humic and / or asphaltic substances is carried out in admixture with a charcoal, the characteristics of which are subsequently determined by the process according to one or the other. 'other of claims 1 and 20 <Desc / Clms Page number 33> 60 - Process for determining the composition of a charcoal, characterized in that the carbonization is carried out "in vitro" of this charcoal, in that the elemental composition of this charcoal is determined, in that carbonizes "in vitro" a little evolved carbon, with a high oxygen content (unit humic carbon), in that the elementary composition of this carbon is determined, in that it is carbonized "in vitro" in the same conditions a natural asphalt, hard, crushable, free of oxygen, whose thermal decomposition curve is appropriate (unit asphaltic material) in that the average oxygen content and the average volatile matter value at 900 C of a sufficient number of semi-cokes obtained at 600 C ( unit semi-coke) and in that the composition of the coal studied is expressed in unit humic coal value, in unit asphaltic material value and in unit semi-cok value. 70 - Method for determining the coking properties of a charcoal to be used in any field of coal use where the specific coking properties of the latter partially or totally determine the efficiency rate of its use, characterized in what is carried out in the "in vitro" carbonization of known coal or of the known mixture of coals,: 'which gives complete satisfaction in the field of use envisaged, in that it has been determined, from the data of this carbonization "in vitro" and from the data of the chemistry of the carbonification, and of those of the chemistry and mechanism of coking, the overall rate of swelling and foaming of sem-coke, the overall rate of contraction and cracking of semicoke and coke, the global rate of carbonization pressure of known coal or of the known mixture of coals, the overall rate of coke-grade stability, the exothermicity of the carbonization reactions of the known coal or of the known mixture of coal, in that the "in vitro" carbonization of the carbon is carried out. coal whose coking properties are to be determined, in that the coking properties of this coal are expressed - as was done for the known coal or the known mixture of coals and in that the coking properties of the coal studied are compared with those of the known coal or of the mixture known coals. 8 Processes as described above. in appendix 4 drawings.