BE823010A - PROCESS FOR MANUFACTURING A GRANULAR SULPHIDE MATERIAL - Google Patents

Abstract

An infusible and insoluble granular S-contg. material is prepd. by reacting a heavy petroleum fraction and sulphur while stirring in the presence of reaction medium. The products can be used as fillers, reinforcing agents, oil absorbants, intermediates for CS2 prodn. etc. and are esp. useful for the prodn. of granular carbon and activated carbon. The reaction medium reduces the viscosity of the reaction mixt. (giving a denser product of higher mechanical strength), suppresses agglomeration, and suppresses carbonisation, the product is highly reactive (e.g. for CS2 prodn.) and can be converted into activated carbon with a very high specific surface (>2000 m2/g).

Description

         

  Process for making a granular sulphide material, granular carbon or granular activated carbon

  
The present invention relates to a method of making an infusible and insoluble granular sulphide material by reacting a heavy petroleum material and sulfur while stirring in the presence of a reaction medium and optionally in the presence of a reaction medium.

  
 <EMI ID = 1.1>

  
Further, the invention relates to a process for making granular carbon, which process comprises carbonizing the granular sulphide material described above, and also relates to a process for manufacturing granular activated carbon, which process includes carbonizing and activating the material. granular sulphide described above.

  
 <EMI ID = 2.1>

  
by reacting a heavy hydrocarbon material such as as-

  
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rents produced such as fillers, reinforcing agents, oil absorbents and metal collectors, while

  
that the sulfurized material has excellent properties as an intermediate in the synthesis and manufacture of carbon disulfide, carbon articles, ion exchangers, adsorbents, etc., and one can also s 'expect such a material to offer various application possibilities. Accordingly, methods of making such sulfur-containing material have long been studied and some of these methods are described, for example, in the specification of US Patents No. [deg.] 2,447,004 , 2,525,343, 2,539,137,
2,585,454 and 3,248,303, as well as in the specification of French patent n [deg.] 1,479,451. In these known processes, infusible sulfur-containing materials are formed by adding sulfur to a heavy hydrocarbon such as asphalt, etc., then reacting them by heating.

   However, in these processes, a significant drawback is that hydrogen sulfide bubbles formed by the reaction with sulfur become incorporated to a large extent in the reaction product. In other words, when a hydrocarbon such as asphalt is reacted with sulfur, the viscosity of the reaction product increases significantly as the reaction proceeds, while the product becomes an infusible sulphide material and insoluble passing through a rubbery or viscous state. When

  
From this reaction course, the hydrogen sulfide bubbles forming during the reaction break up and easily emerge from the reaction system in the early stages of the reaction when the viscosity of this reaction system is relatively low but, over time As the reaction proceeds, the viscosity of the reaction system increases, thus making the release of bubbles difficult, while ultimately only a spongy sulfide material having low bulk density and low mechanical strength is obtained.

   This drawback can be overcome to some extent by adjusting the rate of temperature rise so that the reaction proceeds slowly, but in this case a difficulty is encountered because a long time is required to complete the reaction. reaction, thus greatly reducing the efficiency.

  
A second problem is that the infusible sulfur product will agglomerate in the reaction vessel to form large lumps. The removal of this material in large pieces, its transformation into granules by crushing or by grinding and molding are totally inefficient operations requiring a complicated step, so that the manufacturing process is not economical. In US Pat. Nos. [Deg.] 2,447,005 and 2,447,006, methods are described which make it possible to alleviate the disadvantage described above by spraying a uniform liquid mixture of a heavy and heavy hydrocarbon. sulfur

  
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products with heating, but these methods are not suitable from a practical point of view, since they require complicated apparatus and specific techniques.

  
A third problem is that the reaction temperature adopted in order to obtain the infusible sulfuric material is very high. In US Pat. No. 3,248,303, it is stated that It is necessary to heat the reaction system to temperatures above 450 [deg.] C to obtain an infusible product, but when the reaction system is heated to this elevated temperature, carbonization of the sulfurized material inevitably occurs.

   The carbonized material can be a useful material as well as the various carbonaceous materials and this is one of the important uses of the sulphide product but, since the latter offers other possibilities of uses than a carbonized material, the carbonization by heating at high temperature limits the uses of the sulphide product.

  
As indicated above, the conventional methods of manufacturing sulfur-containing materials give rise to various difficulties in the properties of the products and the processes themselves, so that there is a demand to develop a new process for the manufacture of sulfur-containing materials. 'a sulfurized material not exhibiting these difficulties.

  
Carbon articles are widely used in different industrial fields such as general chemical industry, electrochemical industry, electrical communications industry, atomic energy industry, etc., as electrically conductive materials, materials refractories, chemical resistant materials, construction materials, lubricants, machine parts, etc. These carbon articles are generally prepared by grinding a carbonaceous material, kneading it with a binder such as pitch, synthetic resin, etc., and then molding the mixture into a shape suitable for the intended application.

   Plain graphite, anthracite, hard coal, coke and coal have mainly been used as carbonaceous material for the manufacture of the carbon articles described above, but it is not always easy to ensure a stable supply. of these high quality raw materials.

  
As a result, petroleum raw materials which can be supplied in large quantities and at low cost have been valued and the petroleum coke industry in which these raw materials are used has acquired some importance.

  
this. A process for the manufacture of petroleum coke is generally in a delayed coking process of the type described.

  
in "Hydrocarbon Processing", 49 (9) 180 (1970). However, the

  
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The fluid does not provide high quality carbon articles and therefore is generally used as a fuel. On the other hand, the coke produced by the coking process

  
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large lumps accumulating in a coking drum from which the coke must then be removed while, moreover, this process is not suitable for continuous operation, / ion more than for mechanization and automation and, for example, elsewhere, the operating efficiency of the device is very low. In addition, the efficiency of the carbonization is not always satisfactory.

  
Accordingly, it is desirable to develop a new process for manufacturing carbonaceous materials without having to handle materials in large pieces reducing the efficiency.

  
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a process in which fusible molded articles such as pitch, etc., are transformed into infusible molded articles, by subjecting these molded articles to chemical treatment or heat treatment in an oxidizing atmosphere, and then subjecting the resulting infusible materials to a carbonization treatment.

  
The transformation to the infusible state is carried out by treating the

  
 <EMI ID = 8.1> nitric acid, an aqueous solution of chromic acid, an aqueous solution of potassium permanganate, etc., at a temperature below the softening point of the meltable material, as described in the patent application .Japanese published n [deg.]
31195/1973. However, this process is accompanied by corrosion of the apparatus due to the use of the oxidizing material or else, it presents a drawback - because a long period is necessary for the transformation into infusible material. desired.

  
Therefore, in view of the aforementioned difficulties which are encountered in conventional processes for the manufacture of carbonaceous materials, it is desirable to develop a new process for the manufacture of granular carbon which can be carried out using a raw material obtainable by large quantities and at low cost without the formation of powdered carbon offering possibilities of unlimited uses and, moreover, without having to resort to a specific operation to transform the fusible material into granules.

  
In addition, activated carbon is an extremely important material as an industrial adsorbent and it is used in a large number of fields, including not only adsorbents in the food industry and chemical industry, but also adsorbents. adsorbents for domestic refrigerators and water purifiers. Likewise, recently it has become evident that activated carbon is very effective in preventing and suppressing pollution of the environment, for example, air pollution and water pollution and, in this regard, it is It is desirable to develop a technique which makes it possible to economically supply a large quantity of good quality activated carbon.

   So far, activated charcoal has been made using wood or coconut shells as the main raw material, but these raw materials cannot be expected to provide a stable reserve of a large amount of charcoal. Recently, activated carbon has been manufactured using hard coal as a raw material, but the supply of hard coal for obtaining good quality activated carbon is limited, so this technique also poses a significant problem in ensuring a secure supply. and stable of a large amount of good quality raw materials.

  
In view of these different points of view, attempts have been made recently to manufacture activated carbon from a raw material such as a heavy petroleum hydrocarbon, of which a large supply can be ensured at a low price. For example, a process is known in which an alkali metal compound such as potassium sulphide, sodium hydroxide, sodium carbonate and potassium thiocyanate is added to asphalt or pitch, this addition being followed by carbonization, after which the carbonized material is activated; A process is also known in which an asphalt or pitch reaction product is carbonized and activated with sulfuric acid or sulfur.

   However, in the process in which an alkali metal compound is added, the latter must be removed by washing in a subsequent step,

  
so that this process is not practical. Likewise, in the process in which sulfuric acid or sulfur is used, sulfuric acid or sulfur must not remain in the activated carbon and, therefore, the step of removing this additive is superfluous. . However, in the process in which sulfuric acid is used, the treatment of the latter is dangerous since it is present in a large amount while, on the other hand, corrosion of the apparatus is a problem.

  
On the other hand, in the process in which sulfur is used, although hydrogen sulfide may be formed during the manufacturing step, corrosion of the apparatus does not pose a particular problem and Hydrogen sulfide can easily be regenerated to sulfur by a Clauss reaction or catalytic decomposition. Therefore, the sulfur formed can be used

  
several times, so that the process is then economically advantageous. The activated carbon obtained by the process in which sulfur is used has excellent properties the same or better than those of the activated carbon obtained from coconut charcoal, while the yield of activated carbon is high. However, in this case, the sulfurized material is unfortunately obtained in the form of a spongy product in large pieces while, as indicated above, it is difficult to. making a sulfurized material in the form of discrete granules of a desired particle size and of sufficiently high mechanical strength.

  
Likewise, the method of making the above granular carbonaceous solid material generally falls within the class comprising a method of crushing a product into large pieces, as well as a method of molding or agglomerating a powdered product into one. granular product using a suitable binder. In the first method, it is impossible to selectively manufacture a granular carbonaceous material whose grains have a defined particle size, while the yield of grains of the desired particle size is low. Likewise, the activated carbonaceous material obtained by crushing has drawbacks in that it tends to be deteriorated during its handling due to its irregular and angular shape.

  
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one generally obtains a granular material formed by molding mixing a powder of the base material and a binder, molding the mixture into granules, then subjecting the latter

  
heat treatment. Consequently, as a result of the handling of the powder, this method has disadvantages because the operating efficiency is low and, since the binding force existing between the binder and the grains of the powder is low, the grains of the material formed tend to be powdered by friction. Likewise, in the molding process, it is very difficult to obtain a fine granular material whose grains have a particle size of between a few microns and about 1 mm.

  
In addition to the processes described above, there is also known a process for the manufacture of granular carbon and granular activated carbon, in which process very viscous pitch with a high softening point is molded into granules which are then brought to granules. the infusible state. However, in this case, although an excellent granular carbon of high mechanical strength can be obtained compared to conventional products, since no binder is used, extremely precise techniques are required to achieve fusible material such as pitch in an infusible state without deforming it and, in

  
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granular, the grains of which have a particle size greater than about 1 mm.

  
The present invention makes it possible to meet the demands set out above, while avoiding the aforementioned difficulties and a characteristic of the present invention resides in the fact

  
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while stirring in the presence of a reaction medium and optionally also in the presence of an infusible and insoluble solid material, the infusible and insoluble granular sulphide material can also be charred or charred and activated.

  
In other words, by adopting the present invention, one can manufacture a granular sulfurized material, granular carbon or granular activated carbon having the desired particle size, satisfying the intended purposes and having excellent mechanical strength without having to resort to granulation by crushing

  
the grinding and molding of a solid material into large pieces and also without having to use a specific apparatus for granulation. The expressions “infusible” and “insoluble”, used in the description of the invention, mean that the granular material is insoluble in the reaction medium, the heavy petroleum material and the sulfur which are the materials used in the invention, in the sulfurization conditions of the process of the latter, this material also being infusible under the carbonization conditions; for example, even during a heating

  
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not undergo fusing, deformation, softening or thermal melting.

  
In the process of the present invention, by selecting the appropriate reaction conditions, one can obtain granular materials having any desired particle size.

  
between a few microns and several centimeters, for example, between about 1 micron and about 2 cm. The infusible and insoluble sulphide material obtained by the process of the present invention is characterized in particular by particularly high properties with regard to surface resistance and abrasion resistance compared to the properties obtained in granular sulphide materials produced by crushing. . The granular carbon obtained by the process of the present invention is also characterized by high reactivity, in particular, as an intermediate product in the manufacture of other carbon compounds such as tetrachloride.

  
carbon and carbon disulfide, compared to conventional materials. In addition, the granular activated carbon obtained by the process of the present invention is also characterized by a specific surface area greater than about 2,000 m2 / g (the specific surface area of commercially available products is usually about 500 to 1,000 m2 / g ), this specific surface being easily obtainable.

  
Further, the granular materials obtained by the process of the present invention are mainly granular or granular and asymmetric materials, but depending on the manufacturing conditions, disc or needle-shaped materials can be obtained. In any case, the surfaces of these materials are smooth, the granular product is superior as regards

  
its dimensional stability and fluidity, while it also has excellent mechanical strength, for example, excellent surface resistance. Likewise, in the process of the present invention, a dehydrogenation reaction and a sulfur polycondensation reaction take place, thereby forming a sulphide material of a three-dimensional lattice structure having high heat resistance, so that the

  
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The thermal reaction is noticeably less when the material is carbonized by heating while, therefore, the yield of carbonized product is very high. Likewise, during carbonization, the sulphide material is carbonized in the form of a solid phase without passing through the molten state and, therefore, one can obtain granular carbon having little tendency to undergo graphitization and thus, when granular carbon is activated,

  
excellent quality activated carbon having a microcrystalline structure can be obtained.

V

  
The heavy petroleum material used as a starting material according to the present invention is one which is liquid or solid at normal temperature (e.g., about 20 to
30 [deg.] C) and which has a softening point of less than about
400 [deg.] C, preferably less than 300 [deg.] C, a boiling point
(under normal pressure, for example, at about 1 atmosphere) on

  
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weight. Likewise, the heavy petroleum material used according to the present invention is a heavy petroleum residue and this heavy petroleum material derives from petroleum refining operations such as distillation, thermal cracking, catalytic cracking, solvent extraction. , acid treatment and the like. Among these heavy petroleum materials, there is, for example, a heavy residue obtained by distilling a crude oil

  
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ple, a residue having a boiling point greater than about
300 [deg.] C and an H / C atomic ratio of about 1.0 to 1.9), a heavy residue obtained from the extraction of crude oil, a residue from the distillation of crude oil under normal pressure or a residue from the distillation of crude oil under reduced pressure with a solvent such as propane, butane, pentane, hexane, cyclohexane

  
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about 350 [deg.] C, an H / C atomic ratio of about 0.5 to 1.8 and a softening point of about 5 to 300 [deg.] C), a heavy residue obtained by cracking crude oil, a distillation oil or a residue of a distillation oil under normal pressure or under reduced pressure (for example, of a boiling point above about 300 [deg.] C and of an H / C atomic ratio of about 0.2 to 1.7), as well as a heavy residue obtained by cracking, at an elevated temperature, a heavy material obtained during the extraction of a distillation residue from this material under normal pressure or a residue of distillation of this material under reduced pressure with a solvent (for example, of a boiling point greater than about 300 [deg.] C and an atomic H / C ratio approximately 0.2 to 1.7).

   Among the heavy petroleum materials which can be used according to the present invention, there are specifically, for example, various straight-run asphalts, heavy oils, air-blown asphalt, asphaltic bitumen, asphalt recovered during the process. solvent asphalt separation, kerosene or light oil catalytic cracking residue, kerosene thermal cracking residue

  
or light oils, a residue of cracking of naphtha, a residue obtained by thermal cracking or hydrocracking of a heavy fraction or of a residue, etc. Among these materials, the heavy materials of the asphalt series are excellent raw materials, since they make it possible to obtain, with a high yield and under relatively moderate conditions, a product having excellent thermal properties. regards the infusible nature, hardness and form. The raw materials described above can be used individually or as a mixture. Since these materials are used as the main raw materials according to the present invention, the term "raw material" will be used in the specification below to simplify the designation of these materials.

  
The reaction medium used in the process of the present invention is a hydrocarbon which is liquid at normal temperature and which has a boiling point of between about 50 [deg.] C and about 400 [deg.] C, preferably between about 70 [deg.] C and about
300 [deg.] C under normal pressure, this reaction medium also advantageously having low reactivity with sulfur (to form a polycondensation product) compared to the raw material used with sulfur. Among the reaction media-

  
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ple, having a boiling point of about 50 to 400 [deg.] C and an H / C atomic ratio of about 1.9 to 2.3), aromatic hydrocarbons (for example, those having a point d boiling between about 80 and 280 [deg.] C and an H / C atomic ratio of about 1.0 to 1.6), as well as petroleum fractions (for example, those with a boiling point of about 50 to 400 [deg.] C and an H / C atomic input of about 1.7 to 2.3). Among the preferred reaction media are, for example, aliphatic hydrocarbons such as hexane, octane and liquid paraffins, as well as aromatic hydrocarbons such as benzene, toluene, xylene and tert- butyl-benzene. These materials can be used individually or as a mixture.

   Further, among the preferred reaction media according to the present invention are petroleum fractions having a boiling point of between about 50 and about
400 [deg.] C under normal pressure obtained by distillation

  
 <EMI ID = 18.1>

  
Highly saturated paraffins with an H / C atomic ratio greater than about 1.8, for example, aliphatic hydrocarbons and petroleum fractions of the type described above have very low reactivity with sulfur. In addition, low boiling aromatic hydrocarbons (such as benzene, toluene, xylene, tert-butyl-benzene, etc.) also react very slowly with sulfur compared to heavy petroleum residues. The high boiling point naphthenic and aromatic hydrocarbons which have a complicated structure and which are the major constituents of heavy oil residues, as well as the saturated olefinic hydrocarbons readily react with sulfur at a high temperature. temperature included

  
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the raw material is an important consideration intervening in the choice of the reaction medium used. When setting

  
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used can be retrieved for repeated use.

  
The main purpose of the reaction medium used in the process of the present invention is to reduce the viscosity of the liquids of the reaction system in order to improve the transfer and dispersion of the raw material, sulfur and reaction product while, in reducing the viscosity of liquids, the hydrogen sulfide formed can be easily released from the reaction product. Further, by stirring the reaction system having reduced viscosity, the reaction product disperses well, thereby facilitating the formation of a granular product.

   Accordingly, the reaction medium used in accordance with the present invention can be one capable of reducing the viscosity of the reaction system and properly dispersing the raw material, as well as the reaction product in the reaction system, so that the reaction medium should not necessarily completely dissolve the raw material and the sulfur in it. Likewise, in the process of the present invention, the use of a reaction medium having

  
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This is due to the fact that an infusible and insoluble granular sulphide material is readily obtained at a relatively low temperature of, for example, between about 200 and about 230 [deg.] C. We do not yet fully understand the reason for this characteristic but, although we do not wish to limit ourselves to any theory, it is believed that since the meltable and soluble components selectively dissolve in the reaction medium, the proportions of the components fuses and soluble in the product

  
 <EMI ID = 22.1>

  
It is an infusible and insoluble granular sulfur product.

  
The amount of the reaction medium used according to the present invention depends on the type of starting material, the. type of the reaction medium, the amount of infusible and insoluble solid material optionally present, the amount of sulfur, the reaction conditions, etc., but.

   when, as the raw material, a mixture of a material having a high reactivity with sulfur and a material having a relatively low reactivity with the latter is used, for example, a residue from the distillation of crude oil under normal pressure, the material having a low reactivity contributes to cause the reaction medium to promote the dispersion of the reaction product and a granular sulphide product is obtained without having to add any other reaction medium and, therefore, in this case, it can be considered that the residue Crude oil distillation under normal pressure is a type of mixing a residue of crude oil distillation under reduced pressure and a reaction medium.

   However, when the viscosity of the whole reaction system increases sharply as the reaction with sulfur proceeds, thus making it difficult to form a dispersion by stirring as when using asphalt as a raw material, the D-

  
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haitable that the reaction medium is always present during the reaction, but the reaction medium can be added depending on the viscosity of the reaction product. A suitable viscosity for the reaction system is generally less than about
2,000 centistokes and preferably less than 400 cen-tistokes at 98.9 [deg.] C. In other words, the raw material is reacted with the sulfur in the absence of a reaction medium or in the presence of a small amount of the reaction medium and, when the viscosity of the reaction system increases, the reaction medium can be added. In some cases, this way of proceeding is preferred.

  
As will be indicated in the examples below, the particle size of the granular sulfurization product formed changes greatly depending on the amount and type of reaction medium and, as a general rule, when the amount of the reaction medium used increases in the same way as the quantity. compatibility of the reaction medium with the raw material and sulfur, the particle size of the granular sulfurization product formed decreases. Accordingly, in order to obtain a sulfurized product having a de-

  
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exactly finish the amount of reaction medium based on the amounts of raw material and sulfur, type of reaction medium and other reaction conditions. For example, when forming a granular sulfurization product from about 1 part by weight of asphalt and about 1.5 parts by weight of sulfur, it is necessary to use at least about 0, 5 part by weight of light oil when this is used as a reaction medium and, when more than about 20 parts by weight of light oil are used, the sulfurized product is obtained in the form of very fine granules.

   However, in this case, if the amount of light oil serving as the reaction medium is less than about 0.5 part by weight, the viscosity of the whole reaction system increases sharply, so that it is difficult to disperse the reactants. by agitation. In addition, when, as the reaction medium, an aromatic hydrocarbon such as toluene is used, the change in particle size is more accentuated and, therefore, in order to obtain a granular sulfur product having a desired particle size, the amount of the reaction medium must be determined in a very precise manner.

  
The reaction medium or a liquid composition containing the reaction medium used in the process of the present invention can be used repeatedly and a part of the reaction medium can sometimes be consumed as a result of the reaction with sulfur but, even in this case, the middle re-

  
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taken without giving rise to any difficulty in supplementing the quantity of the reaction medium consumed.

  
The infusible and insoluble solid material used in the process of the present invention is a solid carbonaceous material insoluble in the raw material, sulfur and the reaction medium, while it is infusible under the reaction conditions described above and is can be transformed into carbon or into a gas during a carbonization step or in a heat treatment during the activation step. Among the preferred infusible and insoluble solids, there are, for example, the infusible and insoluble granular sulfur product, the granular carbon and the granular activated carbon which are obtained by carrying out the process of the present invention or else. these same materials crushed, pulverized and molded.

   Further, as infusible and insoluble solids, petroleum coke, hard coal, coke and coal can be used.

  
To the infusible and insoluble solid material, optionally, an inorganic compound such as a metal oxide can be added, for example, calcium oxide, aluminum oxide, iron oxide, etc. The infusible and insoluble solids can be used individually or as a mixture.

  
The reason for using the infusible and insoluble solid material according to the present invention is that the granulation in the step of making a granular sulfur product is facilitated, while a granular sulfuric material having the desired particle size with high efficiency. Likewise, as will be understood by reading the Examples and Comparative Examples below, the addition of the infusible and insoluble solid to the reaction system makes it possible to completely prevent the adhesion of the reaction intermediate to the elements of the reaction vessel. such as its walls, its agitator, its baffles, etc., as well as the agglomeration of the reaction product; this addition reduces

  
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sulphide obtained, while increasing the yield of a granular product whose particle size is within the desired range. The mechanism by which these effects are obtained by the addition of the infusible insoluble solid is not yet fully understood, but the latter is believed to act as a nucleus for the formation of the granular product, as the solid moves. in the reaction medium by stirring or that the reaction intermediate product is incorporated

  
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the solid material also abrading the intermediate reaction product attached to the interior walls, etc., of the reaction vessel.

  
Another reason why the infusible and insoluble solid is used is that, among the granular products obtained by the process of the present invention, those having particle sizes other than that desired, are returned wholly or partially to the reaction system as infusible and insoluble solid material with or without crushing to achieve an appropriate particle size and ultimately only form a granular product with the distribution

  
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identifies the particle size of the infusible and insoluble solid

  
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this material may be greater or less than that of the product

  
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the effect of the infusible and insoluble solid material is more accentuated as the particle size of the material present in the reaction system decreases, usually a material is employed.

  
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particle size less than about 10 mm, preferably 0.01

  
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However, in the process of the present invention one can obtain the desired granular sulfurized product, the desired granular carbon formed by carbonization of the sulfurized granular product or the desired activated granular carbon formed by carbonization and activation of the sulfurized granular product without add the above infusible and insoluble solid material.

  
When using the infusible insoluble solid material, it is preferable that its amount is about 0.02 to 2 parts by weight per part by weight of the total amount of the raw material and the reaction medium.

  
When performing the method of this unused /

  
&#65533; vention, since the amount of sulfur / depends on the reactivity of the raw material, the type of reaction medium, the reaction conditions, etc. and, as shown in the examples, since the particle size of the sulfurized granular product differs significantly depending on the amount of sulfur used, even though factors contributing to the reaction, for example, raw material, etc., are the same, the amount The amount of sulfur used must be chosen with precision in order to obtain a sulfurized granular product having the desired granuloma. Generally speaking, preferably about 0.2 to 5 parts by weight, more preferably 0.3 to 3 parts by weight of sulfur per part by weight of raw material is used. The amount of the reaction medium u-

  
 <EMI ID = 34.1>

  
i

  
 <EMI ID = 35.1>

  
The actuator generally does not exceed about 20 parts by weight, preferably 7 parts by weight based on the weight of the raw materials. The effect of the amount of sulfur added is

  
the following: As a general rule, when the amount of sulfur is small, the particle size of the product decreases and, when the amount of sulfur used is less than about 0.2 part by weight per part by weight of raw material, the nature infusible tends to become insufficient. The sulfur can be added all at once, in increments or continuously and, in the latter case, the particle size of the granular sulfur product formed differs greatly depending on the speed and duration of the sulfur addition. The sulfur used in the process of the present invention is elemental sulfur which can be in the solid or molten state. Sulfur can be added to the reaction system before heating the latter, or it can be added all at once or gradually to the reaction system when the temperature of the latter has reached the temperature.

  
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In the process of the present invention, the reaction of the raw material with sulfur proceeds easily and an infusible and insoluble sulfur product is obtained in a short time. By adding a catalyst, for example, a Lewis acid, especially a metal halide such as aluminum chloride, zinc chloride, ferric chloride, etc., in an amount of about 0.01 to 0.5 part by weight, preferably

  
from 0.03 to 0.3 part by weight per part by weight of sulfur, the reaction rate can be increased and further reduced

  
the reaction temperature.

  
The term "agitation" used in this specification means that the materials contained in the reaction vessel are maintained in a fluid state and the materials contained in the reaction system are uniformly dispersed using physical means, while the chemical reaction is evenly activated by improving mass transfer and heat transfer in the reaction system. Accordingly, there is no particular limitation with respect to the method of agitation and any operation and any agitation means having different structures suitable for achieving the objects described above can be used. . For example, one can use, for this purpose, a system with

  
 <EMI ID = 37.1>

  
shaking blades, liquid flow system, gas jet system, liquid shaking system, etc. Likewise, in order to improve the effect of stirring, foreign matter, for example, drops of liquid which are not compatible with the reagents, for example, drops, are effectively dispersed in the reaction system. water, or even solid particles such as ceramic balls, thus creating a violent turbulence in the liquid which surrounds them or, as a variant of the means described above, it is sometimes effective to carry out the reaction while the raw material, the sulfur and the reaction medium are dispersed in a foreign liquid material having a low viscosity, for example, water.

   When the reaction system is not stirred, a lumpy sulfurized product accumulates in the reaction vessel and a granular sulfurized product is not obtained.

  
The reaction of the present invention can be carried out in a continuous or batch system. For example, the reaction

  
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accommodation of the multistory type.

  
In the process of the present invention, the suitable reaction temperature for the formation of the granular sulfur product by the reaction between the raw material and the sulfur is between about 170 and about 400 [deg.] C, preferably between about 200 and about 300 [deg.] C. The reaction time can be reduced by raising the reaction temperature but, if this temperature is greater than about 400 [deg.] C, there are drawbacks due to the fact that the losses of the reaction medium increase and that one obtains, as by-product, a chunky sulfurized material other than the desired granular sulfurized product, which material accumulates on the interior walls of the reaction vessel. Therefore, it is difficult to ensure the smooth progress of the reaction.

   At a reaction temperature above about 200 [deg.] C, the sulfurized granular product is formed in a very short time. In this case, when the reaction period is short, a sulfurized granular product having a low density is obtained, but in this case, by further continuing the reaction, the strength and density of the sulfurized granular product can be increased. In addition, it is not always necessary to completely react the raw material and the sulfur or,

  
on the contrary, since a large amount of sulfur is required and the reaction time increases to carry out the reaction completely, it is desirable to abandon unreacted materials and to recycle them to the reaction system for the purpose of carrying them out. reuse.

  
In the process of the present invention, the reaction is carried out in the liquid phase. The reaction can be carried out, preferably, substantially at atmospheric pressure. However, it is possible to adopt a pressure greater than atmospheric pressure and sufficient to suppress any tendency for the reaction medium to volatilize at the operating temperatures when the boiling point of the reaction medium is lower than the operating temperature in question.

  
The reaction can also be carried out under a pressure between atmospheric pressure and approximately

  
100 kg / cm2, preferably between normal pressure and approximately
30 kg / cmg.

  
The sulfurized granular product obtained by the process of the present invention does not have a softening point and hence the product retains its granular form in the subsequent high temperature carbonization treatment. Carbonization is readily accomplished by heating the sulfurized granular product to temperatures between about 400 and about
1200 [deg.] C, preferably between 450 and about 1100 [deg.] C, under an atmosphere of an inert gas such as nitrogen, hydrogen sulfide, carbon monoxide or a mixture of these gas.

  
The granular carbon obtained by the pre-

  
 <EMI ID = 39.1>

  
granular by activating the granular carbon in any customary manner with an oxidizing atmosphere. Alternatively, granular activated carbon can be obtained by heating the granular sulfurized product to a temperature of about 700 to
1100 [deg.] C directly in a mild oxidizing atmosphere such as water vapor or flue gas, so that the product is simultaneously carbonized and activated. According to the present invention, the activation can also be carried out using carbon dioxide, oxygenated gas, etc. Among these activation methods, activation with steam is preferred.

  
Preferably, as oxidizing gas, water vapor is used.

  
One can also use carbon dioxide or flue gases containing about 1 to 30%. oxygen with or without water vapor.

  
In addition, the sulfurized granular product or the granular carbon obtained by the process of the present invention can obviously be crushed into particles of a desired particle size, in order to then be carbonized or activated, or else it can be pulverized, then transformed into pellets. using an appropriate binding agent, prior to carbonization or activation.

  
The tooth material consists of the reaction vessel used in carrying out the process of the present invention, may be a material inactive to the reaction materials under the reaction conditions and, as the material for the reaction vessel, one can advantageously to use, for example, stainless steel, titanium, enamelled hardware, etc.

  
The invention will be described more specifically with reference to the examples and the comparative examples below, but it is understood that these examples are given simply by way of illustration and that they in no way limit the scope of the invention. Unless stated otherwise, in these examples. all parts, all percentages, all ratios, etc. are by weight.

  
EXAMPLE 1

  
In a reaction vessel of 1 1 made of stainless steel, equipped with a rotary and electromagnetic type stirrer, as well as a reflux condenser, 200 g of a light oil (hereinafter referred to as "light oil" is deposited, having a boiling point

  
 <EMI ID = 40.1>

  
an H / C atomic ratio of 1.9 and a specific weight (15/4 [deg.] C)

  
of 0.835), 100 g of asphalt obtained by separating asphalt in a distillation residue under normal pressure using propane (hereinafter referred to as "propane separating asphalt" having, at 25 [deg.] C, a penetration of 18 in accordance with Japanese Industrial Standard JIS K 2530; 21%. by weight of components insoluble in n-pentane; a sulfur content of 5.7% by weight; an H / C atomic ratio of 1.41), as well as 150 g of sulfur; these materials are reacted for 4 hours at a temperature of 230

  
at 235 [deg.] C under normal pressure while stirring at 900 rpm. During the reaction, a large amount of a gas is formed, mainly consisting of hydrogen sulfide. At the end of the reaction, the reaction mixture is removed and subjected to centrifugal filtration to obtain 136 g of a sulfurized granular product consisting of disc-shaped grains of length.

  
1 to 18 mm, with a width of 1 to 7 mm and a thickness of 1 to

  
3 mm, a small amount of a chunky sulphide material

  
 <EMI ID = 41.1>

  
reaction place. The sulfur content of the granular product sul-

  
 <EMI ID = 42.1>

  
at a temperature of 400 to 1200 [deg.] C, this product does not melt.

  
Further, the lumpy sulphide material is a solid material attaching to the bottom and walls of the reaction vessel, and further, the oily material is a liquid material.

  
at normal temperature containing light oil, unreacted asphalt, etc.

COMPARATIVE EXAMPLE 1

  
In the same reaction vessel as that described in Example 1, the light oil, the propane separating asphalt and the sulfur are charged in the same quantities as those used in Example 1 and these are reacted. materials for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure without agitating the system. Upon completion of the reaction, the reaction mixture was removed and 220 g of infusible, insoluble, chunky sulphide material was found to form without any formation of granular sulphide material.

  
EXAMPLE 2

  
When the same process as that described in Example 1 is followed by bringing the stirring speed to 1200 revolutions / minute, 151 g of a sulfurized granular product is obtained consisting of grains in the form of discs smaller than those of product obtained in Example 1 (length: 1 to 17 mm; width: 1 to 4 mm; thickness: 1 to 3 mm) and 119 g of an oily material are recovered. In this case, less of the lumpy product is formed.

  
EXAMPLE 3

  
In the same reaction vessel as that. described in Example 1, 400 g of the light oil, 200 g of the propane separating asphalt and 300 g of sulfur are charged, then these materials are reacted for 4 hours at a temperature of 230 to
235 [deg.] C under normal pressure while stirring at a speed of

  
1200 revolutions / minute. Upon completion of the reaction, the reaction mixture is removed from the vessel. In this way, 321 g of a sulfurized granular product is obtained consisting of grains in the form of fine needles 1 to 5 mm long and 0.4 to 2 mm in diameter.

  
EXAMPLE 4

  
400 g of light oil, 200 g of propane separation asphalt and 250 g of sulfur are charged into the same reaction vessel as that described in Example 1, then these materials are reacted for 4 hours at a temperature. from 230 to 235 [deg.] C under normal pressure and while stirring at a speed of 1200 revolutions / minute to obtain 317 g of a spherical granular product whose grains have an average particle size of about 0.7 mm. Less product is formed in large pieces.

  
EXAMPLE 5

  
Into the same reaction vessel as that described in Example 1, 400 g of light oil, 200 g of propane separating asphalt and 200 g of sulfur are charged, then these materials are reacted for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure, while stirring at a speed of 1200 revolutions / 'minute to obtain 268 g of a spherical granular product whose grains have an average particle size of about 0.03 mm .

  
EXAMPLE 6

  
In the same reaction vessel as that described in

  
 <EMI ID = 43.1>

  
separation with propane and 150 g of sulfur, then these materials are reacted for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure, while stirring at a speed of 1200 rpm to obtain 263 g of a spherical granular sulphide product

  
 <EMI ID = 44.1>

  
In this case, less material is formed in large pieces.

COMPARATIVE EXAMPLE 2

  
In the same reaction vessel as that described in Example 1, 100 g of the propane separating asphalt and 150 g of sulfur are charged, then the reaction is carried out at a temperature.

  
 <EMI ID = 45.1>

  
a speed of 1200 revolutions / minute. As the reaction proceeds, the viscosity of the materials contained in the reaction vessel increases sharply and, 20 minutes after the start of the reaction, it becomes impossible to agitate the system.

  
When the reaction was continued in situ for 4 hours, 208 g of a lumpy sulfurized material was obtained, while no sulfurized granular product was obtained. The product is a solid pumice-like material at room temperature and upon rapid heating of the pumice stone to 400 [deg.] C the product partially melts.

  
EXAMPLE 7

  
400 g of the light oil, 200 g of residual Kuwait reduced pressure oil (specific weight) are charged into the same reaction vessel as that described in Example 1.
(15/4 [deg.] C) 1.03, components insoluble in n-heptane:

  
 <EMI ID = 46.1>

  
sulfur, then these materials are reacted for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure while stirring

  
at a speed of 900 revolutions / minute, to obtain 121 g of a sulphide granular product consisting of disc-shaped grains 10 to 15 mm long, 4 to 8 mm wide and thick -

  
 <EMI ID = 47.1>

  
EXAMPLE 8

  
400 g of residual Kuwait normal pressure oil (specific weight (15/4 [deg.] C): 0.966; components insoluble in n-heptane are charged to the same reaction vessel as that described in Example 1. : 2.6% by weight; sulfur content:
4.1% by weight) and 200 g of sulfur, then these materials are reacted for 3 hours at a temperature of 240 to 245 [deg.] C under normal pressure, while stirring at a speed of 900 revolutions / minute to obtain 194 g of a granular product consisting of grains

  
in the form of discs with a length of 5 to 10 mm, a width of

  
3 to 5 mm and a thickness of 1 to 3 mm.

  
EXAMPLE 9

  
400 g of liquid paraffin (initial boiling point: 280 [deg.] C), 200 g of propane separation asphalt and 300 g of sulfur are charged into the same reaction vessel as that described in Example 1. , then these materials are reacted for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure while stirring at a speed of 1000 revolutions / minute to obtain 110 g <EMI ID = 48.1>

  
and a thickness of 1 to 4 mm.

  
EXAMPLE 10

  
200 g of an oil from a catalytic cracking cycle by means of a fluid are charged into the same reaction vessel as that described in Example 1, this oil having a boiling point of 330 to 420 [deg .] C, 200 g of propane separating asphalt and 300 g of sulfur, then these materials are reacted for 4 hours at 230 - 235 [deg.] C under normal pressure while stirring at a speed of 500 rpm. minute to obtain 260 g of a product

  
 <EMI ID = 49.1>

  
EXAMPLE 11

  
In the same reaction vessel as that described in Example 1, 300 g of tert-butyl-benzene are charged, 200 g of the asphalt separation. propane of the type described in Example 1 and 300 g of sulfur, then these materials are reacted for 4 hours at a temperature of 230 to 235 [deg.] C under a pressure of 15 kg / cm2, while stirring at a speed of 700 revolutions / minute to obtain 120 g of a sulfurized product in spherical grains with an average particle size of 0.6 mm.

  
EXAMPLE 12

  
In the same reaction vessel as that described in Example 1, 145 g of the oily material recovered in Example 1, 70 g of light oil, 65 g of propane separation asphalt and 150 g of sulfur, then these materials are reacted for 4 hours at 230 - 235 [deg.] C under normal pressure while stirring at a speed of 900 rpm to obtain 129 g of a granular product consisting of disc-shaped grains 6 to 15 mm long, 3 to 9 mm wide and 1 to 4 mm thick.

  
EXAMPLE 13

  
Into the same reaction vessel as that described in Example 1, 400 g of light oil and 200 g of propane separating asphalt are charged and, after heating the reaction system to a temperature of 230 to 235 [deg. ] C, 300 g of sulfur are gradually added thereto under normal pressure at a rate of 1 g per minute, while stirring at a speed of 500 revolutions / minute. Then, the reaction was continued for 1 hour, then the reaction mixture was subjected to centrifugal filtration to obtain
428 g of a sulfurized product in spherical grains with an average particle size of 0.005 mm.

  
EXAMPLE 14

  
400 g of light oil and 300 g of sulfur are charged into the same reaction vessel as that described in Example 1, then, after heating the mixture to a temperature of 230 to

  
 <EMI ID = 50.1>

  
200 g of propane separation asphalt at a rate of 1 g per minute. Further continuing the reaction for 1 hour, 416 g of a sulfurized product in spherical grains with an average particle size of 0.8 mm is obtained.

  
EXAMPLES 15 to 18

  
When heating each of the sulfurized granular products obtained in Examples 1, 3, 10 and 13 at 450 [deg.] C, each

  
 <EMI ID = 51.1>

  
16), 75% by weight (example 17) and 52% by weight (example

  
18) compared to sulfurized granular products respectively.

  
EXAMPLE 19

  
The granular carbon consisting of disc-shaped grains obtained in Example 15 is crushed into fine grains with a diameter of 1 to 1.4 mm and 50 g of these grains are activated with steam. 'water for 70 minutes at 850 [deg.] C to obtain 21 g of granular activated carbon having a specific surface of 2250 m2 / g

  
 <EMI ID = 52.1>

  
sulfur content of the activated carbon is 1.2% by weight.

  
Further, the specific surface area is a value measured by the Brunauer-Emmett-Teller method which is an area measurement method in which the adsorption of nitrogen is used, while the adsorption value of methylene blue using a buffer solution (adjusted to pH 7) containing 300 mg of methylene blue per liter. The desired amounts of the buffer solution described above and the fine grains of the obtained activated carbon are weighed out, and then these amounts are loaded into a flask for shaking. The above materials are stirred vigorously for 30 minutes, then

  
the activated carbon is filtered. The amount of methylene blue remaining in the filtrate is determined from the adsorption capacity.

  
 <EMI ID = 53.1>

  
The value thus calculated is the adsorption value per unit weight of activated carbon. In the following examples, these values are also measured by the same methods as those described above.

  
EXAMPLE 20

  
From granular carbon in air-shaped grains

  
 <EMI ID = 54.1>

  
whose grains are 1 to 1.4 mm long and 0.4 to 1 mm in diameter, then activated with water vapor for 60 minutes at 850 [deg.] C without crushing it and thus obtains 22 g of an activated carbon having a specific surface area of 1820 m2 / g and an adsorption of methylene blue of 336 mg / g.

  
EXAMPLE 21

  
When activated, with steam, 50 g of the granular carbon consisting of spherical grains and obtained in example
17, for 70 minutes at 850 [deg.] C, 23 g of an ac-

  
 <EMI ID = 55.1>

  
EXAMPLE 22

  
When activating, with water vapor, 50 g of the spherical granular carbon obtained in Example 18, for 40 minutes at
850 [deg.] C, 23 g of a spherical granular activated carbon are obtained having a specific surface area of 1820 m2 / g and an adsorption of

  
 <EMI ID = 56.1>

  
EXAMPLES 23 to 28

  
The crushed activated carbon obtained is deposited each time

  
 <EMI ID = 57.1>

  
Examples 20. 21 and 22, a commercially available crushed activated carbon (diameter: 1.0 to 1.1 mm; specific surface area: 970

  
 <EMI ID = 58.1>

  
commercially available molded and spherical type activated carbon (diameter: 1 to 1.5 mm; specific surface area: 970 m2 / g; adsorption of methylene blue: 170 mg / g) in a glass tube with an internal diameter 20 mm and a length of 200 mm, then the glass tube is rotated for 10 hours at a rate of

  
10 revolutions / minute. Next, the weight of the powder is measured

  
 <EMI ID = 59.1>

  
age of the powder in relation to the total material. The powder percentages of these activated carbons are respectively: 0.1% by weight, less than 0.01% by weight, less than 0.01% by weight, less than 0.01% by weight, 0.3% by weight. weight and 2.8% by weight, which demonstrates that the activated carbons obtained by the process of the present invention form a powder much more difficult than the commercially available activated carbons.

  
EXAMPLES 29 to 32

  
In the same reaction vessel as that described in

  
 <EMI ID = 60.1>

  
pane, 225 g of sulfur and 75 g of the granular sulfur product with a particle size of 0.5 to 1 mm, obtained by the process of the invention

  
 <EMI ID = 61.1>

  
a quantity of 150 g (example 29), 300 g (example 30),
450 g (Example 31) and 600 g (Example 32), these materials are reacted in each case for 4 hours at a temperature of
230 to 235 [deg.] C under normal pressure, while stirring at a speed of 900 revolutions / minute. During the reaction, a large amount of a gas is formed, mainly consisting of hydrogen sulfide. Then, the reaction mixture is removed from the reaction vessel and subjected to centrifugation filtration to obtain an infusible and insoluble grain sulfur product.

  
 <EMI ID = 62.1>

  
Table 1. A smaller amount of reaction product is observed adhering in the form of large pieces to the walls of the vessel.

COMPARATIVE EXAMPLE 3

  
In the same reaction vessel as that described in Example 1, 150 g of the asphalt separation with propane, 225 g of sulfur and the sulfurized product in grains with a diameter of 0.5 to 1 mm obtained by the process of the invention, then the reaction is carried out at a temperature of 230 to 235 [deg.] C while stirring at a speed of 900 revolutions / minute. As the reaction proceeds, the viscosity The material contained in the reaction system increases sharply, and about 20 minutes after the temperature of the reaction system has reached the reaction temperature, it becomes impossible to agitate the system. When the reaction was continued in situ for 4 hours, a granular sulfurized product was not obtained and only a lumpy sulfurized product formed.

   On cooling, the product turns into a solid material similar to pumice. When this material is heated rapidly to 400 [deg.] C, the product partially melts.

  
Table 1

  

 <EMI ID = 63.1>


  
(*): percent by weight (the granular sulfur product added

  
is eliminated) =

  
(**): sulfurized product in large pieces fixed to the walls of the reaction vessel, etc.

  
As can be seen from the results of Table 1, the particle size distribution of the sulfur product formed changes depending on the amount of the reaction medium used and, in Comparative Example 3 in which no reaction medium is used. , no granular product is formed.

  
EXAMPLES 33 to 37

  
In the same reaction vessel as described

  
in Example 1, 200 g of the asphalt separation with propane, 400 g of light oil and 100 g of the sulphide product in grains with a particle size of 0.5 to 1 mm obtained by the process are charged

  
of the present invention then, after adding to the mixture,

  
sulfur in an amount of 200 g (example 33), 250 g (example 34), 275 g (example 35), 300 g (example 36) or 400 g
(Example 37), the reaction is carried out for 4 hours at a temperature

  
 <EMI ID = 64.1>

  
a speed of 900 revolutions / minute to obtain, in each case, an infusible and insoluble sulfurized granular product whose grains have a particle size distribution of the type indicated in Table 2.

  
Table 2
 <EMI ID = 65.1>
 EXAMPLES 38 to 40

  
Into the same reaction vessel as that described in Example 1, 200 g of the propane separating asphalt, 400 g of light oil and 300 g of sulfur are charged and, after adding 20 g (example 38), 60 g (example 39) or 100 g (example 4o) of the granular and crushed sulphide product obtained by the process of the invention (the particle size distribution of the crushed product is as follows: 30% by weight of grains of a particle size

  
 <EMI ID = 66.1>

  
0.1 to 1 mm), the reaction is carried out for 4 hours at a temperature of 230 to 235 [deg.] C while stirring at a speed of 900

  
 <EMI ID = 67.1>

  
nullometric data shown in Table 3. In addition, by way of comparison

  
 <EMI ID = 68.1>

  
Example 1 in which the crushed granular sulfur product is not added.

  
Table 3

  

 <EMI ID = 69.1>


  
(*) Percent by weight of all solids formed by the reaction (including added solid).

  
(**): Material in large pieces attached to the wall of the container

  
reaction, etc.

  
As can be seen clearly from the results

  
 <EMI ID = 70.1>

  
Granular units exhibiting a narrow particle size distribution and no large chunky material attaches to the walls of the reaction vessel or only a small amount attaches to it. Likewise, it is evident that the particle size and shape of the product change depending on the amount of crushed granular sulfur product that is added.

  
EXAMPLES 41 to 43

  
200 g of the propane separation asphalt, 400 g of light oil, 300 g of sulfur and 100 g of the granular sulfur product obtained by the process of the present invention, then the reaction is carried out for 4 hours at a temperature of
230 to 235 [deg.] C while stirring at a speed of 900 rpm.

  
In addition, the particle size of the granular product sulfu-

  
 <EMI ID = 71.1>

  
Table 4 indicates the particle size distributions and the shapes of the granular products obtained by the reaction.

  
Table 4

  

 <EMI ID = 72.1>


  
(*): Percent by weight of all solids formed by the reaction (including added solid).

  
EXAMPLE 44

  
400 g of light oil, 200 g of propane separation asphalt, 300 g of sulfur and 100 g of coal from the Pacific Ocean are charged into the same reaction vessel as that described in Example 1 (content of ash: 13%; volatile matter content: 52%; atomic H / C ratio: 0.94) which are crushed into grains with a particle size of 0.4 to 1 mm, after which the reaction is carried out for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure while stirring at a speed of 900 revolutions / minute; one thus obtains a sulphurized product in grains of a large

  
 <EMI ID = 73.1>

  
EXAMPLE 45

  
400 g of light oil, 100 g of propane separating asphalt and 150 g of sulfur are charged into the same reaction vessel as that described in Example 1, then the reaction is carried out for 2 hours at a temperature of 230 to 235 [deg.] C while stirring at a speed of 900 revolutions / minute to obtain a sulfurized granular product whose grains have an average particle size of about 0.2 mm. When a further 200 g of propane separating asphalt and 250 g of sulfur are added to the reaction mixture

  
and when the reaction is carried out for an additional 4 hours, a sulfurized granular product is obtained, the grains of which have an average particle size of about 0.8 mm.

  
EXAMPLE 46

  
Into the same reaction vessel as that described in Example 1, 200 g of residual oil of reduced pressure from Kuwait of the type described in Example 7, 400 g of light oil are charged,
250 g of sulfur and 100 g of the sulfurized granular product obtained by the process of the present invention, which are crushed into grains with a particle size of less than 0.25 mm, then the reaction is carried out for 4 hours at a temperature of 230 to 235 [deg.] C while stirring at a speed of 1200 revolutions / minute to obtain a sulfurized granular product consisting of needle-shaped grains with a length of about 1 to 2 mm and a diameter of 'about 0.4 to 1 mm.

  
EXAMPLE 47

  
Into the same reaction vessel as that described in Example 1, 400 g of the same residual Kuwait normal pressure oil as described in Example 8, 300 g of sulfur and 100 g of the sulfurized granular product are charged. whose grains have a particle size of 0.5 to 1 mm and which is obtained by the process of the present invention, then the reaction is carried out for 4

  
 <EMI ID = 74.1>

  
tess of 900 revolutions / minute to obtain a sulfurized product in spherical grains with an average particle size of about 0.5 mm.

  
EXAMPLE 48

  
200 g of propane separation asphalt are charged into the same reaction vessel as that described in Example 1,
300 g of tert-butyl-benzene, 300 g of sulfur, as well as the sulfurized granular product whose grains have a particle size of 0.5 to 1 mm and which is obtained by the process of the present invention, then carried out reaction at a temperature of 230 to
235 [deg.] C under a pressure of 15 kg / m2, while stirring at a speed of 500 revolutions / minute to obtain a sulphide product in spherical grains with an average particle size of about 0.2 mm.

  
EXAMPLE 49

  
In the same reaction vessel as that described in Example 1, 400 g of light oil, 300 g of sulfur and
100 g of the sulfurized granular product, the grains of which have a granular

  
 <EMI ID = 75.1>

  
present invention then, after heating the mixture to a temperature of 230 to 235 [deg.] C under normal pressure, is gradually added 200 g of ... separation asphalt with propane at a rate of 1 g per minute, while stirring at a speed of 500 revolutions / minute. Then, by carrying out the reaction for 1 hour, a sulfurized product in spherical grains with an average particle size of about 0.7 mm is obtained.

  
EXAMPLE 50

  
Into the same reaction vessel as that described in Example 1, 400 g of light oil, 200 g of propane separating asphalt and 100 g of the sulfurized granular product, the grains of which have a particle size of 0.5 to 1 mm and which is obtained by the process of the present invention, then 300 g of sulfur are gradually added to the mixture at a rate of 1 g per minute.

  
 <EMI ID = 76.1>

  
stirring at a speed of 900 revolutions / minute. Thereafter, the reaction is continued further for 1 hour, then the reaction mixture is removed from the reaction vessel and a spherical grain sulfurized product having an average particle size of about 0.005 mm is obtained.

  
EXAMPLE 51

  
The sulfurized granular product is used, the grains of which have a particle size of 1 to 1.4 mm and which is obtained in Example 29; this product is subjected to carbonization by heating at

  
 <EMI ID = 77.1>

  
thus obtains the granular carbon indicated in Table 5.

  
EXAMPLE 52

  
The sulfurized granular product is used, the grains of which have a particle size of 0.15 to 0.25 mm and which is obtained in Example 32; this product is treated as described in example 51

  
and the granular carbon shown in Table 5 is obtained.

  
EXAMPLE 53

  
The sulfurized granular product is used, the grains of which have a particle size of 0.5 to. 1 mm and which is obtained in Example 34; this product is treated as described in Example 51 and the granular carbon shown in Table 5 is obtained.

  
EXAMPLE 54

  
The sulfurized granular product obtained in Example 42 is used and is subjected to a treatment as described in Example 42.

  
 <EMI ID = 78.1>

  
5.

COMPARATIVE EXAMPLE 4

  
Using a rotary granulator in the usual way- <EMI ID = 79.1>

  
charcoal passing through a sieve with a 0.05 mm mesh, together with tar pitch as a binding agent, then heated to 45,000 for 2 hours under a nitrogen atmosphere.

  
 <EMI ID = 80.1>

  
Table 5

  

 <EMI ID = 81.1>


  
(*): The sample is placed in a glass tube with a diameter of

  
 <EMI ID = 82.1>

  
amount of 20 ml, then the glass tube is rotated for 10 hours at a speed of 10 revolutions / minute. The weight of the powder thus formed with a particle size of less than 0.07 mm is measured and the percentage of powder vis-à-vis the total material is indicated.

  
As can be seen from the results of Table 5, the granular carbons obtained by the process of the present invention have a very low percentage of powder and, therefore, it is easily understood that the granular carbons obtained by the process of the present invention invention have excellent mechanical strength.

  
EXAMPLE 55

  
When the granular carbon obtained in the example is activated

  
 <EMI ID = 83.1>

  
Using a fluidized activation oven in the usual manner, the granular activated carbon is obtained as shown in Table 6.

  
EXAMPLE 56

  
When the granular carbon obtained in Example 53 is activated with water vapor for 60 minutes at 850 [deg.] C using a fluidized activation oven, the granular activated carbon is obtained as shown in Table 6.

  
EXAMPLE 57

  
The granular carbon obtained in Example 54 is treated as described in Example 55 to obtain the granular activated carbon indicated in Table 6.

  
Table 6

  

 <EMI ID = 84.1>


  
(*): Value measured by the Brunauer-Emmett-Teller method

  
using nitrogen absorption.

  
(**): Measurement performed using a buffer solution (pH: 7)

  
containing 300 mg of methylene blue per liter.

  
Comparison sample 1 is commercially available crushed activated carbon, while comparison sample 2 is commercially available spherical activated carbon.

  
As can be seen clearly from the results shown in Table 6, the granular activated carbons obtained by the process of the present invention are, with regard to the surface area and the adsorption of methylene blue, superior to the articles available. commercially and, in addition, they have excellent properties in terms of powder percentage or mechanical strength.

  
EXAMPLE 58

  
200 g of the propane separating asphalt, 400 g of light oil, 250 g of sulfur and 100 g of the crushed granular sulfur product (crushed into grains) are charged into the same reaction vessel as that described in Example 1. with a particle size of less than 0.5 mm), which is obtained by the process of the present invention, then the reaction is carried out for 4 hours at a temperature of 230 to 235 [deg.] C under normal pressure and all stirring at a speed of 900 revolutions / minute. When removing the reaction mixture from the reaction vessel and subjecting it to. filtration by centrifugation gives 410 g of a sulfurized product in spherical grains and 313 g of a filtrate (recovered oil).

   A portion of the recovered oil is analyzed to determine the content of light oil and unreacted asphalt and thus, the amounts of propane separating asphalt and light oil consumed in the reaction are calculated.

  
Then, to the recovered oil, the fresh asphalt separating with propane and light oil are added in the quantities corresponding to the consumed quantities of these components and, after

  
having added 180 g of sulfur and 100 g of the sulfurized granular product (crushed into grains with a particle size of less than 0.5 mm), the reaction is carried out again. By repeating the same process, 5 times the oil recovered is used and the sulfurized granular product shown in Table 7 is thus obtained. From the results of Table 7, it is understood that the reaction medium recovered
(light oil) can be used in situ repeatedly without any difficulty.


      

Claims (1)

Table 7 Number of repeated uses <EMI ID = 85.1> Although the invention has been described in detail and with reference to its specific embodiments, those skilled in the art will understand that various modifications can be made thereto without departing from its spirit and its scope. 1. A method of manufacturing an infusible and insoluble granular sulphide material, characterized in that it consists reacting a heavy petroleum material and sulfur while stirring in the presence of a reaction medium. 2. Method according to claim 1, characterized in that the heavy petroleum material is a residue obtained by distillation of crude oil, a residue of catalytic cracking of kerosene, a residue of catalytic cracking of a light oil, a residue of thermal cracking of kerosene, a residue from thermal cracking of a light oil, a residue from the cracking of naphtha, a residue obtained by thermal cracking or hydrocracking of a heavy petroleum fraction, a residue obtained by thermal cracking or hydrocracking of a residual oil, or a mixture of these products. 3. Method according to claim 2, characterized in that the heavy petroleum material is asphalt. 4. Method according to claim 1, characterized in that the reaction medium is an oil fraction having <EMI ID = 86.1> 5. Method according to claim 4, characterized in that the petroleum fraction is naphtha, kerosene, light oil or a mixture thereof. 6. Process according to claim 1, characterized in that the reaction medium is an aromatic hydrocarbon, an aliphatic hydrocarbon or a mixture thereof. 7. Process according to Claim 6, characterized in that the aromatic hydrocarbon is benzene, toluene, xylene or tert-butyl-benzene. 8. A method according to claim 6, characterized in that the aliphatic hydrocarbon is hexane, cyclohexane, octane or liquid paraffin. 9. The method of claim 1, characterized in that the proportion of sulfur is between about 0.2 and about 6 parts by weight per part by weight of the heavy petroleum material. 10. A method according to claim 1, characterized in that the reaction is carried out at temperatures between <EMI ID = 87.1> 11. The method of claim 1, characterized in that this reaction is carried out in the presence of a metal halide of de'Lavis acid as a catalyst in an amount of about 0.01 to 0.5 part by weight per part. by weight of sulfur. 12. The method of claim 1, characterized in that the reaction is carried out in the presence of an infusible and insoluble solid material. 13. Process for manufacturing granular carbon, characterized in that it consists in carbonizing the sulphide material <EMI ID = 88.1> claim 1. 14. The method of claim 13, characterized in that the carbonization is carried out at a temperature of between about 400 and 1200 [deg.] C under an atmosphere of an inert gas. 15. A method of manufacturing granular activated carbon, characterized in that it consists in activating the granular carbon obtained by the method according to claim 13. 16. The method of claim 12, characterized in that the proportion of the infusible and insoluble solid material is between about 0.02 and about 2 parts by weight per part by weight of the total amount of the heavy petroleum material and the reaction medium. 17. Process for manufacturing granular carbon, characterized in that it consists in carbonizing the infusible and insoluble granular sulphide material obtained by the process according to claim 12. 18. Process for manufacturing granular activated carbon, characterized in that it consists in activating the granular carbon ^ obtained by the method following .la claim 17.