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.
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.
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 density||550 g/cm3|
|the specific surface||460 m2/g|
|the total pore volume||to 0.72 cm3/g|
|including: - the mesopores||0,55 cm3/g|
|the micropores||85 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 density||552 g/cm3|
|the specific surface||425 m2/g|
|the total pore volume in N2About||of 0.71 cm3/g|
|including: - the mesopores||0,51 cm3/g|
|the micropores||105 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
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to methods of preparing catalysts based on sulfurized styrene/divinylbenzene copolymer and thermoplastic polymer material, which are used in processes for preparing alkyl tert-alkyl ethers, hydration of olefins, dehydration of alcohols, preparation of esters, and the like. Invention provides molded ionite catalyst consisted of sulfurized styrene/divinylbenzene copolymer in the form of mixture of powdered copolymers with macroporous and gel structure and, as thermoplastic material, propylene polymers and propylene/ethylene copolymers. Preparation of catalyst is accomplished by extrusion at temperature of heating extruder cylinder 140-200°C and temperature of forming head equal to temperature of the last heated zone of heating cylinder.
EFFECT: increased catalytic activity.
10 cl, 3 tbl, 15 ex
FIELD: alternative fuel production and catalysts.
SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.
EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.
6 cl, 2 tbl, 16 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.
EFFECT: increased yield of lower olefins.
3 cl, 2 tbl, 18 ex
FIELD: supported catalysts.
SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.
EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.
5 cl, 9 ex
FIELD: petroleum processing catalysts.
SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.
EFFECT: increased catalytic activity.
2 cl, 1 tbl, 3 ex
FIELD: hydrocarbon conversion catalysts.
SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.
EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.
4 cl, 1 tbl, 8 ex
FIELD: composite materials.
SUBSTANCE: invention relates to catalyst carriers and methods for preparation thereof. Novel porous composite material particles are proposed comprising alumina component and swelled clay component finely dispersed in alumina component in amount effective to raise hydrothermal stability, pore volume, and/or pore mode in the mesopore region in composite material particles as compared to swelled clay-free material. Also proposed are composite material particles and agglomerate particles obtained therefrom as well as a method for hydroprocessing of petroleum feedstock using agglomerates as hydroprocessing catalyst carrier.
EFFECT: increased hydrothermal stability and pore volume.
44 cl, 24 dwg, 19 tbl, 28 ex
FIELD: inorganic compounds technologies.
SUBSTANCE: invention provides porous composite particles containing alumina component and residue of at least one additional crystal growth inhibitor component dispersed within alumina component, wherein indicated composite particles have (A) specific surface area at least 80 m2/g; (B) average nitrogen-filled pore diameter 60 to 1000 Å; (C) total nitrogen-filled pore volume 0.2 to2.5 cm3/g and (D) average particle size 1 to 15 μm, and where, in indicated composite particles, (i) alumina component contains at least 70 wt % of crystalline boehmite with average crystallite size 20 to 200 Å, γ-alumina obtained from indicated crystalline boehmite, or mixture thereof; (ii) residue of additional is obtained from at least one ionic compound containing ammonium, alkali metal, alkali-earth metal cation, or mixtures thereof and wherein anion is selected from group comprising hydroxyl, silicate, phosphate, sulfate, or mixtures thereof and is present in composite particles in amounts between 0.5 and 10 % of the summary weight of alumina and additional components. Invention also provides a method to obtain composite particles, agglomerated particles prepared therefrom, and a method for hydroprocessing of petroleum feed using above-mentioned agglomerates.
EFFECT: avoided unnecessary calcination before addition of metals to increase average pore size and use of organic solvents for azeotropic removal of water.
36 cl, 2 tbl, 22 ex
FIELD: catalyst manufacture technology.
SUBSTANCE: invention relates to catalyst carriers used in various heterogeneous catalyst applications and as accumulator cells, galvanic and fuel cells, In particular, utilization of geyserite as catalyst carrier is described.
EFFECT: increased temperature and chemical stability of carrier.
FIELD: gas treatment catalysts.
SUBSTANCE: invention, in particular, relates to internal combustion engine exhaust gas neutralizers. Method of invention comprises rolling refractory metallic tape into block by way of overlapping its smooth and corrugated sides to form channels, performing ultrasound-assisted chemical cleaning of thus rolled tape in alkali solution followed by joining alternate layers of metallic tape with each other by diffusion welding in vacuo within a range of 5·10-5-1·10-5 mm Hg using stepwise heating to 1250 ± 10°С and isothermal exposure to this temperature for 12-17 min to form monolithic structure consisting of triangular and trapezoidal channel at density up to 600 channels per 1 inch2. Invention further describes carrier for catalytic exhaust gas neutralizers representing monolithic metallic structure in the form of cylindrical block or block with oval cross-section, which block consists of parallel channels, 200-600 per 1 inch2, density of channels varying along the cross-section of carrier: from center and extending to 0.55 0,7 diameter if cylindrical block or large axis of oval cross-section, density of channels is 400-600 per 1 inch2 and farther it decreases to 200 or 400 channel/inch2, respectively.
EFFECT: simplified manufacture technology and increased strength of monolithic cellular structure.
4 cl, 4 dwg, 1 tbl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.
EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.
1 dwg, 1 tbl, 12 ex