Method of production of carbon carrier for catalysts

FIELD: production of carbon carrier for catalysts.

SUBSTANCE: proposed method includes heating of moving layer of granulated furnace black used as backing, delivery of gaseous or vaporous hydrocarbons into soot layer followed by their thermal decomposition on soot surface forming layer of pyrocarbon at forming of layer of pyrocarbon and activation of material compacted by pyrocarbon at temperature of 800-900°C and unloading of finished product. Granulated furnace black at specific surface of 10-30 m2/g and adsorption rate of 95-115 ml/100 g is used as backing for compacting with pyrocarbon. Then, product is subjected to activation for obtaining total volume of pores of 0.2-1.7 cm3/g. Black is compacted by pyrocarbon at two stages: at first stage, granulated black is compacted to bulk density of 0.5-0.7 g/cm3, after which material is cooled down and screened at separation of fraction of granules of 1.6-3.5 mm; at second stage, this fraction is subjected to repeated pyrolytic compacting to bulk density of granules of 0.9-1.1 g/cm3.

EFFECT: enhanced economical efficiency; increased productivity of process.

3 ex

 

This invention relates to the technology for carbon carriers of various catalysts and sorbents.

A method of obtaining porous carbon material, which can be used as a carrier for catalysts. This method includes: loading during rotating at high angular velocity reactor granular carbon black with a primary particle size of 200(specific surface area of 120 m2/g), heating the reactor with soot external heater to 900°and the flow in the layer continuously stir soot gaseous hydrocarbons. After the processing of hydrocarbons and soot carburizing of carbon black pyrocarbon due to their thermal decomposition gas and cease served for quite a long time, water vapor, thereby activating coated with pyrocarbon granules of carbon black (Patent RF №1706690 on CL IPC 01 J 20/20).

The disadvantage of this method of producing the porous carbon material is its low efficiency caused by the use as a substrate for carburizing expensive carbon black with high surface area.

A method of obtaining carbon carrier catalysts comprising heating a horizontally rotating layer of granulated carbon black with a specific surface area of 30-100 m2g, the gaseous or vaporous hydrocarbons in the moving layer with subsequent thermal decomposition and deposition of pyrocarbon on soot. Heating of the moving layer of soot are using an external electric heating to heat the layer to 950°, then in the layer continuously stir soot serves a mixture of gaseous hydrocarbons. The process is carried out for 5 hours, then stir in the layer of material instead of the hydrocarbon serves a steam-air mixture. Once activated carbon granules media have the form of hollow globules, which are associated into larger formations (RF Patent No. 1352707 on CL 01 J 37/10, 35/10, 21/18).

The disadvantages of this method of obtaining carbon carrier catalysts is the low productivity and economic efficiency of the process. This disadvantage increases with increasing specific surface area is used as the substrate of soot.

The aim of the present invention is to improve economic efficiency and productivity of the process.

The proposed method of obtaining carbon carrier for catalysts includes heating a moving layer of granulated carbon black with a specific surface area of 10 to 30 m2/g and the amount of adsorption of dibutyl phthalate 95-115 ml/100 g is used as the substrate. Heating of the moving layer of soot is performed with the use of what Finance high-temperature products of complete combustion of auxiliary fuel to the temperature of decomposition of gaseous or vaporous hydrocarbons. In the moving layer of soot serves gaseous or vaporous hydrocarbons which decompose on the surface of soot particles with the formation of a layer of pyrocarbon. This process of carburizing granulated carbon black lead in two stages. In the first stage soot compacted to achieve a bulk density of 0.5-0.7 g/cm3after which the process is stopped, the soot is cooled and subjected to sieving with the release fraction of granules with a size of 1.6 to 3.5 mm In the second stage heating and carburizing is subjected to only the layer composed of pellets of this size. When reaching the bulk density of the material, 0.9-1.1 g/cm3carry out the activation process steam or a mixture of water vapor from the combustion of auxiliary fuel at a temperature of 800-900°until the value of the total pore volume of 0.2-1.7 cm3/year of Finished product after cooling is unloaded.

Distinctive features of the proposed technical solution is used as the substrate of the furnace granulated carbon black with a specific surface area of 10 to 30 m2/g and the amount of adsorption of dibutyl phthalate 95-115 ml/100 g, as well as activation of the compacted by the pyrocarbon material until the value of the total pore volume of 0.2-1.7 cm3/year

Another feature of this invention is the holding sealing soot pyrocarbon in two with the adiya's. In the first stage granular soot compacted to achieve a bulk density of 0.5-0.7 g/cm3. Then produce a cooling mass of the material and sieving emitting fraction of granules with a size of 1.6 to 3.5 mm. then, in the second stage, this fraction is subjected to re-pyrolytic compaction to achieve a bulk density of granules 0.9-1.1 g/cm3.

Offered for bid is a set of essential features can improve the performance of the process and its efficiency by reducing costs.

Use as a substrate granulated furnace carbon black with a specific surface area in the range 10-30 m2/g and the amount of adsorption of dibutyl phthalate 95-115 ml/100 g enables to obtain porous carbon carrier for catalysts with a predominance of mesopores.

Furnace carbon black in the above range, the specific surface area and amount of adsorption dibutylphtalate characterized by high structure that ensures the penetration of gas - hydrocarbon, thermally decompose with the formation of pyrolytic layer of carbon on the depth of the pellets. The latter, in turn, promotes the formation of interconnected mesopores when you activate coated with pyrocarbon of soot particles and further increases the proportion of the catalytically active surface.

Bottom is th limit value of the specific surface of carbon black, equal to 10 m2/g, due to the technological capacity of furnace carbon black production process. The use of carbon black with a specific surface area greater than 30 m2/g leads to lower economic performance of the process of obtaining carbon carrier for catalysts, since the larger the value of specific surface area of carbon black, so it is more expensive and the more expensive of the substrate increases the cost of the material.

The lower limit of the amount of the dibutyl phthalate adsorption - 95 ml/100 g due to the fact that this worsens the conditions for the formation of mesopores, and the upper limit of 115 ml/100 g is limited by the conditions of efficient technological process of production of soot.

Two-stage compaction of granules of carbon black pyrocarbon due to the fact that in the process of pyrolytic decomposition of gaseous hydrocarbons in a rotating layer of granulated carbon black condition considered horizontally isothermal surface layer, usually not observed, and the height of the layer there is a temperature gradient (up to 100° (C)caused by the segregation of granules in size. As a result of segregation of the loaded weight of the granulated carbon black (0.2-6.0 mm) is divided into several layers, in different temperature conditions. There is no uniform mixing layer of the substrate. Granules of large dimensions form the upper mixed layer mass and have the t highest temperature, granules with a size of 1.0-3.0 mm in the position gap between the small of 0.2-1.0 mm and large granules and have a lower temperature due to the low thermal conductivity of carbon black. The intensive feeding of the pellet substrate by pyrocarbon occurs in the whole range of granule size. For the purposes of using the carbon material as a carrier for catalysts the preferred fraction of granules in the range of 1.6 to 3.5 mm the Selection of this fraction of the total mass of the substrate before the carburizing by sieving into different fractions is not possible due to the destruction of the less powerful by the strength of the granules and the formation of large amounts of dust. If the preliminary seal to expose the entire mass of carbon black to achieve a bulk density of 0.5-0.7 g/cm3then the destruction of the granules at the screening and selection of the target faction is not happening. The lower limit value of the bulk density (0.5 g/cm3) due to the mechanical strength of the pellets of carbon black, which is still insufficient to pellets without destroying withstood the loads occurring during sieving. The upper limit value of the bulk density of 0.7 g/cm3) due to the lower efficiency of the process due to the over consumption of hydrocarbon gas. And then, after sieving, pyrolytic seal is subjected to only the target faction that C is acetelyne reduces the flow rate of hydrocarbon gas source pyrocarbon. It achieves high efficiency seal of soot particles by pyrocarbon before reaching the bulk density of the granules of 0.9-1.1 g/cm3. The limits of the value of the bulk density of the target product based on the requirements of the terms of use of the product for the intended purpose. The same is due and limits the total volume of the pores of the catalysts used in different processes, different.

The effectiveness of the proposed method and the necessity of its modes of implementation to achieve the goal is illustrated by the following examples.

Example 1 (the prototype). In a preheated 400°With horizontal rotating reactor load 200 kg of carbon black with a specific surface area of 50 m2/g (the market value of 15 rubles per kg). Then the reactor is heated to 850°and in layer continuously stir soot serves propane-butane mixture containing 50% propane and 50% butane. After pyrolytic seal soot for 20 hours to the bulk density of 1.0 g/cm3the material weight is 350 kg Forth in the mixed layer carbon material instead of propane-butane mixture for 15 hours serves a steam-air mixture. The total pore volume of the obtained material is 1.7 cm2/g and the total mass of 175 kg For separation fraction with a grain size of 1.6-3.0 mm produce Rasse the product. The mass of the target fraction is 87 kg

Properties of the obtained product:

bulk density550 g/cm3
the specific surface460 m2/g
the total pore volumeto 0.72 cm3/g
including: - the mesopores0,55 cm3/g
the micropores85 mm3/g

Example 2 (present invention). The process of carbonization of carbon black with a specific surface area of 50 m2/g lead in example 1, but when the bulk density is equal to 0.6 g/cm3, carburizing stop, the material is cooled and produce his sieving into different fractions. The selected weight fraction with a particle size of 1.6-3.5 mm 150 kg of this material is loaded into the reactor and in the layer continuously stir the material serves a propane-butane mixture containing 50% propane and 50% butane. After carburizing material for 15 hours to the bulk density of 1.0 g/cm3the material weight is 250 lbs. Activation material is conducted according to example 1 to obtain a carbon material with a total volume of pores to 0.72 cm3/year mass of the obtained material is 120 kg, and its properties are similar to properties of the material obtained in example 1.

Example 3 (p the present invention). The processes of carbonization and activation are as in example 1, but the substrate using an oven granulated carbon black with a specific surface area of 20 m2/g and the amount of dibutyl phthalate adsorption of 105 ml/100 g (the market value of such carbon black 10 rubles per kg). The initial material weight - 200 kg, after carburizing - 250 kg, after activation of 175 kg, and after sieving with a target allocation fraction - 87 kg

Properties of the obtained product:

bulk density552 g/cm3
the specific surface425 m2/g
the total pore volume in N2Aboutof 0.71 cm3/g
including: - the mesopores0,51 cm3/g
the micropores105 mm3/g

Thus, from the comparison of the above examples 1 and 3 shows that replacing the substrate with a higher specific surface area at lower (50 m2/g 20 m2/g) did not significantly affect the parameters of the porous structure of the obtained carbon material, but can significantly reduce the cost of the product due to the use of cheaper substrates (the price of carbon black used in example 1 and a half times higher rates of carbon black in example 3).

From the analysis of example 2 it is proposed to the text of the application method, including the use of the furnace granulated carbon black with a specific surface area of 10 to 30 m2/g and the amount of adsorption of dibutyl phthalate 95-115 ml/100 g, pre-compaction to the bulk density of 0.6 g/cm3the sieving of the material obtained with the separation fraction with a particle size of 1.6-3.5 mm, further his seal to the bulk density of 1.0 g/cm3and activation of the resulting product, allows to increase the yield of the target product almost doubled to 125 kg, compared to 87 kg of example 1. This leads to increased productivity and efficiency.

The obtained carbon media and prepared on the basis of a palladium catalyst had the same properties activity as the prototype. This catalyst was used in Hydrotreating processes of terephthalic acid in the production of polyester materials, but also in the process of disproportionation of gum rosin and decarbonylation furfural.

The method of obtaining carbon carrier for catalysts comprising heating a moving layer of granulated carbon black is used as the substrate, the flow in the layer of soot gaseous or vaporous hydrocarbons, their thermal decomposition on the surface of soot particles with the formation of a layer of pyrocarbon and activation hardened by pyrocarbon material at a temperature of 800-900°With the latter is the fact that the unloading of the finished product, characterized in that the substrate for sealing the pyrocarbon use oven granulated carbon black with a specific surface area of 10 to 30 m2/g and the amount of adsorption of dibutyl phthalate 95-115 ml/100 g, while the seal soot pyrocarbon lead in two stages: the first stage granular soot compacted to achieve a bulk density of 0.5-0.7 g/cm3, and then produce a cooling mass of the material and sieving emitting fraction of granules with a size of 1.6-3.5 mm, and then in the second stage, this fraction is subjected to re-pyrolytic compaction to achieve a bulk density of granules 0.9-1.1 g/cm3with the subsequent activation of the obtained product until the value of the total pore volume of 0.2-1.7 cm3/year



 

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