A method of obtaining a carrier for catalyst for synthesis of hydrocarbons and method for producing catalyst for synthesis of hydrocarbons

 

(57) Abstract:

The inventive carrier for catalyst for synthesis of hydrocarbons produced by the joint grinding finely ground silica and water-soluble zirconium compounds in the presence of water at a content of 28 to 47 wt. % solids. During grinding the pH of the mixture is 8.7 to 9.5, which is supported by adding an organic base. The addition of organic acids to reduce pH to 8.3. The resulting mixture ekstragiruyut by adding surface-active agent. Dried and calcined. Silicon dioxide is used in the form of silica gel or precipitated silica or pyrogenic silica, preferably with an average particle diameter of 50 μm. Before using silicon dioxide is washed with a solution of ammonium carbonate. As the water-soluble zirconium compounds used carbonate ammunition. The amount of zirconium is 8 to 15 wt. percent of silicon dioxide. For the preparation of the catalyst the resulting carrier is impregnated with an active component. Dried and calcined. 2 S. p. , 10 C. p. F.-ly, 2 tab.

The invention relates to processes for obtaining media used in Praiano catalyst carrier or catalyst, mainly in the field of Fischer-Tropsch catalysts.

The preparation of hydrocarbons from gaseous mixtures comprising hydrogen and carbon monoxide, when the contact of these compounds with a specific catalyst at elevated temperatures and pressures are well known in the literature as the Fischer-Tropsch synthesis.

Catalysts are often used for this purpose include one or more metals from group VIII of the Periodic Table mainly from the group of iron, on a supporting carrier, optionally in combination with one or more metal oxides and/or other metals as promoters of catalysts. The metal oxide promoters catalysts typically are selected from groups IIa, IIIb, IVb and/or Yb. The periodic Table, as well as of the lanthanides and/or actinides. The metal promoter is typically selected from groups VIIb and/or VIII of the Periodic table.

Very suitable Fischer-Tropsch catalysts, mainly catalysts containing cobalt and Zirconia on silica media described in the literature.

Fischer-Tropsch catalysts, as shown above, are usually obtained by combining the carrier and one or more compounds of the metal, i.e., deposition of metals, or separately or together, on the media of Rania in the presence of water followed by extrusion of the mixture formed. All technologies for the solvent is usually removed by volatilization of the products obtained, followed by drying and calcination of the dried products. Then, the calcined product activate the recovery of the hydrogen containing gas.

It has been observed that when using silica as a carrier to obtain a Fischer-Tropsch catalysts based on cobalt, in some cases formed hydrosilicate cobalt. These hydrosilicate cobalt does not show significant catalytic activity, while the recovery of these hydrosilicates in the catalytically active metal is cobalt laborious and requires strict conditions. Therefore, it is suggested to apply to the media first another metal oxide, mainly zirconium on the basis of its positive effect on the activity, stability and selectivity of the Fischer-Tropsch catalysts based on cobalt, followed by the application of cobalt. Because this requires treatment in several stages, was made an intensive study to provide a simple process for the production of porous media catalyst, preferably silica, at least partially covered with one or more other oxides of metalization. Mainly researches were focused on the development of extrudable media, for example, silica carriers, based on issues arising from the use of more or less spherical particles, for example, silica spheres, issues such as high pressure drops, inhomogeneous distribution (diameter, diameter of pores) and problems of heat transfer. Next, the ratio of the surface area and volume, more appropriate in the case of extrudates, mainly three or polylobate particles than in the case of spheres.

A known method of producing extrudates of silica, in which a silica is mixed with water and a compound of an alkali metal, followed by melting and extrusion of the mixture and then drying the extrudate. However, the use of compounds of alkali metal often causes the need to wash the extrudates of silica in a solution of ammonium nitrate and nitric acid to remove alkali metal ions, because the presence of alkali metal ions often impairs the catalytic functionality of the extrudates. Another known process of extrusion of silica leads to products having only low compressive strength.

Now found that eeny extrusion of silica together with the dissolved compound of a metal from group IVb, without the use of compounds of alkali metal. Finely divided silica and a water-soluble compound IVb group, mainly alkaline, water-soluble compound of zirconium together crushing in the presence of water followed by extrusion of the mixture and arbitrarily drying and/or calcination of the extrudates. The extrudates based on silica/metal oxide of group IVb, thus obtained, show good compressive strength and very good for Fischer-Tropsch catalysts having a high activity, high selectivity and good stability.

Therefore, the invention relates to a process for production of extrudates that are suitable for use in the manufacture of catalysts and carriers of catalysts, including the melting of the mixture of finely divided silica, water-soluble compounds of the group IVb and water, the mixture has a solid content of 20-50% by weight, and the extrusion of the mixture.

Finely divided silica, which is used in the process of the invention normally comprises silica particles having an average diameter of less than 100 μm, preferably between 15 and 80 microns, more preferably between 35 and 65 microns.

Silica, which may be Ipoteka. The word amorphous, when used in combination with silica, determines the absence of a crystal structure as defined by the diffraction of X-rays. Some short-range order can be determined by the diffraction of electrons, but this order is not determined by the diffraction of X-rays. The degree of porosity can be determined, for example, pore volume and/or surface area.

The silica used in the process of the invention is silicagel, more or less coherent, rigid, continuous three-dimensional grid of particles of colloidal silica. The amount of silicon dioxide is usually between 96 and 96.5% by weight. The size of the aggregated particles is usually between 3 and 25 μm, while the size of individual particles is typically between 1 and 100 nm. The surface area may vary between 150 and 900 m2/g, and is often between 200 and 700 m2/, Mainly suitable silica gel is silica gel, dried by spraying. It is preferable not to use annealed silica gel, silica gel, which is heated to a temperature of about 500aboutC and above.

The preferred type of silica used in the processes of this invention, apasmara, not be related in a massive grid of the gel during the preparation processes. The amount of silicon dioxide is typically between 80 and 99.5% by weight. The size of the aggregated particles is usually between 3 and 65 μm, while the size of individual particles is usually between 3-30 nm. The surface area can vary between 0 and 900 m2/g, and is often between 45 and 700 m2/,

Precipitated silica can be prepared from a solution of a silicate, preferably sodium silicate or potassium, using a relatively low concentration of silicate compared with the preparation of the silica gel, the addition of acid, preferably sulfuric acid or hydrochloric acid. Precipitation is separated from the mother liquor by filtration. Mainly, preferably in the processes of the invention use a pressed filter cake obtained after filtration of the reaction product, as described above, more preferably washed and/or dried by spraying pressed filter sediment. Flushing can be performed with water, but preferably with an electrolyte solution having a pH lower than 6. Can be used an organic acid, for example, fluorohydrogen or nitric acid,="ptx2">

Another preferred silica, which is used in the processes of the invention is pyrogenic or silica in the form of fly ash. This type of silica is usually produced of high-temperature processes, such as evaporation of silica, usually sand, when 2000aboutWith cooling, the formation of anhydrous particles of amorphous silica. Another process is the oxidation of vapors of silicon tetrachloride with oxygen or hydrogen and/or methane and hydrolysis in the flame vapor esters of silicon. Fumed silica tends to have less density than other types of silica. The amount of silicon dioxide is usually more than 99,5% by weight. The size of the aggregated particles is typically between 1 and 10 μm, often between 2 and 5 μm, while the size of individual particles is typically between 1 and 100 nm. The surface area may vary between 10 and 500 m2/g and is often between 15 and 400 m2/,

When the silica, such as silica gel, is gradually heated to a high temperature, it loses water. The water content in the samples of silica is often determined by mass loss on ignition. The silica sample is weighed and placed in a furnace where it is heated PR is the rest of the sample. The difference in mass is the mass loss during annealing or the amount of water present in the sample. Also, the procedure can be used to determine weight loss during calcination other samples.

Purity silica, which is used in the processes of the present invention, preferably more than 97% by weight relative to the samples free of water, preferably more than 98% , more preferably less than 99% . It is preferable to use silica, which contains sodium in an amount of less than 10000 wt. hours per million, more preferably less than 6000 Mas. hours per million, more preferably less than 2000 wt. hours in a million. The amount of sulfate is less than 7500 Mac. hours per million, preferably less than 4500 wt. hours per million, more preferably less than 1500 wt. hours in a million.

The silica that is used in the processes of the invention may be activated prior to use to improve frequency. You can use water or electrolyte solution. Wash solution had a pH of preferably less than 6. Priemlemye wash solutions are aqueous solutions of organic acids such as aliphatic acid having 1 to 12 operatsialarini atoms. Can be used very suitable aliphatic acids such as Muravyova acid, acetic acid, propionic acid and butyric acid. Mainly, preferably acetic acid. Very suitable dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid and phthalic acid. The above-mentioned acids may have substituents in the form of alkoxy groups, especially those with less than five carbon atoms, hydroxyl groups and piano groups. In addition to drilling fluids containing organic acids, you can also use washing solutions containing inorganic acids as hydrogen fluoride, chlorine, hydrogen, bromo, hydrogen, nitric acid, nitrous acid and perchloric acid. Further, it is possible to use salts of the aforementioned acids, for example, ammonium salts, or mixtures of the aforementioned acids and one or more salts.

Suitable pore volume source for processing silica particles is between 0.6 and 1.5 ml/g, preferably between 1.15 and 1.35 ml/g Suitable surface area is between 100 and 500 m2/g, preferably between 200 and 400 m2/, Suitable pore diameters are between 8 and 50 nm, predniso of the invention, preferably between 30 and 45% by weight, more preferably about 40% . The amount of water should be at least that would get a mixture that has the proper consistency for extrusion. Suitable volume of the aqueous impregnating solution corresponds to the pore volume of the silica, which is impregnated, plus ten percent.

Water-soluble compound of the group IVb, which is used in the process may be any water-soluble compound of the group IVb or mixtures thereof, and preferably be a water-soluble compound of zirconium. Preferably the connection is used from the IVb group, which gives an alkaline solution when dissolved in water. Suitable compounds of group IVb may be salts derived from organic acids, mainly acetic acid and propionic acid, but you can also use the connection type derivatives of acetylacetone. Other connections will be halide IVb group, hydroxy halide IVb group and the derivatives of cyclopentadienyl, i.e. zirconocene. The preferred compound is ammonium zirconium carbonate, ether as such or as a stable solution, for example, a solution, stabilized organic acid, such as vinokurenie in water give basic solutions can be used in the processes of this invention. The amount used of the metal of the IVb group will generally be between 3 and 100% by weight, based on the amount of the water-free silica. Preferably, the amount of metal of the IVb group will be between 5 and 60% , more preferably between 10 and 40% .

After mixing the components, the mixture is homogenized for a period of time, usually between 10 and 120 minutes, preferably between 15 and 90 minutes the Mixture components is conducted by mixing silica and compounds of group IVb, followed by the addition of water. In a preferred example, the compound of group IVb first dissolved in water, after which the solution was added to the silica. The latter procedure leads to the production of extruded articles having a very homogeneous distribution of connections from the IVb group on the silica. During the process of grinding, the mixture gets a certain amount of energy. The amount of energy is between 0.05 and 50 W-h/min/kg, preferably between 0.5 and 10 W/h/min/kg, a grinding Process is performed at a temperature of between 15 and 50aboutWith, although you can use lower or higher temperatures. Due to supply energy to the temperature at the end of grinding will be higher than at the beginning. In Tradate, i.e., the extrudates having high compressive strength, mainly after drying and/or calcination preferably you can add a certain amount of basic compound to the mixture. Mainly, it is preferable to add the ammonia, the ammonia liberating compound or an organic amine, or ammonium compounds to the mixture, because these compounds is not allocated after the annealing. The preferred compound of the organic amine is ethanol amine.

The basic compound is preferably added to the mixture after adding water, because otherwise a large number of primary connection could get into the pores of the silica, which is associated with a small or completely lack the strength of the extrudates. Therefore, the process performed is shown by, requires less primary connection, which makes the process cheaper, because less of the primary connection must be removed prior to or during calcination. In the case of connection of the base metal of the IVb group number primary connection may be reduced or may be eliminated, which is attractive from a technical point of view (less pollution, better product), as well as from an economic point of view.

Quantity is to be measured combined Steklyannyy electrode, taking equal aliquots of the mixture and water, and intensively stirring for one minute, to obtain a homogeneous suspension. It is preferable to obtain a mixture having a pH between 8.5 and 11.5, preferably between 9.0 and 11.0 in.

After grinding the mixture can be extruded in any conventional extruder. Machine screw type may be used for the extrusion of the mixture through a plate holder with a hole of desired shape and size. Strip, obtained by extrusion, randomly after cutting to the desired length, usually dried and arbitrary temper. Can be the preferred cylindrical extrudates, but you can also get other forms, such as forms, mentioned in U.S. patent No. 4 028 227. It is preferable to obtain the three-bladed extrudates. Very suitable hollow cylinders, such as cylinders with a Central empty space, which has a radius of between 0.1 and 0.4 radii of the cylindrical extrudate, and external (or twisted) trilobate can be used. Suitable (nominal) diameter can vary between 0.5 and 5 μm, preferably between 1 and 3 mm

It turned out that the extrusion of mixtures having a high pH, it will be more difficult than in mixtures having a pH in the range of what t acidic compounds. It is preferable to use an organic acid, since these acids do not leave traces after drying and calcination. For example, a suitable organic acid will be alsinoideae acid having 1 to 12 carbon atoms, preferably 1 to 6 uglerodnych atoms, and dicarboxylic acids, preferably containing 1 to 6 carbon atoms. You can use a very suitable alsinoideae acid, such as Muravyova acid, acetic acid, propionic acid and butyric acid. Mainly preferred acetic acid. Very suitable dicarboxylic acids are oxaluria acid, malonic acid, succinic acid, glutaric acid and phthalic acid. These acids may have substituents type of alkoxy groups, especially those with less than five carbon atoms, hydroxyl groups and cyano groups. In addition to organic acids, can also be used inorganic acids such as fluorohydrogen, florodora, Pomodoro, nitric acid, nitrous acid, Perlina acid.

To improve thermal properties of the mixture in the extruder, to the mixture you can add a surface-active agent or a polyelectrolyte. Adding surface-active AG is erudirovannogo product. Might be further improved formation of macropores in the calcined catalytic material, which can increase the catalytic properties of these products. As surface-active agents may be cationic surface-active agents such as fatty amines, Quaternary ammonium compounds, aliphatic monocarboxylic acid, an ethoxylated alkylamines followed, polyvinylpyridine, connection sulfoxide, sulfone, phosphonium and jodie, anionic surface-active agents, such as alkylated aromatic compounds, acyclic monocarboxylic acids, fatty acids, from sulphonated aromatic cyclothymia, sportswhat, esters of scheduleview, sulfated fats and oils, and salts of phosphoric acid and non-ionic surface-active agents such as polyoxyethylene ALKYLPHENOLS, polyoxyethylene alcohols, polyoxyethylene the bonds alkylamines, polyoxyethylene alkylamide, the polyalcohol and acetylene glycols. The amount of the improver of fusibility will be between 2 and 8% (weight/weight), preferably between 3 and 5% (weight/weight). The preferred breed of fusibility is solid under the trademark NaloO.

It is possible to extrusion admixture smexy titanium, zirconium or aluminum. Other impurities, which can be used are, for example, the oxides of gallium, indium, thorium, uranium, magnesium and zinc. The amount of each of the added compounds, such as shown above, will be up to 20% by weight, calculated on the amount of silica carrier, preferably up to 10% , more preferably up to 5% . The largest total number does not exceed 50% by weight, calculated on the quantity of silica carrier, preferably does not exceed 30% , more preferably does not exceed 15% .

This invention also relates to the extrudates obtained in accordance with the processes described earlier.

This invention also relates to processes for having the form of pastes suitable for the preparation of extrudates, in accordance with the processes described previously, as well as by having the form of pastes.

This invention still further relates to processes for the production of extrudates calcined silica, comprising the calcination of the extrudates of silica obtained in accordance with processes of the present invention, as described herein previously, at a temperature between 400 and 1000aboutWith, preferably between 600 and 900aboutWith, and to extradataitem equipment. As progulivayusheysa gas you can use hot air or exhaust gas obtained, for example, the combustion of liquid or gaseous hydrocarbons, but it is also possible to use other gases such as nitrogen, argon and carbon dioxide.

Extrudates of silica mainly after drying and calcination can be used to produce catalysts, mainly catalysts that can be used in processes for the conversion of hydrocarbons, such hydrobromide, hydrocracking and hydrodemetallization heavy hydrocarbon oils, reactions for the synthesis of hydrocarbons, epoxidation olefinic unsaturated compounds with organic peroxides during the hydration of olefinic unsaturated compounds with the corresponding alkanes, with the hydration of aromatic compounds, amides, NITRILES, cyanides, etc., when the dehydration of alcohols when cleaning the exhaust gases.

The extrudates for use in hydrodemetallization get the most suitable by calcination of zirconium bearing silica extrudate, to which is added molybdenum after calcination.

Extrudates of silica is preferably used in the campaign. Very suitable Fischer-Tropsch catalysts, as well as very appropriate processes in which the catalysts can be applied, are described in the European patent N 127220.

The catalysts used for the synthesis of hydrocarbons can be obtained by introducing a suitable catalytically active metal on the extrudate. Therefore, the invention also relates to the production of catalysts or their precursors that are suitable for obtaining hydrocarbons, including the introduction of a suitable catalytically active metal, preferably cobalt, silica extrudate as opisyvalos earlier. The metal can be harmful to the dried and/or calcined extrudates one or more known methods, for example, mixing, impregnation, deposition, etc. is Preferable to use impregnation. The impregnation can be carried out by contact of the appropriate connection of methanol in the presence of a fluid, usually in the form of a solution of the appropriate connection of the metal. As metal compounds can be used organic compounds. The liquid used can be organic and inorganic. Can also be used mixtures of liquids. Preferred compounds of cobalt are neola is. what about all the procedures for obtaining liquid, which is used to introduce the metal is removed from the composition, and then dried composition is usually made red-hot and arbitrarily reduced. Cobalt is preferably used as the catalytically active metal. Other suitable metals that can be used are, for example, Nickel, iron, and ruthenium. Can also be used in mixture. The amount of catalytically active metal, which is deposited on the carrier, suitable is between 3 and 100 million masses. hours at 100 million by weight. hours of silica in the carrier, preferably between 10 and 80 million by weight. am still more preferably between 20 and 60 million Mac. PM If you want to extrudates you can also enter one or more metal oxide or promoters, or before the introduction of the catalytically active metal, or after the introduction of the catalytically active metal. The promoters also you can enter up to, and after, the introduction of a catalytically active metal. Suitable metal oxide promoters can be selected from groups IIa, IIIb, IVb and Vb of the Periodic table, as well as actinides and lanthanides. Can also be used chromium. Can be used magnesium, Kalemie metal promoters can be selected from the group VIIb or VIII of the Periodic table. Can be used rhenium and noble metals from group VIII is mainly ruthenium, platinum and palladium. The amount of the promoter is between 0.1 and 150 million by weight. hours at 100 million by weight. hours of silica in the carrier.

The invention relates to processes for obtaining hydrocarbons by contact of the mixture of carbon monoxide and hydrogen with a catalyst suitable for the production of hydrocarbons from synthesis gas, and the catalyst obtained in accordance with the processes described above. Prior to contact of the catalyst with a hydrogen/carbon monoxide mixture catalysts are typically activated by reduction with hydrogen or hydrogen-rich recycle gas. Recovery is very fitting can be performed at a temperature between 200 and 350aboutC and a pressure of between 2 and 20 bar. Temperature, total pressure and partial pressure of hydrogen in the mixture can vary, thus, to obtain optimum catalytic functionality.

Conversion of a mixture of hydrogen and carbon monoxide can be performed at a temperature between 125 and 350aboutWith, preferably between 175 and 250aboutC and a pressure of between 5 and 100 bar, preferably between 12 and 50 bar.

The material containing hydrogen and mono is accordance with this invention, has the H2/CO molar ratio higher than 1.5, preferably between about 1.75 and 2.25. If the incoming material is of N2/CO molar ratio lower than 1.5, it is necessary to increase the ratio to values between 1.5 and 2.5, preferably between about 1.75 and 2.25. It has been observed that, when conversione hydrogen and carbon monoxide is recycled over the catalyst, it is possible to select conditions such that the catalyst is contacted with a synthesis gas having a significantly lower H2/Co ratio than that of the incoming gas to synthesis. From here it is possible to improve the selectivity to longer chain hydrocarbons.

The catalysts obtained in accordance with the described processes, when used for the conversion of hydrogen/carbon monoxide mixtures, give mainly paraffin product, whose high-boiling part can be transferred with high yield in average distillate when using catalytic hydrobromide. Incoming material for hydrobromide is at least part of the product whose initial boiling point lies above the final boiling point of the heaviest part of the medium distillates required as a final product, but the product can also be used as the settlement of the obtained medium distillates (reduction of unsaturated compounds and oxygenates, hydroisomerization). Catalytic hydrobromide is executed when the contact fraction, which is subjected to treatment at elevated temperature and pressure and in the presence of hydrogen with a catalyst containing one or more metals with hydrogenation activity, supported on the carrier. Examples of suitable catalysts are the catalysts containing Nickel and/or cobalt, and optionally molybdenum and/or tungsten, supported on a carrier such as aluminum or kremnezemami. In the catalytic hydrobromide it is preferable to use a catalyst containing one or more noble metals from group VIII of the Periodic table supported on a carrier. The amount of noble metal present in the catalyst may vary within wide limits, but is often between 0.05 and 5 wt. % . Noble metals of group VIII, which may be present are platinum, palladium, ruthenium, iridium, osmium, or mixtures thereof, platinum is preferred. The amount of metal of group VIII in the catalyst is preferably 0.1 to 2 wt. % and in particular 0.1 to 1 wt. % examples of suitable carriers are silica, aluminum, magnesium, Zirconia, zeolites and mixtures thereof, preferably round 175 to 400aboutC, the partial pressure of hydrogen is 10 to 250 bar, a space velocity of 0.1 to 5 kg/l h and the ratio of hydrogen/oil of 100 to 5000 Nl/kg of the Catalytic hydrobromide preferably carried out under the following conditions: a temperature of 250 to 350 C, the partial pressure of hydrogen between 25 and 100 bar, a space velocity of 0.25 to 2 kg/l h and the ratio of hydrogen/oil 250 to 2000 Nl/kg

The invention also relates to hydrocarbon products obtained using the catalysts described previously, to the right of the obtained products, as well as to indirect products received.

P R I m e R 1. Got a mixture having the following composition: silica (silica gel average particle size of 18 microns, a pore volume of 1.3 cm3/g, a surface area of 325 m2/g), ammonium zirconium carbonate (14% by weight, calculated as ZrO2at SIO, SIS2and water, the mixture had a loss on ignition of 59% , the solids content of 41% . The mixture was rasmalai within 30 minutes spent extrusion through a flat mouthpiece, dried at 120aboutWith and probalily at 700aboutC. Received a cylindrical extrudant with acceptable compressive strength. The content of ZrO2, 10.4 wt. % (based on SiO2).

P R I m m e R 2. Repeating example 1, but after the size of the second acid, continued grinding for 10 minutes In this case, the extrusion was carried out more easily. Got the cylindrical extrudent having the same strength as in example 1.

P R I m e R 3. Repeated example 2, using 4% by weight of polyelectrolyte (NalcO) to improve the extrusion process. The polyelectrolyte was added after the second grinding operation. After adding the grinding continued for other 10 minutes Received a cylindrical extrudates having the same compressive strength as in example 2.

P R I m e R 4. Repeated example 3. Instead of cylindrical extrudates produced three-lobed, with a nominal diameter of 1.4 mm was Received trilastin extrudates with good compressive strength (0.8 MPa).

P R I m e R 5. Mixture was prepared having the following composition: silica (silica gel, 800 g), monoethanolamine (40 g) and water (900 g). A mixture obtained by adding water to the silica, followed by the addition of mono-ethanol amine, after which the mixture was stirred for 45 minutes was added To the mixture solution of zirconium acetate (440 g, containing 22% by weight of zirconium, calculated as ZrO2), after which the mixture (loss on ignition of 60% containing solids 10% ) was extraditables using 3% parametr of 1.7 min), having an acceptable compressive strength (0.3 MPa). The content of ZrO2of 8.9 wt. % (based on SiO2.

P R I m e R 6. Repeating example 1, but using pyrogenic silica (Aerosil. 380, the surface area of 380 m2/g). After grinding the obtained mixture having a pH of 8.7, and a loss on ignition of 60% , which is very well extraditables. Got three extrudates (effective pore diameter of 1.4 mm), having a narrow distribution of pore sizes and good compressive strength.

P R I m e R 7. Repeating example 4, but using silica (precipitated silica, average particle size 50 μm, the surface area of 450 m2/g). Got three extrudates with good compressive strength.

P R I m e R 8. Repeating example 4, but using silica (precipitated silica, average particle size 50 μm, the surface area of 450 m2/g), which was washed several times with a solution of ammonium carbonate. Got reclamatii extrudate with good compressive strength.

P R I m e R 9. Mixture was prepared from 2105 g of silica powder (average particle size of 17 μm, a pore volume of 1.3 cm3/g), the surface area of 310 m2/g), 1620 g of ammonium zirconium carbonate 35 g of acetic acid. 26.4 elrin flat mouthpiece. After drying and calcination (800aboutC for 1 h) three extrudates (effective diameter of 1.4 mm) received a medium having the following properties; compressive strength of 1.0 MPa, the surface area of 262 m2/g, pore volume of 0.8 mm/g, a pore diameter of 12.7 nm. The zirconium content was 12% by weight, based on silica.

P R I m e R 10. Carriers of catalysts obtained in examples 1 to 9 was used to obtain a Fischer-Tropsch catalysts by impregnation their cobalt (25 parts by weight of cobalt per 100 million by weight. including silica). Impregnation was performed using a concentrated solution of cobalt nitrate. After impregnation of carriers impregnated particles were dried has probalily. After activating the hydrogen-activated catalyst particles in contact on a fixed main reactor gas and the synthesis (N2/CO ratio of 1.1, the input pressure of 29 bar). Got heavy resin. Temperature for 100 STY, changed for all samples between 214 and 234aboutC, C5- selectivity varied between 82 and 88% . For example, the carrier obtained in example 4 resulted in 100 STY temperature 214aboutC and C5the selectivity of 88% . For media obtained in example 7, these figures amounted to 226aboutWith and 87.5% ramesam, the average particle size of 50 microns, a surface area of 450 m2/g), ammonium zirconium carbonate (20% by weight, calculated as ZrO2at SIO, SIS2and water, the mixture had a loss on ignition of 73%, the solids content of 28% . The resulting mixture was razmelchite for 20 minutes To obtain a mixture having a loss on ignition of 72% , was added an aqueous solution of acetic acid (70% by weight). The mixture was then rasmalai within 10 minutes Added polyelectrolyte (NalCO) (4% by weight) and the resulting mixture was further rasmalai within 5 minutes the Mixture was extrudible using Delrin flat mouthpiece. Received three extrudates were dried (330 to 350aboutC) and probalily (800aboutC for one hour). The resulting catalyst had the following properties: compressive strength to 0.88 MPa, the surface area of 371 m2/g, pore volume of 1.07 ml/g, a pore diameter of 19,10 nm and the content of ZrO213,3% by mass.

P R I m e R s 12 - 15. The General procedure of example 11 was repeated further four times. Properties of the obtained extrudates are given in table. 1.

P R I m e R 16. The carrier of the catalyst obtained in example 15 was used to obtain a Fischer-Tropsch catalysts by impregnation with cobalt (21,8% by weight of cobalt). The impregnation was carried out using city catalyst was placed on a fixed basis, activated by reduction with hydrogen and contacted with the gas for the synthesis of (N2/CO ratio of 1.1, the input pressure of 36 bar). Received heavy oil at STY 95 g/l/h and a temperature of 214aboutWith with WITH5the selectivity to 89.5% .

P R I m e R s 17-20. Received four separate download extrudates using the General procedure of example 11 of the following components: Precipitated silica 2257 g (particle size 50 μm, the surface area of 450 m2/g) Ammonium zirconium carbonate 1161 g of Acetic acid (5% ) 116 g Polyelectrolyte (NalCO) (4% ) 93 g Water 3620 g

Extrudates from each load washed in an aqueous solution of ammonium acetate (1M) for 30 min and probalily within a further period of 1 h at 500aboutC. the obtained extrudates were impregnated with cobalt by immersion in an aqueous solution of cobalt nitrate (18% by weight) for 8 h at 80aboutAnd then probalily for 2 h at 500aboutC.

To test their functionality in the Detective-Tropsch catalysts, catalyst particles from download loaded on a fixed basis and made contact with the gas to synthesis (N2/The ratio of 1.10 inlet pressure 25 bar). The functionality of each of the catalyst resulted in the table. 2 on the basis of the temperature to the ptx2">

European patent N 127220, CL 01 J 23/86, published. 1984.

1. A method of obtaining a carrier for catalyst for synthesis of hydrocarbons, including impregnation of the silica-water-soluble compounds of zirconium in the presence of water followed by extrusion of the resulting mixture, drying and calcination, wherein the impregnation lead by co-grinding finely ground silica and water-soluble zirconium compounds in the presence of water at a content of 28 to 47 wt.%. solid substances.

2. The method according to p. 1, characterized in that the silicon dioxide has an average particle diameter of 50 μm.

3. The method according to PP. 1 and 2, characterized in that use silicon dioxide selected from the group consisting of silica gel, precipitated silica or pyrogenic silica.

4. The method according to PP. 1 to 3, characterized in that the silicon dioxide before use wash solution of ammonium carbonate.

5. The method according to PP. 1 to 4, characterized in that as the water-soluble zirconium compounds using ammonium carbonate zirconium.

6. The method according to PP. 1 to 5, characterized in that the amount of zirconium is 8 to 15% by weight of silicon dioxide.

7. the. to 7, characterized in that the pH of the mixture reached by adding an organic base.

9. The method according to PP. 1 to 8, characterized in that the pH value is reduced to 8.3 by adding organic acids.

10. The method according to PP. 1 to 9, characterized in that the mixture to be extraction process, add surface-active agent.

11. The method according to PP. 1 to 10, characterized in that the mixture contains solid substances 40 wt. % .

12. A method of producing a catalyst for synthesis of hydrocarbons, including impregnation of the silica-water-soluble compounds of zirconium in the presence of water, the subsequent extrusion of the resulting mixture, drying and calcination followed by impregnation, drying and calcination of the obtained carrier, characterized in that as the carrier using a carrier obtained by grinding finely ground silica and water-soluble zirconium compounds in the presence of water at a content of 28 to 47 wt. % solids.

 

Same patents:

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

FIELD: physical or chemical processes and apparatus.

SUBSTANCE: method comprises saturating the initial gas mixture that is comprises agents to be oxidized with vapors of hydrogen peroxide. The photocatalyst is made of pure titanium dioxide that contains one or several transition metals.

EFFECT: expanded functional capabilities and enhanced efficiency.

7 cl, 2 dwg, 1 tbl, 11 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.

EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.

13 cl, 1 tbl, 24 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.

EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.

17 cl, 3 tbl, 25 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides catalyst composed of heteropolyacid: phosphorotungstic acid and/or phosphoromolybdenic acid, at least one precious metal deposited on essentially inert inorganic amorphous or crystalline carrier selected from group including titanium dioxide, zirconium dioxide, aluminum oxide, and silicon carbide, which catalyst retains characteristic structure of heteropolyacid confirmed by oscillation frequencies of the order 985 and 1008 cm-1 recorded with the aid of laser combination scattering spectroscopy and which has specific surface area larger than 15 m2/g, from which surface area in pores 15 Å in diameter is excluded. Method of converting hydrocarbon feedstock containing C4-C24-paraffins in presence of above-defined catalyst is likewise described.

EFFECT: increased catalyst selectivity and enhanced hydrocarbon feedstock conversion.

5 cl, 7 tbl, 7 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.

EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: process is effected in reactor containing compacted bed of supported catalyst including group VIII metal, in particular cobalt, said metal being partially present in its metallic form. Supported catalyst has, on its outside surface, catalytically active metal. Compacted bed is characterized by having hollow volume more than 50 vol % and specific surface area more than 10 cm2/cm3, which is calculated as total outside surface of particles divided by bed volume.

EFFECT: improved economical efficiency of process.

8 cl, 3 tbl, 7 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: catalyst preparation methods.

SUBSTANCE: catalyst containing crystalline anatase phase in amount at least 30% and nickel in amount 0.5 to 2% has porous structure with mean pore diameter 2 to 16 nm and specific surface at least 70 m2/g. When used to catalyze photochemical reaction of isolation of hydrogen from water-alcohol mixtures, it provides quantum yield of reaction 0.09-0.13. Preparation of titanium dioxide-based mesoporous material comprises adding titanium tetraalkoxide precursor and organic-nature template to aqueous-organic solvent, ageing reaction mixture to complete formation of spatial structure therefrom through consecutive sol and gel formation stages, separating reaction product, and processing it to remove template. Invention is characterized by that water-alcohol derivative contains no more than 7% water and template consists of at least one ligand selected from group of macrocyclic compounds, in particular oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or complexes of indicated macrocyclic compounds with metal ions selected from group of alkali metals or alkali-earth metal metals, or f-metals consisting, in particular, of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, and cerium used in amounts from 0.001 to 0.2 mole per 1 mole precursor. Sol is formed by stirring reaction mixture at temperature not higher than 35°C. Once formation of spaced structure completed, mixture is held at the same temperature in open vessel to allow free access of water steam and, when template is removed from the mixture, mixture is first treated with nickel salt solution and then with alkali metal borohydride solution until metallic nickel is formed.

EFFECT: increased sorption and photocatalytic properties of catalyst and enabled reproducibility of its property complex.

7 cl, 68 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention proposes combination of protective layer against chlorine compounds and copper-containing catalyst bed. Protective layer is formed from molded members prepared from particles of led carbonate and/or basic led carbonate with weight-average particle size less than 10 μm. Catalytic reaction in presence of above-defined combination is also described.

EFFECT: prevented deactivation of copper-containing catalyst operated with process gas containing chlorine compounds.

11 cl, 3 tbl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides catalyst for production of methyl ethyl ketone via oxidation of n-butenes by oxygen and/or oxygen-containing gas, which catalyst is composed of aqueous solution of molybdeno-vanado-phosphoric heteropolyacid or mixture of the latter with its salt and 5·10-4 to 1·10-2 M palladium stabilized by phthalocyanine ligand at palladium-to-phthalocyanine molar ratio 0.5-2. Mo-V-phosphoric heteropolyacid is depicted by formula H19P3Mo18V7O84. concentration of vanadium being 0.4 to 2.2 g-atom/L. Oxidation of n-butenes is carried out continuously in two steps at temperature 15 to 90оС. Catalyst is regenerated in contact with oxygen or oxygen-containing gas at 140-190оС and oxygen pressure 1-10 gauge atm.

EFFECT: enhanced process efficiency due to increased stability of catalyst components.

7 cl, 1 dwg, 6 tbl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: catalyst is prepared by impregnating alumina with cobalt chloride solution followed by drying and activation, the latter being effected by treating catalyst first with hydrogen sulfide/hydrogen mixture at 380-420оС and then with hydrogen at 200-260оС. Invention also provides catalyst for production methylmercaptan through hydrogenolysis of dimethyl sulfide containing 8.0-15.0% cobalt sulfide applied onto alumina treated by above-indicated method. Process is carried out at dimethyl sulfide supply velocity 13.4 to 128.7 mole/h per 1 g catalyst.

EFFECT: increased methylmercaptan production productivity.

3 cl, 1 tbl, 15 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: 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: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

FIELD: petrochemical synthesis catalysts.

SUBSTANCE: invention discloses a method for preparation of palladium catalyst comprising impregnation of alumina carrier with palladium chloride solution in presence of aqueous hydrochloric acid, treatment with reducing agent (hydrogen), washing with water, and drying, said carrier being preliminarily decoked exhausted catalyst containing alumina and group I and/or II, and/or VI, and/or VIII metals and subjected to washing with aqueous hydrochloric or nitric acid and then with water. Exhausted ethylene oxide production catalyst or methylphenylcarbinol dehydration catalysts can also be suitably used.

EFFECT: increased selectivity and activity of catalyst.

2 cl, 2 tbl, 21 ex

Up!