KR800000425B1 - Process for producing granular activated carbon - Google Patents

Abstract

Granular active carbon, useful as absorbents for oil, was prepd. by reaction of S with high mol. wt. petroleum products at 170-400≰C in the presence of reaction media. Thus, light oil(b.p 185-350≰C) 200, C3H8-extracted asphalt 100, and S 150 were stirred at 230-5≰C for 4 hr and 900 rpm to give 145 g oil, a small amt. of agglomerated product, and 136 g granulate with length, width, and height 1-18, 1-7 and 1-3mm, resp., and S content 26%, which does not melt when heated rapidly from 400 to 1200≰C.

Description

Method for producing granular activated carbon

The present invention relates to a method for producing granular activated carbon which is useful as an industrial adsorbent or an adsorbent for household products and is also used for removing and preventing contamination.

Insoluble and insoluble granular sulfides obtained by reacting heavy hydrocarbons such as asphalt and pitch with sulfur are useful for various purposes such as various fillers, reinforcing agents, oil absorbents and metal scavengers, and sulfides are carbon disulfides, carbon particles, and ion exchanges. It shows excellent properties as an intermediate material in the synthesis and production of agents and adsorbents and can be used in various applications. Therefore, the method of producing such sulfides has been sought for a long time, among which US Patent Nos. 2,447,004; 2,252,343; 2,539,137; 2,585,454 and 3,248,303 and French Patent No. 1,479,451 and the like. These known methods are to prepare insoluble sulfides by adding sulfur and reacting by heating to a cohydrocarbon such as asphalt. However, a major disadvantage of this method is that the bubbles of hydrogen sulfide generated by the reaction with sulfur are mixed in a large amount in the reaction product. In other words, when reacting hydrocarbons such as asphalt with sulfur, the viscosity of the reaction product increases significantly as the reaction proceeds, and the product passes through a rubbery or viscous phase to become an insoluble and insoluble sulfide. In the initial stage of the reaction, when the viscosity is relatively low, it is easily ruptured and removed from the reaction system. However, as the reaction proceeds, the viscosity of the reaction system increases, making it difficult to remove bubbles, resulting in a sponge-type sulfide having low mechanical strength and low bulk density. This disadvantage can be slightly improved by adjusting the rate of increase of the reaction temperature so that the reaction proceeds slowly, but the efficiency is greatly reduced because it takes too long to complete the reaction.

The second problem is that insoluble sulfides clump together in the reaction vessel. Removing and crushing or crushing agglomerates to form granules or molding these agglomerate materials is very inefficient and uneconomical as it requires a difficult process. The processes described in US Pat. Nos. 2,447,005 and 2,447,006 minimize the above drawbacks by spraying a homogeneous liquid mixture of bihydrocarbons and sulfur into the heated reaction zone to allow the reaction to take place under heating, but in practical terms In view, these processes are inadequate because they require specific skills and complex equipment.

The third problem is that the reaction temperature for obtaining infusible sulfides is too high. In US Pat. No. 3,248,303, it is noted that in order to obtain an insoluble product, the temperature of the reaction system must be heated to 450 ° C. or higher, but sulfides inevitably carbonize at such high temperatures. Carbonized materials are also useful as various carbon materials and are one of the important uses of sulfides, but sulfides have other uses, so carbonization due to high heat limits the use of sulfide products.

As described above, since the manufacturing process of the existing sulfides has many difficulties in the properties of the product and the process itself, the development of a new process that is not accompanied by such disadvantages is urgently required.

Carbon is widely used as electrical conductors, refractory materials, chemical durable materials, structural materials, lubricants, and machine parts in various industries such as general chemical industry, electrochemical industry, telecommunication industry, and nuclear industry. These carbon particles are made by grinding a carbon material, kneading with a side mixture such as pitch or synthetic resin and then molding the desired shape. Natural graphite, anthracite coal, coal, coke, and charcoal are mainly used as carbonaceous materials for making the carbon particles, but it is not always easy to stably supply these raw materials of good quality.

Therefore, petroleum raw materials that can supply a large amount at low prices are highly appreciated, and the petroleum coke industry using these raw materials has become an important industry. The production process of petroleum coke is classified as belonging to the delayed coking process described in "Hydrocarbon Processing, 49 (9) 780 (1970)". Powdered coke obtained by the liquid coking process cannot produce high-quality carbon particles, so it is mostly used as fuel. Coke made by the delayed coking method is very useful for producing various carbon particles, but this process has the big disadvantage that it is very difficult to remove the lumps accumulated in the coking drum and to crush the lumps. Therefore, the mechanization and continuous efficiency are very low and the carbonization efficiency is not satisfactory. .

Therefore, there is a need for a new carbon material manufacturing process that does not need to produce agglomerate quality that lowers work efficiency and has no limited use of powdery carbon. As one process to meet such demands, there is a method of converting a fusible casting such as pitch into an insoluble material by heat treatment or chemical treatment under an oxidizing atmosphere and then carbonizing the infusible material. The transition to an infusible state may include the use of soluble gases such as nitrogen dioxide, oxygen, ozone, sulfurous acid, chlorine, bromine air, sulfuric acid, phosphoric acid and nitric acid, as disclosed in Japanese Patent Application No. 31,195 / 1973. It is achieved by treating with an oxidizing liquid such as aqueous solution of chromic acid, aqueous solution of potassium permanganate at a temperature lower than the softening point of the fusible material. However, this process has the disadvantage that the reaction time takes too long to obtain the desired incompatible material due to the corrosion of the apparatus due to the use of the oxidizing material.

Therefore, in view of the above disadvantages in the conventional process for producing a carbon material, many raw materials can be used at a low price, a powder-limited carbon is not produced, and a special process for grinding the fusible material is required. There is a need for a new process for producing granular carbon.

In addition, activated carbon is a very important substance as an industrial adsorbent, and is used as an adsorbent in the food industry and the chemical industry, and is used in many fields such as an adsorbent or a water purifier of a household refrigerator. Recently, it has been found that activated carbon is very effective in removing and preventing environmental pollution such as air pollution and water pollution. Therefore, it is necessary to develop a method for supplying a large quantity of high quality activated carbon at a low price. Conventionally, activated carbon was produced using wood or corn bark as a main raw material, but it was not possible to smoothly supply large amounts of activated carbon using these raw materials. Recently, activated carbon is manufactured using coal as a raw material. At this time, since coal which can provide quality activated carbon can be obtained only in a limited area, this method also has a big problem in stably supplying a large amount of raw materials.

In this regard, recent attempts have been made to make activated carbon using raw materials such as petroleum heavy hydrocarbons, which can be supplied in large quantities at low prices. For example, alkali metal compounds such as potassium sulfide, sodium hydroxide, sodium carbonate and potassium thiocyanate are added to pitch or asphalt, carbonized and activated to carbonized material. Also obtained by reacting asphalt or pitch with sulfur or sulfuric acid Methods of carbonizing and activating the product are also known. However, the alkali metal addition process is not practical since the alkali metal compound must be washed away in the next step of the process. In addition, in the method using sulfuric acid or sulfur, sulfur or sulfuric acid does not remain in the activated carbon, so there is no need to remove these additives. However, the method using sulfuric acid is dangerous because the use of sulfuric acid in a large amount and there is a problem that the apparatus is corroded. In the method using sulfur, hydrogen sulfide is generated during the reaction, but corrosion of the apparatus is not a problem. Hydrogen sulfide is easily recovered as sulfur by a clauss reaction or catalytic decomposition. Therefore, it is an economically advantageous way to reuse the recovered sulfur. The properties of activated carbon obtained by using sulfur are the same as or better than those of the activated carbon obtained in the coal char, and thus the yield of activated carbon is high. The sulfides are then obtained in sponge-like masses, which are difficult to obtain in the form of discrete granules with sufficiently high mechanical strength and the desired size.

The process for producing the granular carbonaceous solids mentioned above is divided into a process of crushing the product in the form of agglomerates and a process of molding or agglomerating the powdered product into granules using a suitable binder. In the former process, selective production of granular carbonaceous material of a predetermined size is not possible and yield of granular cakes of a desired size is low. Activated carbonaceous material obtained by crushing finely is made of very small pieces or powders, or irregular and angular, which is easy to be damaged when handling. On the other hand, mold granules are usually obtained by mixing a powder of a base material and a binder, molding the mixture into granules, and then heating the mixture. Therefore, since the working efficiency is low because the powder is handled, and the binding force between the binder and the powder particles is weak, there is a disadvantage that the granules tend to become powder by friction. In addition, the process for obtaining granules with a particle size of about 1 mm at several microns is very difficult.

In addition to the above method, a method for producing granular activated carbon is known in which granules are made of granules having a very high softening point into granules, and the granules are made of an infusible material. In this case, since no binder is used, a good granule product having a very high mechanical strength is obtained compared to a normal activated carbon material, but a very precise technique is required to make a fusible material such as pitch in an insoluble state without destroying the material. It is very difficult to obtain granular activated carbon of about 1 mm or more.

The present invention satisfies the above requirements and eliminates the disadvantages.

In the presence of a reaction medium (if necessary, in the presence of an insoluble, insoluble solid), the petroleum heavy fraction is reacted with sulfur with stirring to carbonize and activate this insoluble, infusible granular sulfide. According to the present invention, granular activated carbon having a desired size can be produced with excellent mechanical strength without the need to crush, grind or mold agglomerate solid materials, and without the unique mechanism for granulation. As used herein, the term "insoluble, infusible" means that the granules are not soluble in the reaction medium, petroleum heavy oil and sulfur used under the sulfiding conditions of the process of the present invention and are heated to carbonization conditions, such as 400 to 1,200 ° C. It does not melt, decompose, soften or melt by heat.

The size of the granules produced by the present invention can be obtained by varying from several microns to several centimeters (eg lμ-2 cm) by adjusting the reaction conditions as necessary.

Insoluble, insoluble, and sulfide materials obtained by the present invention have a very high surface tension and a high resistance to abrasion compared to granulated sulfides made by crushing. The granular carbide obtained by the present invention has a very high reactivity as an intermediate in the process for producing carbon compounds such as carbon tetrachloride and carbon disulfide, compared with conventional materials. The granular activated carbon according to the present invention can easily obtain a specific surface area of more than 2,000 m ² / g each (the specific surface area of commercially valuable products is usually about 500 to 1,000 m ² / g).

In addition, the granules obtained by the present invention are in the form of granules or granules similar to those of discs or ruminants, depending on the reaction conditions. In all cases, the surface of the material is smooth, with good stability and fluidity, and mechanical strength such as surface tension. In the process of the present invention, the dehydrogenation and condensation polymerization reactions occur with sulfur, so that sulfides having a three-dimensional network structure having high heat resistance are produced. high. In the carbonization of sulfides, carbonization is carried out directly to the solid state without neglecting the molten state. Thus, granulated carbon having a resistance to graphitization is obtained. When activated, the granular carbon obtains very good activated carbon having a microcrystalline structure.

The petroleum heavy oil used as a starting material in the present invention is liquid or solid at room temperature (20: 20 to 30 ° C.), and has a softening point of 400 ° C. or lower, preferably 300 ° C. or lower, and a boiling point of 300 ° C. or higher under normal pressure. It is preferably at least 400 ° C. and a hydrogen to carbon ratio of about 0.2 to 1.9, preferably 0.4 to 1.7 and a carbon content of 80 to 96% by weight. The petroleum midstream used in the present invention is obtained as a heavy residue of the pomegranate during the purification process such as distillation, pyrolysis, catalytic decomposition, solvent extraction and acid treatment of petroleum. Examples of the above petroleum oil fraction include heavy residues obtained by midstreaming crude oil under atmospheric pressure or reduced pressure (boiling point of about 300 DEG C or higher, H / C atomic ratio: about 1.0 to 1.9); Heavy residue obtained by extracting crude oil, heavy residue obtained by distilling crude oil under normal pressure, or residue obtained by distilling crude oil under reduced pressure with a solvent such as propane, butane, pentane, hexane, cyclohexane or benzene (boiling point is about 350 ℃ or more, H / C atomic ratio: about 0.5 to 1.8 and a softening point of 5 to 300 ° C.); Heavy residue obtained by decomposing crude oil, distilled oil or residues thereof under normal pressure or reduced pressure (boiling point: about 300 ° C. or higher, H / C atomic ratio; about 0.2 to 1.7); And a heavy residue obtained by decomposing these middle stream residues at atmospheric pressure at an elevated temperature, or a residue obtained by distilling them with a solvent under reduced pressure (boiling point below 300 ° C., H / C atomic ratio; about 0.2 to 1.7 ).

Specific examples of petroleum heavy oil fractions that can be used in the process of the present invention include pyrolysis residues of various types of straight asphalt, heavy acid acid asphalt, cutback asphalt, asphalt kerosene or diesel recovered by solvent deasphalting. And residues obtained by pyrolysis or hydrogen decomposition of naphtha, heavy fractions or heavy residues. Among these, asphalt-based heavy oils are excellent raw materials because they have excellent insolubility, hardness and high yield even under relatively weak conditions. The above raw materials are used alone or in mixtures. Hereinafter, "raw material" as used in the present invention shall refer to the above materials.

The reaction medium used in the present invention is a hydrocarbon having a boiling point of 50 ° to 400 ° C. (preferably 70 ° to 300 ° C.) at normal temperature and is reactive to sulfur (condensation polymerization). Form a still life) should be low. Suitable reaction media include aliphatic hydrocarbons (boiling point 50 to 400 ° C., H / C atomic ratio 1.9 to 2.3), aromatic hydrocarbons (boiling point 80 to 280 ° C, H / C atomic ratio 1.0 to 1.6) and petroleum fraction (boiling point 50 to 50). 400 ° C, H / C atomic ratio 1.7 to 2.3). Preferred are aliphatic hydrocarbons such as hexane, octane, liquid paraffin and aromatic hydrocarbons such as benzene, toluene, xylene, tert-butylbenzene. These can be used individually or as a mixture. Furthermore, petroleum fractions having a boiling point of 50 to 400 ° C. at atmospheric pressure such as naphtha fraction, kerosene fraction and diesel fraction obtained by mid-cruising crude oil are preferred as the reaction medium of the present invention. Highly saturated paraffinic hydrocarbons, such as aliphatic hydrocarbons and petroleum fractions above, have a very low reactivity with sulfur. Moreover, low-boiling aromatic hydrocarbons (benzene, toluene, xylene, tertiary butylbenzene, etc.) also react very slowly with sulfur compared to petroleum residues. Since boiling point and silver naphthenic hydrocarbons, aromatic hydrocarbons and unsaturated olefinic hydrocarbons easily react with sulfur at 170 to 400 ° C. with a complex structure mainly composed of petroleum residues, when selecting a reaction medium, the degree of unsaturation of raw materials is important to be considered. do. In fact, in the process of the present invention, the reaction medium can be recovered and reused.

An important purpose of using the reaction medium in the process of the present invention is to lower the viscosity of the liquid phase material of the reaction system to promote the movement and dispersion of the raw materials, sulfur and reaction products and to easily remove the formed hydrogen sulfide from the product. In addition, by stirring the reaction system to reduce the viscosity, the reaction product is well dispersed, thereby promoting the formation of granule product. Therefore, the reaction medium does not have to completely dissolve the raw material or sulfur. Since the process of the present invention uses a reaction medium having high compatibility with the raw material, it has an advantage of easily obtaining insoluble and insoluble granular sulfide even at a relatively low temperature of about 200 to 230 ° C. The reason for this is not yet clear, but it is thought that insoluble and insoluble sulfides are easily separated because fusible and soluble components are selectively dissolved in the reaction medium, thereby reducing the soluble and fusible portions of granular sulfides.

The amount of reaction medium used depends on the type of raw material, the type of reaction medium, incompatibility, insolubility, the amount of solids (if any), the amount of sulfur, and the reaction conditions. For example, when using a mixture of a material with high reactivity with sulfur and a material with low reactivity such as atmospheric distillation residue of crude oil as a raw material, the low reactivity material acts as a reaction medium to help disperse the reaction product. In this case, the atmospheric distillation residue of crude oil is regarded as a mixture of the reaction medium of the vacuum distillation residue of crude oil. As the reaction proceeds when reacting with sulfur using asphalt as a raw material, it is necessary to add a reaction medium when it is difficult to form a dispersion simply by stirring because the viscosity of the reaction system is greatly increased. In addition, the reaction medium is preferably present at all times during the reaction, but the reaction medium should be added according to the viscosity of the reaction product. In general, a suitable viscosity of the reaction system is at most 2,000CS at 98.9 ° C, preferably at most 400CS. That is, the raw material may be reacted with sulfur in the absence of a reaction medium or in the presence of a small amount of the reaction medium, and the reaction medium may be added when the viscosity increases. In some cases this is the preferred method.

As shown in the following examples, the size of the granular sulfide product formed varies greatly depending on the type and amount of the reaction medium. As the amount of the reaction medium increases, the compatibility of the reaction medium with raw materials and sulfur increases, The resulting granular sulfide product is reduced in size. For example, in order to obtain sulfides having a size of 1 μm to 2 cm, it is necessary to precisely determine the amount of reaction medium based on the amount of raw materials and sulfur, and determine the type of reaction medium and other reaction conditions. For example, to obtain granular sulfide from 1 part by weight of asphalt and 1.5 parts by weight of sulfur, at least 0.5 parts by weight of diesel is required when diesel is used as a reaction medium. Obtained. At this time, if the amount of light oil as the reaction medium is less than 0.5 parts by weight, the viscosity of the entire reaction system is greatly increased, and it is difficult to disperse the reactants only by stirring. In addition, when an aromatic hydrocarbon such as toluene is used as the reaction medium, the size of the granules is more remarkable, and in order to obtain granules of a desired size, the amount of the reaction medium must be determined very precisely.

The reaction medium used in the method of the present invention or the liquid composition containing the reaction medium can be reused, and even if a portion thereof is consumed by reacting with sulfur during the reaction, it is continuous without any difficulty to replenish the consumed reaction medium. Can be used as

The insoluble, insoluble solid material used in the present invention is a solid carbonaceous material which is insoluble in raw materials, sulfur and reaction medium, does not melt under the above reaction conditions, and can be converted into carbon or gas in the heat treatment confirmation of the carbonization step or the activation step. It is a substance. Examples of insoluble, insoluble solid materials include insoluble granular sulfides produced by the process of the present invention, granular carbon and granular activated carbon, and materials made by grinding, pulverizing or molding such materials. Petroleum coke, coal, coke and charcoal may also be used as insoluble, insoluble solids. If necessary, inorganic oxides such as metal oxides, such as calcium oxide, aluminum oxide and iron oxide, can be added to the insoluble, insoluble solid material.

Insoluble, insoluble solids may be used alone or in black mixtures.

The reason for using an insoluble, insoluble solid material is to promote granulation and produce granules of desired size with high efficiency in the preparation of granular sulfides. As shown in Examples and Comparative Examples, insoluble and insoluble solid materials are added to the reaction system to prevent the reaction intermediate from adhering to the walls or baffle plates or stirrers of the half vessel, or to prevent the reaction products from agglomerating. The size of the granular sulfide thus obtained is made constant and the yield of granules having a desired size is increased.

The mechanism of the effect obtained by the addition of insoluble and insoluble solids is not yet complete, but it acts as a key for the formation of granule products while the insoluble, insoluble solids are stirred and moving in the reaction medium, or the reaction intermediates are insoluble, It is thought that it is incorporated into the insoluble, solid material filling and rubs off the reaction intermediate which will stick to the reaction bump.

Another reason for the use of insoluble, insoluble solids is due to the granulation products obtained by the process of the present invention, in which the granules of the desired size are returned to the reaction system as insoluble, insoluble solids without shredding or crushing some or all of the granules of desired size. This is because only granules of the desired size are produced by making the granules of a suitable size.

There is no particular limitation on the size of the insoluble and insoluble solid materials used and may be larger or smaller than the desired granules. However, in general, as the size of the granules of the material in the reaction system decreases, the effect of insoluble and insoluble solids is more significant. Therefore, the size of the granular insoluble insoluble solids is 10 mm or less, preferably 0.01 to 5 mm. do.

However, in the method of the present invention, granular sulfide of a desired size or granular activated carbon obtained by carbonizing and activating the granular sulfide can be obtained without the addition of an insoluble and insoluble solid substance.

When insoluble and insoluble solid materials are used, the amount is from 0.02 to 2 parts by weight based on the total weight of the raw materials and the reaction medium.

In the practical aspect of the present invention, the amount of sulfur depends on the reactivity of the raw materials, the type of reaction medium, the reaction conditions, and the like. As shown in the examples, the size of the granular sulfide product depends on the amount of sulfur used when reaction factors such as the raw materials are the same. The amount of sulfur used must be accurately selected to obtain granules of the desired size. Usually, 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight of sulfur, per 1 part by weight of raw material is used. The amount of reaction medium varies depending on the type of raw material and the reaction medium. Usually, the amount of the reaction medium should be 20 parts by weight, preferably 7 parts by weight or less, based on the weight of the raw material, from an economic point of view. The effect by the addition of the amount of sulfur is as follows. When the amount of sulfur is small, the size of the product decreases, and when the amount of sulfur is less than 0.2 parts by weight of the raw material, the insolubilization phenomenon becomes insufficient. Sulfur can be added all at once or intermittently or continuously and in the third case the size of the granular sulfide changes depending on the rate of sulfur addition and the time taken for the addition. Sulfur used in the process of the invention is a solid or molten sulfur element. Sulfur may be added to the reaction system before the reaction system is heated, or may be added to the reaction system all at once or little by little after the temperature reaches the reaction temperature.

In the process of the present invention, the raw material and sulfur easily react to obtain an insoluble sulfide product in a short time. 0.01 to 0.5 parts by weight, preferably 0.03 to 0.3 parts by weight, of metal halides such as aluminum chloride, zinc chloride, Lewis acid such as ferric chloride, and preferably 0.03 to 0.3 parts by weight of sulfur may increase the reaction rate and shorten the reaction time. Can be.

In this specification, "stirring" is to keep the materials in the reactor in the liquid phase, to uniformly disperse the materials of the reaction system in a physical manner, and to promote the reaction of the chemical reaction by promoting the mass and heat transfer of the reaction system. Therefore, the stirring method is not limited, and any stirring method or apparatus that can achieve the above object can be used. For example, a shaker, agitator blade rotating device, agitator blade shaker, liquid flow device, gas injection device, liquid shake device, etc. may be used for this purpose. In order to enhance the stirring effect, it is also effective to disperse foreign substances compatible with the reactants in the reaction system such as water droplets or pottery pieces to cause severe turbulent flow of liquid around them in the reaction system. It is also sometimes effective to improve the method by dispersing raw materials, sulfur-reactive media, and the like in water with low-viscosity foreign matter. If the reaction system is not stirred, agglomerates of sulfide products are lumped in the reaction vessel and granulated sulfide products are not obtained.

The reaction of the invention is carried out in a batch system or in a continuous system. For example, the main reaction can be carried out continuously using a multistage stirred bath.

Suitable reaction temperatures for reacting the raw material with sulfur in the process of the present invention to produce granular sulfide products are from 170 ° to 400 ° C, preferably from about 200 to 300 ° C. The reaction time can be reduced by increasing the reaction temperature, but when the reaction temperature exceeds 400 ° C., the loss of the reaction medium increases, and granular sulfide products having a desired size are produced as by-products and condensate on the inner wall of the reactor. This result makes the smooth operation of the reaction difficult. When the reaction temperature is higher than 200 ℃ granular sulfide is formed in a short time. In this case, a short reaction time results in a low density granule product, but the reaction can be continued to increase strength and viscosity. Moreover, it is not always necessary to completely react the raw material and sulfur. On the other hand, a large amount of sulfur is required to complete the reaction and the reaction time is long, so that unreacted materials are left and reused in the reaction system.

The process of the present invention carries out the reaction in a liquid phase, preferably in an atmosphere. When the melting point of the reaction medium is lower than the operating temperature, a pressure above atmospheric pressure sufficient to suppress the volatile aroma of the reaction medium may be used at the operating temperature.

The reaction can be carried out at atmospheric pressure to 100kg / cm ² , preferably at atmospheric pressure to 30kg / cm ² .

Since the granular sulfide product obtained by the process of the present invention has no softening point, the granular sulfide product maintains the granular form even at high temperature carbonization. Granular sulfide products can be easily carbonized by heating under an inert gas such as nitrogen, hydrogen sulfide, carbon monoxide or mixtures thereof at 400 ° C to 1,200 ° C, preferably 450 to 1,100 ° C.

This granular carbon can be easily converted to granular activated carbon by activating in a conventional manner using an oxidative atmosphere. In contrast, granular activated carbon can be easily obtained by heating the granular sulfide product to a temperature of 700 to 1,100 ° C. directly in a weak oxidizing atmosphere such as medium or fluid gas, at which time the carbonization and activation of the product are simultaneously performed. An activation method using a gas containing carbon dioxide can also be used in the present invention. Such an activation method is preferable for the activation method of neutralization to steam. Steam is preferably used as the oxidizing gas. Carbon dioxide or fluids containing between 1 and 30% oxygen can be used with or without steam.

The granular sulfide product or granular carbon produced by the method of the present invention may be crushed and activated by crushing to a desired size, or may be made into small particles using a suitable binder prior to carbonization or activation.

The constituents of the reaction vessel used in the present invention are inert to the reactants under the reaction conditions. For example, stainless steel, titanium, enameled iron or the like is suitable as the reaction vessel material.

The following examples illustrate the present invention in detail and the object and scope of the present invention are not limited thereto. All parts, percentages, ratios, etc. in these examples are given by weight unless otherwise indicated.

Example 1

1 g stainless steel reaction vessel equipped with an electromagnet rotating stirrer and reflux condenser, 200 g of light oil (in this case, boiling point 185 to 350 ° C, viscosity 2.14CS (at 50 °), H / C atomic ratio 1.9, specific gravity (15) / 4 ° C) 0.0835), 100 g of asphalt obtained by atmospheric distillation of propane (hereinafter referred to as "propane deasphalted asphalt") and penetration at 25 ° C according to JIS 2,530 18: n-pentane insoluble component 21 %, Sulfur content 5.7%, H / C atomic ratio 1.41) and 150g of sulfur, and reacted at 230 to 235 ℃, stirring at a rate of 900r.pm for 4 hours at atmospheric pressure. During the reaction, a large amount of gas, mainly composed of hydrogen sulfide, is produced. After the completion of the reaction, the reaction mixture was taken out and centrifuged and filtered to give 136 g of granular sulfides having a length of 1 to 18 mm, a width of 1 to 7 mm, and a thickness of 1 to 3 mm, a small amount of agglomerated sulfide and a reaction medium of 145 g. Phase was obtained. Sulfur content in the granular sulfide is 26% and does not dissolve when heated rapidly at 400 to 1,200 ℃.

In addition, the agglomerated sulfide is a solid substance attached to the bottom and the base wall of the reaction vessel, and the oily substance is a substance containing unreacted asphalt when it is liquid at room temperature.

Comparative Example 1

In the same amount of reaction vessel as in Example 1, propane deasphalted asphalt and sulfur were added and reacted at 230 to 235 ° C. for 4 hours without stirring under normal pressure. When the reaction mixture was taken out after the completion of the reaction, insoluble and insoluble agglomerated sulfides 220g were formed, and granular sulfides were not produced.

Example 2

The same process as in Example 1 and only changing the stirring speed to 1,200rpm yielded 151 g of granular sulfide (length 1 to 17mm, width 1 to 4mm, thickness 1 to 3mm) of a smaller size than the product of Example 1 119 g of phase material is recovered. In this case agglomerated sulfides were well formed.

Example 3

400 g of diesel oil, 200 g of propane deasphalted asphalt and 300 g of sulfur were added to the same container as in Example 1, and the reaction was carried out at atmospheric pressure while stirring at a speed of 1,200 rpm for 4 hours at 230 to 235 ° C. for a length of 1 to 5 mm, 321 g of fine fusiform granular sulfides having a diameter of 0.4 to 2 mm are obtained.

Example 4

In the same reaction vessel as in Example 1, 400 g of diesel oil, 200 g of propane deasphalted asphalt, 250 g of sulfur, and stirred at a speed of 1,200 rpm under normal pressure and reacted at 230 to 235 ° C. for 4 hours, the average particle size was about. 317 g of spherical granular sulfides of 0.7 mm are obtained. At this point, agglomerated sulfides are produced less.

Example 5

400g diesel oil, 200g propane deasphalted asphalt, 200g of sulfur in the same container as in Example 1, and stirred at a speed of 1,200rpm while reacting at atmospheric pressure, 230 to 235 ° C for 4 hours, the average size is about 0.03mm 26 g of spherical granular sulfide are obtained.

Example 6

In the same reaction vessel as in Example 1, 400 g of diesel oil, 100 g of propane deasphalted asphalt, 150 g of sulfur, and stirred at a speed of 1,200 rpm for 4 hours at atmospheric pressure and 230 to 235 ° C. were spherical with an average size of about 0.2 mm. 263 g of granular sulfide are produced. In this case less agglomerated sulfides were produced.

Comparative Example 2

100 g of propane deasphalted asphalt and 150 g of sulfur were added to the same reaction vessel as in Example 1 and reacted at atmospheric pressure at 230 to 235 ° C. while stirring at a speed of 1,200 r.p.m. As the reaction proceeds, the viscosity is greatly increased, and stirring is impossible after 20 minutes of starting the reaction. If it is reacted for 4 hours as it is, only 208g of agglomerated sulfide is obtained, but a granular sulfide is not obtained. At this time, the product was a solid material such as pumice at room temperature and only partially dissolved even when heated to 400 ° C. rapidly.

Example 7

In the same reaction vessel as in Example 1, 400 g of diesel oil, 200 g of Kuwait reduced-pressure residual oil (1.30 at specific gravity of 15/4 ° C., n-haptan insoluble component 5.6%, sulfur content 5.6%) and 300 g of sulfur and 900r The reaction was carried out at atmospheric pressure at 230 to 235 ° C. for 4 hours with stirring at a rate of .pm to obtain 121 g of disc-shaped granular sulfide having a length of 10 to 15 mm, a width of 4 to 8 mm, and a thickness of 1.5 to 3 mm.

Example 8

400 g of Kuwait atmospheric pressure residual oil (0.966 at specific gravity of 15/4 ° C, 2.6% of n-heptane insolubles, 4.1% of sulfur) and 200 g of sulfur were added to the same reaction vessel as in Example 1, while stirring at a speed of 900 r.pm. The reaction was carried out at 240 to 245 ° C. for 3 hours to obtain 194 g of a granular sulfide in a plate shape having 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 (IBP at 280 ° C.), 200 g of propane deasphalted asphalt, and 300 g of sulfur were added to the same reaction vessel as in Example 1, followed by 4 hours of reaction at atmospheric pressure and 230 to 235 ° C. while stirring at a speed of 1,000 rpm. 110 g of disc-shaped granular sulfides having a length of 7 to 13 mm, a width of 3 to 6 mm and a thickness of 1 to 4 mm were obtained.

Example 10

200 g of FCC-cyclo oil having a boiling point of 330 to 420 ° C., 200 g of propane deasphalted asphalt, and 300 g of sulfur were added to the same reaction vessel as in Example 1, followed by 4 hours of reaction at atmospheric pressure and 230 to 235 ° C. while stirring at a rate of 500 r.pm. 260 g of spherical granular sulfides having an average size of 1.5 mm were obtained.

Example 11

Into the same reaction vessel as in Example 1, 300 g of tert-butyl benzene 200 g of propane deasphalted asphalt 300 g of sulfur were stirred at a speed of 700 r.pm and reacted at 230 to 235 ° C. for 4 hours under 15 kg / cm ² pressure. 120 g of spherical granular sulfides having an average size of 0.6 mm were obtained.

Example 12

145 g of the oily material recovered in Example 1, 70 g of diesel oil, 65 g of propane deasphalted asphalt, and 150 g of sulfur were added to the same reaction vessel as in Example 1, and stirred at a speed of 900 r.pm at 4Om at 230 to 235 ° C. The reaction was carried out to obtain l29 g of granular sulfide having a raw shape having a length of 6 to 15 mm and a width of 3 to 9 mm and a thickness of 1 to 4 mm.

Example 13

In the same reaction vessel as in Example 1, 400 g of diesel oil, 200 g of propane deasphalted asphalt, and the reaction system were heated to 230 to 235 ° C., and 300 g of sulfur was stirred at a rate of 500 r.pm at 1 g per minute at normal pressure. Apply slowly The reaction was continued for another hour, and then the reaction mixture was centrifugally filtered to give 428 g of spherical granular sulfide having an average size of 0.005 mm.

Example 14

400 g of light oil and 300 g of sulfur were added to the same reaction vessel as in Example 1, and the mixture was heated to 230 to 235 ° C. under normal pressure, and 200 g of propane deasphalted asphalt was slowly added to 1 g per minute. After the reaction was continued for another 1 hour, 416 g of a caliber granular sulfide having an average size of 0.8 mm was obtained.

Example 15-18

The granular sulfides obtained in Examples 1, 3, 10 and 13 were heated to 450 ° C. and carbonized, respectively, while generating a gas mainly hydrogen sulfide so that the granular carbon was 55% relative to the granular sulfide 1 (Example 15) and 64. % (Example 16), 75% (Example 17), and 52% (Example 18) were obtained.

Example 19

The disk-like granular carbon obtained in Example 15 was finely crushed to a diameter of 1.0 to 1.4 mm, and then 50 g was activated at 70 minutes by 850 ° C. using steam to have a specific surface area of 2,250 m ² / g and methylene blue adsorption of 525 mg / g. 21 g of phosphorus granular activated carbon is obtained. The sulfur content in this activated carbon is 1.2%. In addition, the specific surface area was measured by the BET method, which is a surface area measurement method using nitrogen adsorption, and methylene blue adsorption was measured by titration with a buffer solution containing 300 mg / L methylene blue (pH 7.) The quantity is weighed and placed in a shake flask, shaken vigorously for 30 minutes and the activated carbon is filtered out The amount of methylene blue in the remaining filtrate is measured by absorbing light at a wavelength of 665 mμ. In the following examples, adsorption was also measured by this method.

Example 20

From the fusiform granular carbon obtained in Example 16, granular carbon having a length of 1 to 1.4 mm and a diameter of 0.4 to 1 mm was selected without crushing and activated by steam at 850 ° C. for 60 minutes to achieve a specific surface area of 1,820 m ² / g and an adsorption degree of methylene blue 336 mg. 22 g of activated carbon was obtained.

Example 21

50 g of the spherical granular carbon obtained in Example 17 was activated by steam at 850 ° C. for 70 minutes to obtain 23 g of granular activated carbon having a specific surface area of 2,178 m ² / g and methylene blue adsorption degree of 513 mg / g.

Example 22

50 g of the spherical granular carbon obtained in Example 18 was activated by steam at 850 ° C. for 40 minutes to obtain spherical granular activated carbon having a specific surface area of 1,820 m ² / g and methylene blue adsorption degree of 360 mg / g.

[Examples 23-28]

Pulverized activated carbon obtained in Example 19, granular activated carbon obtained in Examples 20, 21 and 22, commercial pulverized activated carbon (1.0 to 1.1 mm in diameter, specific surface area: 970 m ² / g, methylene blue adsorption degree: 185 mg) / g) and commercial spherical activated carbon (diameter 1.0 to 1.5mm, specific surface area: 970m ² / g, methylene blue adsorption: 170mg / g) in a glass tube with an inner diameter of 20mm and a length of 200mm. Rotate for 10 hours. Weigh the powder with a size less than 0.07 mm and determine the percentage of this powder with respect to the whole material. The powder percentage of these activated carbons was 0.1% by weight, 0.01% by weight or less, 0.3% by weight and 2.8% by weight, respectively, indicating that the activated carbon obtained according to the present invention did not form a powder well compared to conventional activated carbon. It means.

Example 29-32

150 g of propane deasphalted asphalt, 225 g of sulfur and 75 g of granular sulfide having a particle size of 0.5 to 1.0 mm obtained in accordance with the present invention were placed in a reaction vessel as in Example 1, and 150 g of diesel oil (Example 29 ), 300 g of diesel oil (Example 30), 450 g of diesel oil (Example 31) and 600 g of diesel oil (Example 32) were added, followed by stirring at a rotational speed of 900 r.pm, respectively, at atmospheric pressure and 230 to 235 ° C. for 4 hours. React. Reactivity Increases large amounts of gas, mainly hydrogen sulfide. The reaction mixture is taken out of the reaction vessel and centrifugally filtered to obtain an insoluble and insoluble spherical granular sulfide having a particle size distribution equal to one. There were few reaction products adhering to the reaction vessel wall in agglomerates.

Comparative Example 3

150 g of propane deasphalted asphalt, 225 g of sulfur, 50 g of granular sulfide having a particle size of 0.5 to 1.0 mm obtained in accordance with the present invention, and stirred at a rotational speed of 900 r. The reaction is carried out at 235 ° C. As the reaction proceeds, the viscosity of the materials in the reaction system increases greatly, and after about 20 minutes, the temperature of the reaction system is reached, making the system unable to stir. After 4 hours of further reaction in this state, no granular sulfide is obtained but only agglomerated sulfides are formed. On cooling, the product turns into a solid material such as pumice. When this material is rapidly heated to 400 ° C., the product partially melts.

TABLE 1

( ^* ): Weight percent (added granular sulfides are removed)

( ^** ): Lump sulfide attached to the wall of reaction vessel

As shown in Table 1, the particle size of the granular sulfide was changed according to the amount of the reaction medium used, and in Comparative Example 3 in which the reaction medium was not used, the granule product was not produced.

Example 33-37

200 g of propane deasphalted asphalt, 400 g of diesel oil and 100 g of granular sulfide having a particle size of 0.5 to 1 mm obtained according to the present invention were added to the reaction vessel as in Example 1, and 200 g of sulfur was added to the mixture (Example 33), After adding 250 g (Example 34), 275 g (Example 35), 300 g (Example 36) or 400 g (Example 37), the reaction was carried out at 230 to 235 ° C. for 4 hours under atmospheric pressure while stirring at a rotational speed of 900 r.pm. In each case, an insoluble, insoluble granular sulfide having a particle size distribution shown in Table 2 is obtained.

TABLE 2

( ^* ) Added granular sulfides removed by weight

[38-40]

200 g of propane deasphalted asphalt, 400 g of diesel oil, 300 g of sulfur in the reaction vessel as in Example 1 and 20 g of the granulated granular sulfide obtained in accordance with the present invention (Example 38), 60 g (Example 39) Or 100 g (Example 40), (The particle size distribution of the crushed powder is 30% particles having a size of 0.25mm or less, 30% of particles having a size of 0.25 to 0.5mm, particles having a size of 0.1 to 1.0mm 40%) and then reacted at 230 to 235 ° C. for 4 hours with stirring at a rotational speed of 900 r · pm to obtain insoluble and insoluble spherical granular sulfides having a particle size distribution shown in Table 3. Also for comparison, the results obtained in Example 1 without using pulverized granular sulfides are shown in Table 3.

TABLE 3

( ^* ): Weight percent of total solids formed by the reaction (including added solids)

( ^** ): agglomerates attached to the wall of the reaction vessel

As shown in Table 3, in Example 38-40, granules having a narrow particle size distribution were obtained, and the mass material was attached to the reaction vessel wall slightly or not at all. It can also be seen that by adding the pulverized granular sulfides the size of the particles and the shape of the product changed.

Example 41-43

200 g of propane deasphalted asphalt, 400 g of diesel oil, 300 g of sulfur and 100 g of the granular sulfide obtained according to the present invention were added to the reaction vessel as in Example 1 and stirred at 230 to 235 ° C. while stirring at a rotational speed of 900 r.pm. React for 4 hours. The particle size of the granular sulfide used above is 0.25 mm or less (Example 41), 0.25 to 0.5 mm (Example 42), or 2.8 to 5.0 mm (Example 43). The distribution of the form and particle size of the granules obtained according to the present invention is shown in Table 4.

TABLE 4

( ^* ): Weight percent of total solids formed by the reaction (including added solids)

Example 44

100 g of Pacific Ocean coal (13% ash, 13% volatile component) pulverized into 200 g propane deasphalted asphalt, 300 g sulfur and particles of size 0.4 to 1.0 mm in 400 g diesel oil in the reaction vessel as in Example 1 %, Hydrogen / carbon atom ratio 0.94), and stirred at a rotational speed of 900 r.pm for 4 hours at 230 to 235 ° C. under atmospheric pressure to obtain granular sulfides having a particle size of about 2.5 mm.

Example 45

Into the same vessel as described in Example 1, 400 g of light oil, 100 g of propane deasphalted asphalt and 150 g of sulfur, followed by stirring at 900 r.pm for 2 hours at 230 to 235 ° C. to give an average particle size of about 0.2 mm. Make granular sulfides of size. 200 g of propane deasphalted asphalt and 250 g of sulfur were added to the reaction mixture, followed by further reaction for 4 hours to obtain granular sulfide having an average particle size of about 0.8 mm.

Example 46

100 g of the granular sulfide obtained according to the present invention with 200 g and 400 g of diesel oil and 250 g of sulfur and the granular sulfide obtained according to the present invention in the same container as in Example 1, 100 g of which was shredded to a size of 0.25 mm or less. The reaction was carried out at 230 to 235 ° C. for 4 hours while stirring at 1,200 rpm to obtain a fusiform granular sulfide having a length of about 1 to 2 mm and a diameter of about 0.4 to 1 mm.

Example 47

Into the same vessel as in Example 1, 400 g and 300 g of the Kuwait atmospheric residual oil described in Example 8 and 100 g of granular sulfide having a particle size of 0.5 to 1.0 mm obtained according to the present invention and stirred at 900 r.pm The reaction was carried out at 230 to 235 ° C. for 4 hours to obtain spherical granular sulfides having an average particle size of about 0.5 mm.

Example 48

Into a container as in Example 1 was filled with 200 g of propane deasphalted asphalt, 300 g of tert-butylbenzene and 300 g of sulfur and granular sulfides having a particle size of 0.5 to 1.0 mm obtained according to the present invention, followed by 500 r. The reaction was carried out at a temperature of 230 to 235 ° C. under a pressure of 15 kg / cm ² while stirring at .pm to obtain a spherical granular sulfide having an average particle size of about 0.2 mm.

Example 49

In a container as in Example 1, 400 g of diesel oil, 300 g of sulfur and 100 g of 0.5 to 1.0 mm granular sulfide obtained according to the present invention were charged and the mixture was heated to 230 to 235 ° C. under normal pressure, followed by 500 r. While stirring at a speed of .pm was added at a rate of 1g per minute of 200 g of propane deasphalted asphalt and the reaction was carried out for 1 hour to obtain a spherical granular sulfide having a fungal particle size of 0.7mm.

Example 50

In the same vessel as in Example 1, 400 g of diesel oil, 200 g of propane deasphalted asphalt and 100 g of granular sulfide having a particle size of 0.5 to 1.0 mm obtained according to the present invention were charged and stirred at a speed of 900 r.pm. While applying 300g of sulfur under normal pressure, 230 to 235 ℃ at a rate of 1g per minute is added. After the reaction was continued for another 1 hour, the reaction mixture was taken out of the container to obtain a spherical granular sulfide having an average particle size of about 0.005 mm.

Example 51

The granular sulfides obtained in Example 29, having a particle size of 1.0 to 1.4 mm, were carbonized by heating at 450 ° C. for 2 hours under a nitrogen atmosphere to obtain granular carbon as described in Table 5 below.

Example 52

Granular sulfides having a particle size of 0.15 to 0.25 mm obtained in Example 32 were treated as in Example 51 to obtain granular carbon as described in Table 5 below.

Example 53

Granular sulfides having a particle size of 0.5 to 1.0 mm, obtained in Example 34, were treated as in Example 51 to obtain granular carbon as described in Table 5 below.

Example 54

The granular sulfide obtained in Example 42 was treated as in Example 51 to obtain granular carbon as described in Table 5 below.

Comparative Example 4

The mixture of charcoal powder was passed through a 0.05 mm mesh sieve and formed into spherical granules by using a rotary granulator and coal tar pitch as a binder, and heated to 450 ° under nitrogen atmosphere for 2 hours, and the following Table 5 The granular carbon as described in is obtained.

TABLE 5

( ^* ): 20 ml of sample is placed in a glass tube with a length of 20 mm and an inner diameter of 20 mm. The glass tube is rotated at a rate of 10 r.pm for 10 hours. The weight of the powder having a size of 0.07 mm or less is measured and expressed as a percentage (%) of the total weight of the powder.

As can be clearly seen from the results shown in Table 5, the granular carbon obtained according to the present invention has a very low powder ratio, and thus the granular carbon obtained according to the present invention has a very good mechanical strength. have.

Example 55

The granular carbon obtained in Example 51 was activated for 90 minutes at 850 ° C. by steam according to a conventional method to obtain granular activated carbon as shown in Table 6 below.

Example 56

The obtained tubular granular carbon in Example 53 was activated for 60 minutes at 850 ° C. using steam to obtain granular activated carbon as shown in Table 6 below.

Example 57

The granular carbon obtained in Example 54 was treated as in Example 55 to obtain granular activated carbon as shown in Table 6 below.

TABLE 6

( ^* ): Measured value by BET method using nitrogen absorption

( ^** ): Measured using buffer solution (pH 7) containing 300 mg / l methylene blue.

Comparative Sample 1 shown in the above table is pulverized commercial activated carbon and Comparative Sample 2 is spherical commercial activated carbon.

As can be clearly seen in Table 6, the granular activated carbon obtained according to the present invention is excellent in surface area and methylene blue absorption, and even better in terms of powder ratio and mechanical strength than commercially available.

Example 58

In a same vessel as in Example 1, 200 g of propane deasphalted asphalt, 400 g of diesel oil and 250 g of sulfur and the pulverized granular sulfides (granulated to a size of 0.5 mm or less) obtained according to the present invention were loaded and 900 r. The reaction is carried out at 230 to 235 ° C. for 4 hours under atmospheric pressure with stirring at .pm. The reaction mixture is separated from the vessel and centrifugally filtered to yield 410 g of spherical granular sulfide and 313 g of filtrate (recovered oil). A portion of the recovered oil is analyzed to determine the presence of unreacted asphalt to calculate the amount of propane deasphalted asphalt and light oil consumed in the reaction.

Then, a new amount of propane deasphalted asphalt and light oil are added to the recovered oil corresponding to the amount of components consumed, followed by 180 g of sulfur and 100 g of granular sulfide (granulated to a size of 0.5 mm or less). ) And then react again. By repeating the same process, the recovered oil is used five times. This gives granular sulfides as listed in Table 7 below. From the results shown in Table 7 below, it can be seen that the recovered reaction medium (diesel) can be used as it is without any difficulty.

TABLE 7

Claims (1)

Petroleum intermediates and sulfur are used in the reaction medium (wherein sulfur is used in an amount of about 0.2 to 5 parts by weight per weight part of the petroleum heavy matter, and the petroleum intermediate is liquid or solid at room temperature and is about 400 It has a softening point of less than ℃ ℃, a boiling point of more than about 300 ℃, carbon content of about 80 to 96% by weight of H / C atomic ratio of about 0.2 to 1.9, the reaction medium is a boiling point of about 50 ℃ to 400 ℃, liquid hydrocarbon at room temperature Reactivity with sulfur is lower than that of the petroleum heavy material, and the amount of controlling the viscosity of the reaction system is used to be less than about 2,000CS.) Hard and dense granular material is stirred while stirring at a temperature of about 170 ° to 400 ° C. A method for producing granular activated carbon by reacting for a time necessary for producing, filtering the reaction mixture to separate the oily substance, and carbonizing the recovered insoluble and insoluble granular sulfide.