Method of reforming by using high-density catalyst
FIELD: oil and gas industry.
SUBSTANCE: invention refers to the formed catalyst with specified high density and with specified low ratio of platinum group component to stannum, and deals with application method of catalyst for conversion of hydrocarbons. There described is conversion catalyst of hydrocarbons, which includes platinum group metal, stannum and substrate, and has average bulk density which is more than 0.6 g/cm3, and preferably more than 0.65 g/cm3, in which mass ratio of platinum group metal to stannum is less than 0.9, and preferably less than 0.85, where platinum is platinum group metal in amount of 0.01 to 2.0 wt %, on a per element basis, and where the above catalyst includes associated stannum in specific clusters from stannum and metals of platinum group in quantity of at least 33 wt %, and effective molar ratio of associated stannum to platinum in the above clusters is at least 0.65 as per Moessbauer spectroscopy analysis. There also described is conversion method of hydrocarbons, which involves contact of hydrocarbon material with the above catalyst at conversion conditions of hydrocarbons, converted hydrocarbon, where catalyst includes metal of platinum group, stannum and substrate, has average bulk density which is more 0.6 g/cm3, where mass ratio of metal of platinum group to stannum is less than 0.9.
EFFECT: technological advantages of conversion of hydrocarbon material.
10 cl, 3 ex, 6 tbl
The technical field to which the invention relates.
This invention relates to a molded catalyst with a given high density and with a specified low value component of platinum to tin and relates to a method of applying the catalyst for the conversion of hydrocarbons, for example, reforming raw material of a number of high-octane naphtha aromatic organic compounds.
The level of technology
Installation for the conversion of hydrocarbons, such as installation for the catalytic reforming of naphtha should give large amounts of hydrogen for clean fuels, high-octane product for gasoline and aromatics for petrochemical production. An improved catalyst with a higher density and a lower ratio of platinum-tin allows for reforming to increase productivity to increase production of hydrogen, C5+and/or aromatic products. Compared to catalysts with a low density new catalyst has a higher activity and gives a higher limit clutch (pinning margin). The clutch limit refers to the limit at which the movable layer of the catalyst will flow through technological reactor for the flow of hydrocarbons, which otherwise will cause the catalyst to suspend movement is giving and effectively adhere or stick to the walls of the reactor or the Central pipe. The lower limit of the clutch, usually associated with problems of flow of the moving catalyst, which is the uneven performance of the reactor. For plants for refining already increase the speed of feed of hydrocarbons through their preferences for reforming, catalyst loading higher density may be a simple, effective way to further increase the supply of hydrocarbons. Hydraulic throughput of hydrocarbons in many installations reformer can be increased almost by 20% or more to flow continuously recirculating hydrogen. The reduced formation of coke on the catalysts of higher density is especially important for refineries, where the formation of coke resulting in limited ability for continuous regeneration and where I want to increase the feed rate, but may not increase the speed of the recirculating gas.
Many catalysts containing platinum and tin for use in the reforming of naphtha, are disclosed in the prior art.
US 3,745,112 discloses a catalyst and a method of converting hydrocarbons based on uniformly distributed composite platinum-tin. Specific example of the disclosed catalyst is a combination of a platinum group metal, tin oxide and halogen with lumouksen media where the tin oxide uniformly distributed throughout the alumina carrier with a relatively small particle size.
US 3,920,615 reveals the annealing treatment at least at 800°C, which was used to restore the surface area alumina catalyst to a value of between 10 and 150 m2/, the Catalyst contains a platinum group metal with a second metal, such as copper, and exhibits improved selectivity in the way dehydrogenation of long chain of monoolefins of paraffin as part of the production of alkyl-aryl-substituted sulfonates of.
Patent Canada No 1,020,958 discloses a catalyst comprising at least one element of the platinum group used in the reaction zone with the hydrocarbon and hydrogen in the presence of conditions that serve as the reason for the deposition of coke on the catalyst. The catalyst recovered in a wet oxidation, and the process is repeated as long as the surface area will not be a value between 20 and 90% of the initial value. Then the catalyst is treated for introducing at least one metal promoter, such as tin. The resulting catalyst shows improved stability in use, thus requiring less frequent repair or replacement.
US 6,514,904 discloses a catalyst and process for use rolled atora mainly for the conversion of hydrocarbons and particularly for reforming of naphtha.
US 6,600,082 and US 6,605,566 reveal the reforming and dehydrogenation catalysts prepared using impregnation of an organic compound of tin, in order to achieve interaction with platinum, which is determined on the basis of mössbauer spectroscopy.
Disclosure of inventions
Applicants have found that a catalyst with high density aluminum oxide and a reduced ratio of platinum to tin provides a significant technological advantage in the conversion of hydrocarbons such as naphtha. In particular, applicants have found that a catalyst with high density aluminum oxide provides a reduced coke formation, improved stability or greater activity than expected in the process of reforming.
A broad embodiment of the present invention is a catalyst for the conversion of hydrocarbons, consisting of a substrate with an average bulk density higher than 0.6 g/cm3on which the distributed component of the platinum group and tin, where the mass ratio of the component of platinum to tin is less than 0.9. Preferably the substrate is aluminum oxide with a powder x-ray such that the ratio of the intensities of the peaks at the respective values of two theta of Bragovskogo angle from 34,0 to 32.5 is at least 1.2, and the ratio of intensities Pico is when the respective values of two theta of Bragovskogo angle from 46,0 45,5 to is not more than 1.1. In addition, tin is preferably characterized using mössbauer spectroscopy to determine the amount of tin associated with the platinum group metal within the individual clusters of tin and platinum group metals.
Another embodiment is a method of applying the catalyst in the catalytic reforming process for converting hydrocarbons casalinuovo series, especially in the presence of less than 1 part per million When the catalyst comprises alkali or alkaline earth metal catalyst useful in the process of dehydrogenation.
The aim of the invention is to provide a catalyst of high density with low platinum group metals to tin, which is suitable for the conversion of hydrocarbons. Another goal is to create a catalyst suitable for reforming, which will increase the limit of adhesion, to reduce the formation of coke and takes excellent activity.
Additional goals, options, implementation and details of this invention can be obtained from the following detailed description of the invention.
The implementation of the invention
A broad embodiment of the present invention is a shaped catalyst, which is produced using the substrate particles having an average bulk density greater than 0.6 g/cm3. Prepact the tion, average bulk density is greater than 0.65 g/cm3. The substrate should be homogeneous in structure and possess heat resistance under the conditions used in the method of converting hydrocarbons. Suitable substrates include inorganic oxides, such as one or more oxides of aluminum, oxides of magnesium, zirconium dioxide, chromium oxide, titanium, boron oxide, thorium oxide, phosphate, zinc oxide and silicon oxide. Aluminum oxide is the preferred substrate.
Suitable materials of aluminum oxide is crystalline aluminum oxide, known as gamma alumina, ETA, theta alumina or gamma this give the best results. The preferred aluminum oxide has been described in US 3,852,190 and US 4,012,313 as a side product of the reaction of the Ziegler synthesis of higher alcohols, as described in US 2,892,858. To simplify this alumina in the future will be called "alumina Ziegler". Aluminum oxide Ziegler available from the firm Vista Chemical Company under the trademark Catapal" from Condea Chemie GmbH under the trade mark "Pural". This material is pseudoboehmite extremely high frequency, which, after annealing at high temperature, as has been shown, leads to a gamma alumina of high frequency.
The preferred form of the presented catalyst is a sphere. Sphere oxide is aluminum can be obtained by a well-known manner the oil drops, which includes: forming a suspension of aluminum oxide aluminum oxide Ziegler or Hydrosol of alumina by any of the methods used in this field and preferably by reaction of aluminum metal with hydrochloric acid; combining the obtained Hydrosol or suspension with the appropriate gelatinous agent and dropping the resulting mixture into an oil bath that is supported at elevated temperatures. Droplets of the mixture located in an oil bath up until they harden and take the form of gel spheres. Areas further removed from the oil bath and typically subjected to specific dispersion aging and drying in oil and ammoniacal solution to further improve their physical parameters. The resulting aged and gel particles are then washed and dried at a relatively low temperature from 150° to 205°C and subjected to process annealing at a temperature of from 450° to 700°C for 1 to 20 hours. This processing performs the conversion of the hydrogel of aluminum oxide to the corresponding crystalline gamma-alumina. US 2,620,314 provides additional details and put in the invention as a reference. The use of the term "essentially spherical" refers to the geometric properties of most areas, which is round, and includes minor from the lonene.
An alternative form of the presented catalyst is a cylindrical extrudate. "Essentially cylindrical catalyst defined geometric properties of most of the cylinders, which is all in one direction and linear in the other, except for small deviations, and can be obtained by any well known method of forming, for example by extrusion. A preferred form of the extrudate is produced by mixing alumina powder Ziegler with water and suitable patiserie agents such as nitric acid, acetic acid, aluminum nitrate and similar materials to form an extrudable mass of thick, having a weight loss on ignition (SPT) at 500°C from 45 to 65 wt.%. The obtained mass of thick extruded through having a particular shape and size of the die plate to form extrudate particles, which can be dried at a relatively low temperature from 150° to 205°C and subjected to process annealing at a temperature of from 450° to 700°C for 1 to 20 hours.
In addition, the spherical particles can also be formed from the extrudate by rolling on a rotating disk. The average particle diameter can vary from 1 mm to 10 mm, preferably, about 3 mm.
After forming the catalyst is subjected to at least one of use is the air traffic management. Preferably, this annealing is carried out at conditions selected to create a catalyst containing calcined alumina by x-ray and the desired surface area. This calcination is usually carried out at a temperature of from 700° to 900°C, humidity less than 4 wt.% steam for 15 minutes to 20 hours. More preferably, the calcination is carried out at a temperature of from 800° to 900°C, humidity less than 3 wt.% pair and time from 30 minutes to 6 hours. Usually apply an atmosphere of oxygen with a content of dry air. Dry air is considered the air without additional moisture and vapor removed from the air, which was dried, using chemical methods, such as molecular sieves or silica gel to the level of ambient humidity. In General, the exact period of time is the period that is required in order to achieve the desired physical properties of the calcined aluminum oxide, that is, the surface area and strength of the crushed pieces. The relative amount of surface area of approximately between 5 and 30%. Further, the strength of the crushed pieces can be recovered is not more than 95% of the initial value. Strength can increase as a result of the calcination, so there may be more than 100% of the initial value.
Therefore, if the aluminum oxide to which the processing by annealing has a surface area between 200 and 220 m 2/g, calcined alumina will have a surface area of between 140 and 210 m2/g (measured by BET method/N2, ASTM D3037 or equivalent). Preferably calcined alumina should have a surface area between 150 and 180 m2/, Note that temporary conditions, of course, will vary in proportion to the applied temperature annealing and oxygen content in the atmosphere. Note also that the aluminum oxide to this treatment, the annealing may have a range of surface area between 180 and 240 m2/g, with a preferred range from 200 to 220 m2/g, as shown above.
Excellent results are achieved when the catalyst has an x-ray showing the characteristic intensity peaks at certain positions of the Bragg angles. Especially preferred catalyst has x-ray powder such that the ratio of the intensities of the peaks with the relevant provisions of Brekhovskikh angle two theta 34,0:32,5 equal to at least 1.2 and the ratio of the intensities of the peaks at the respective values Brekhovskikh angle two theta 46,0:45,5 equals the greater of 1.1. The radiograph can be obtained by standard methods of x-ray diffraction on the powder, of which an example is described below. Typically, the radiation source I have is a high-intensity x-ray tube with a copper target, operating at 45 KB and 35 mA. Flat compressed powder samples are scanned in a continuous mode with a step size 0,030° and a dwell time of 9.0 seconds on the diffractometer controlled by a computer. X-ray diffraction bands from K radiation of copper can be recorded on the solid-state detector with Peltier cooling. Data respectively stored in digital format in the control computer. The height of the peaks and their positions are reading with computer graphics as a function of twice the angle theta (two-theta), where theta is the Bragg angle.
Part of the catalyst is a platinum group metal. This component includes platinum, palladium, ruthenium, rhodium, iridium, osmium, or mixtures of these, preferably with platinum. The platinum group metal may exist within the final catalytic composite as a compound such as the oxide, sulfide, halide, oxychlorine and so on, in chemical combination with one or more other ingredients of the composite, or as an elemental metal. Best results are obtained when substantially all of the platinum group metals are in the elemental state and evenly distributed inside the material of the carrier. The platinum group metal may be present in the final catalytic composite in any amount which is catalytically effective, end catalic the ical composite typically contains from 0.01 to 2 wt.% platinum group metal, designed for the item. Excellent results are obtained when the catalyst contains from 0.05 to 1 wt.% platinum.
The platinum group metal may be introduced into the support in any suitable manner such as coprecipitation, ion exchange or impregnation. The preferred method of preparation of the catalyst involves the use of soluble degradable component compounds of the platinum group metal to a relatively uniform impregnation of the material carrier. For example, a component may be added to the substrate by mixing the substrate with an aqueous solution chloroplatinate or chloropyridine, or chloropalladite acids. Other water-soluble compounds or complexes of platinum group metals, including chloroplatinic ammonium latinobarometro acid, trichloride platinum tetrachloride hydrate, platinum, dichlorocarbene dichloride, platinum, dinitrodiphenylamine, tetranitromethane (II) sodium, palladium chloride, palladium nitrate, palladium sulfate, hydrochloride diaminopimelate (II)chloride tetraamminepalladium (II)chloride examinate, carbonylchloride rhodium, hydrate trichloride rhodium, rhodium nitrate, hexachlororhodate (III) sodium, hexanitrate (III) sodium, tribromide iridium, iridium dichloride, iridium tetrachloride, hexanitroethane (III) sodium, chloropyridin potassium or sodium, rhodium oxalate, potassium and so on, can is to be used for impregnation solutions. The use of a compound of chloride of platinum, iridium, rhodium or palladium, such as platinochloride, iridochoroiditis or palaiokastritsa acid or a hydrate trichloride rhodium is preferred as it facilitates the introduction and the metal component of the platinum group, at least minor amounts of preferred halogen in one stage. Hydrochloric, or the like acid is also generally added to the impregnation liquor, in order to further facilitate the introduction of halogen and uniform distribution of the metallic components throughout the material media. In addition, usually preferred to impregnate the carrier material after calcination, in order to minimize the risk of leaching of precious metals of the platinum group.
Typically a platinum group metal dispersed in the catalyst evenly. Preferably, a uniform dispersion of a platinum group metal determine electron probe microanalysis, comparing local metal concentrations with the total metal content of the catalyst. Homogeneous distribution is a synonym for uniform distribution. In an alternative embodiment one or more platinum group metals can be presented as a component of the surface layer, as described in US 4,677,094 included ZV is camping as a reference. "Surface layer" is a layer of catalyst particles adjacent to the surface of the particles, and the concentration of the metal surface layer decreases when moving from the surface to the center of the catalyst particles.
The metal of group IVA (IUPAC 14) is another ingredient of the catalyst of the present invention. The metals of group IVA, germanium and tin are preferable, and tin is particularly preferred. The component can be present as elemental metal, as a chemical compound such as the oxide, sulfide, halide, oxychloride, etc. or as a physical or chemical combination with a porous material carrier and/or other components of the catalytic composite. Preferably a substantial portion of the metal of group IVA is in the final catalyst in an oxidation state greater than for the elementary metal. The metal of group IVA optimally used in quantities sufficient to obtain a final catalytic composite containing from 0.01 to 5 wt.% metal, calculated on an item, the best results were obtained at a content of 0.1 to 2 wt.% metal.
The metal of group IVA can be introduced into the catalyst in any suitable way, in order to achieve a homogeneous dispersion, such as coprecipitation with a porous material carrier, the ion exchange material carrier or impregnation material of the carrier at any stage of receipt. One way to incorporate metal of group IVA in the catalytic composite involves utilization of a soluble degradable compounds of a metal of groups IVA to impregnate and to distribute the metal around the porous material medium. The impregnation of a metal of group IVA is carried out before, simultaneously with or after addition of other components to the material of the carrier. Thus, the metal group IV can be added to the material of the carrier by mixing the material of the carrier with an aqueous solution of a suitable metal salt or a soluble compound, such as bromide, tin chloride, tin (II)chloride tin (IV)chloride pentahydrate of tin (IV); or an oxide, Germany tetraethoxide Germany, Germany chloride (IV); or lead nitrate, lead acetate, chlorate, lead and similar compounds. The use of chlorides of metals of groups IVA, such as chloride, tin (IV)chloride, germanium (IV) or chlorate of lead are particularly preferred, as it promotes the introduction of a metal, and at least minor amounts of preferred halogen for one stage. When combined with hydrochloric acid in the process described above peptization particularly preferred alumina is formed of a homogeneous dispersion of the metal of group IVA in accordance with this invention. In an alternative embodiment of an organic compound of a metal, such as chlorine is d trimacinolone and dichloride titilola, introduced into the catalyst during peptization binder - inorganic oxide, and most preferably during the peptization of the alumina with hydrochloric or nitric acid.
Optionally, the catalyst may also contain a variety of metals of group IVA or other components or mixtures thereof, which act by themselves or in interaction as modifiers of the catalyst to improve activity, selectivity or stability. Some other known catalyst modifiers include rhenium, gallium, cerium, lanthanum, europium, indium, phosphorus, Nickel, iron, tungsten, molybdenum, zinc and cadmium. Catalytically effective amounts of these components can be added to the material of the carrier in any suitable way during or after its receipt or catalytic composite before, during or after will be introduced by the other components. In General, good results were obtained when these components range from 0.01 to 5 wt.% composite, based on each individual element.
Another optional component of the catalyst, particularly suitable for the conversion of hydrocarbons, including dehydration, dehydrocyclization or hydrogenation, is an alkaline or alkaline earth metal. More precisely, this optional component selected from the group consisting of the compounds of alkali metals cesium, rubidium, potassium, sodium and lithium and compounds of alkaline earth metals calcium, strontium, barium and magnesium. In General, good results are obtained when this component is from 0.01 to 5 wt.% composite, calculated on an element. This optional alkali or alkaline earth metal may be introduced into the composite by any known method of impregnation with an aqueous solution of a suitable water-soluble, preferably biodegradable compounds.
As previously indicated, it is desirable to use at least one stage of annealing upon receipt of the catalyst. Optional stage of the invention is the stage of calcination at high temperature, which can also be called a stage of oxidation and which is preferably carried out before the introduction of any metal in the substrate, but can be done after the introduction of metals. When high-temperature annealing occurs before the introduction of any metals, good results are obtained when the oxidation step at a lower temperature, and an optional phase control halogen followed by the addition of any metal.
Conditions for the implementation stage of oxidation at lower temperatures chosen to convert mostly all metal components in the catalytic composite in their respective okisleniu the form. Oxidation step occurs at a temperature of from 370° to 600°C. Typically use an atmosphere of oxygen, including air. Usually stage oxidation is performed in a period of from 0.5 to 10 hours or more, the exact time is the time required to convert mostly all metal components in their corresponding oxidized form. This time, of course, will vary in proportion to the temperature and the oxygen content in the atmosphere.
In addition to the stage of oxidation in the preparation of the catalyst may also be used for phase control of the halogen. Stage regulation halogen can perform a dual function. Firstly, the phase regulation of the halogen may assist in achieving a homogeneous dispersion of the metal of group IVA (IUPAC 14) and any other metal components. In addition, the phase regulation of the halogen may serve to activate the halogen in the final catalytic composite to the desired level. Stage regulation of uses halogen halogen or halogen-containing compound in air or oxygen atmosphere. As the preferred halogen for introduction into the catalytic composite involves chlorine is the preferred halogen or halogenated compound used during the stage of regulation of the halogen is chlorine, HCl or a precursor of these the compounds. In the implementation stage regulation of the halogen with a catalytic composite are in contact with the halogen or halogen-containing compound in air or oxygen atmosphere at an elevated temperature from 370° to 600°C. the Water may be present in the process of contact to assist in the regulation. In particular, when the halogen component of the catalyst is a chloride, it is preferable to use a molar ratio of water to HCl from 5:1 to 100:1. The duration of the stage of halogenation is usually from 0.5 to 5 hours or more. Because of the similarity of conditions stage regulation of halogen may occur during the stage of oxidation. Alternatively, the phase regulation of the halogen may be performed before or after the stage of annealing as required to obtain the catalyst of the present invention. Regardless of the stage of regulation of halogen, halogen content of the final catalyst should be calculated on an item from 0.1 to 10 wt.% the final composite.
If necessary, upon receipt of the catalyst can also be applied to the recovery phase. The recovery phase is to restore the greater part of all metal components of the platinum group to the corresponding elemental metallic state and to ensure a relatively uniform the finely divided dispersion of the component inside the refractory inorganic oxide. Preferably the recovery phase is basically carried out in an anhydrous environment. Preferably regenerating gas is substantially pure, dry hydrogen (i.e. less than 20 parts per million of water). However, you can use other reducing gases such as CO, nitrogen, etc. Usually regenerating gas is in contact with the oxidized catalytic composite at conditions including a temperature recovery from 315° to 650°C for 0.5 to 10 hours or more, effective to restore mainly all metal components of the platinum group in the elemental metallic state. The recovery phase may be performed prior to the loading of the catalytic composite in the conversion zone of a hydrocarbon or may be performed in situ as part of the startup procedure of the process of conversion of the hydrocarbon and/or during the reforming of hydrocarbons. However, if you use the method in situ, should be taken proper precautions: pre-dried raw materials for the conversion of hydrocarbons mainly to the anhydrous state and use mainly anhydrous hydrogen-containing regenerating gas.
Optionally, the catalytic composite may be subjected to pre-acarnania. The optional component is sulfur may be introduced in the catalysis of the tor by any known method.
An important property of the catalyst is the volumetric mass ratio of platinum group component to the metal component of group IVA (IU 14). The preferred component of group IVA is tin, and thus the preferred mass ratio of platinum to tin is less than 0.9. Especially preferred is the volumetric mass ratio of less than 0,85.
By the way, you can investigate the local electronic structure of tin used in the invention (oxidation, environment, chemical bonding)is mössbauer spectroscopy. The isomer shift measures the energy position of the mössbauer absorption, as a function of the electron density of the nuclei of atoms 119 Sn in asorbtion apparatus in comparison with the source, directly characterizes the degree of oxidation of the tin. Quadrupolar splitting, which defines the environment for absorption, is a function of the distribution of nearby charges, and characterize the degree of coordination and accordingly the type of chemical bond in which tin is involved. Mössbauer spectroscopy also provides information regarding the degree of order of the corners of the lattice occupied by tin. Preferably, the catalyst of the present invention contains tin and uses mössbauer spectroscopy to measure amounts of the tin, associated within specific clusters of tin and platinum group metals, where the effective molar ratio of such associated tin is at least 0,65. Accordingly, the number of the associated tin is greater than 33 wt.% total tin, preferably more than 35 wt.%. When using the method further found that the catalysts of the invention at least 10% and preferably at least 15% tin are in restored condition. Under the restored condition implies Sn0.
The catalyst of the present invention is particularly useful as a catalyst for conversion of hydrocarbons. The hydrocarbon subjected to conversion in contact with the catalyst under conditions of hydrocarbon conversion, which include a temperature of from 40° to 550°C., a pressure from atmospheric to 200 atmospheres absolute and the clock speed of the fluid supply from 0.1 to 100 h-1. The catalyst is particularly suitable for catalytic reforming casalinuovo raw materials and can also be used to dehydrocyclization, isomerization of aliphatic and aromatic hydrocarbons, dehydrogenation, hydrocracking, disproportionation, dealkylation, alkylation, transaminirovania, oligomerization and other transformations of hydrocarbons. Now is sabreena provides greater stability and reduced coke formation relative to other known catalysts, when using the catalyst as catalyst for catalytic reforming feedstock casalinuovo series. Preferably raw casalinuovo series has a sulfur content less than 1 part per million. The presented invention also provides greater stability and reduced coke formation relative to other known catalysts for use in the dehydrogenation process, where the catalyst component contains alkali or alkaline earth metal.
The following examples will serve to illustrate some embodiments of the present invention. These examples should not, however, be construed as limiting the scope of the invention, which are formulated in the formula. Within the scope of the invention there are many other possible variants, known to specialists in this field.
Two spherically shaped catalyst a and b, which were obtained on an industrial scale by way of the oil drops, processed dry high-temperature annealing in air containing about 2.5 wt.% water at 860°C for 45 minutes. Then received by way of the oil drops of the substrate after the annealing introduced platinum from an aqueous solution of hexachloroplatinic acid and HCl. It is important that the tin was added to solo of aluminum oxide to obtain drops. The ZAT is obtained catalysts were oxidized in a stream of air time with a bulk velocity (GHSV) of 1000 h -1at 510°C for 8 hours, while injection of a solution of HCl and chlorine gas. The catalyst recovered in a mixture of 425 GHSV of nitrogen and 15 mol.% of hydrogen. Temperature recovery was 565°C and the recovery time is 2 hours. The properties of the catalysts are presented below:
|Sample||Average bulk density, g/cm3||Pt, wt.%||Sn, wt.%||Sn/Pt, mol/mol||Cl, wt.%|
Were obtained characteristics of each reformer catalyst. Each catalyst of 60 cm3was loaded into the reactor in three separate layers to represent the number of reactors of the reforming process. Conditions for testing were: pressure of 517 kPa (75 psig), hourly volumetric rate of fluid 1.7 LHSV h-1, the molar ratio of hydrogen/hydrocarbon of 2.0. For tests used raw liger is in with the bulk composition of the paraffin/naphthenic/aromatic compounds 58,7/30,6 /10,7% vol. and paragneisses from the initial boiling point of 68.3°C to a final boiling point of 160°C according to ASTM D-86. Raw naphtha contains 0.4 wt. parts per million sulfur. For each run was obtained road octane number (RON)equal to 105, and then the temperature was continuously increased to maintain a constant RON. Each run was the same time. After each experimental run, the catalyst was unloaded separately with each layer. A sample of each layer was checked for burning coke, and the results were averaged by mass to calculate the average amount of carbon. Description reformer to 7 barrels of raw materials on m3catalyst (BPCF) [or 39,3 m3raw/m3catalyst] and RON was:
|Sample||Temp, °C||Exit C5+wt.%||The average number of carbon on the catalyst, g/100 cm3|
The samples were analyzed mössbauer spectroscopy to determine the degree of Sn associated with metal Pt. The effective ratio of Sn/Pt shows Sn, which is associated with Pt, and it is different from the volumetric relations Sn/Pt, which includes all of the Sn and Pt in the sample. The effective molar ratio of Sn/Pt calculated by multiplying the volumetric molar relationship Sn/Pt on the part of the Sn associated with Pt, obtained from mössbauer analyses. The obtained mössbauer results and effective relationships Sn/Pt for catalysts a and b:
|Rolled - jam||The volume ratio of Sn/Pt mol/mol||Mössbauer % Sn associated c Pt||The effective ratio of Sn/Pt on the basis of mössbauer spectroscopy, mol/mol|
Two additional catalyst C and D, which contained 0,256 and the 0.375 wt.% Pt obtained by soaking industrial derived substrates (method oil drops) using hexachloroplatinic acid. The catalysts were oxychlorinated at high temperature in the air stream, which contains HCl, water and Cl2and then restored at high temperature is round in a stream of hydrogen for 2 hours, using the same conditions as in Example 1. Properties of catalysts:
|Sample||Average bulk density, g/cm3||Pt, wt.%||Sn, wt.%||Sn/Pt, mol/mol||C Cl, wt.%|
Characteristics of the reforming catalysts C and D were obtained in the same way as described in Example 1. Characteristics of the reformer 7 BPCF [or 39,3 m3raw/m2catalyst] and RON 105 were:
|Sample||Temp., °C||Exit C5+wt.%||The average number of carbon on the catalyst, g/100 cm3|
The samples were analyzed mössbauer spectroscopy to determine the degree of Sn associated with metal Pt. The obtained mössbauer results and effective relationships Sn/Pt for catalysts With and D:
|Catalyst||The volume ratio of Sn/Pt mol/mol||Mössbauer % Sn associated c Pt||The effective ratio of Sn/Pt on the basis of mössbauer spectroscopy, mol/mol|
Mössbauer results for catalysts a, b, C and D showed that the Association % Sn was not increased for Katalizator D with a high content of platinum and high density (Association 33% Sn), as expected based catalyst with a high content of platinum and low density (Association 47% Sn). From testing to determine characteristics of the reformer, the catalyst D showed significantly b is more high, the formation of carbon which is disadvantageous for industrial reformirovan installations. Such an increase in the formation of carbon reflects the low stability and causes a significant corresponding increase in capacity of the regenerator is required to burn a higher amount of carbon. High level of carbon may also be the cause of regeneration so that the refinery should decrease the conversion and/or the feed speed appropriately to minimize the formation of carbon. In addition, the catalyst showed the best activity in the achievement of RON at lower temperatures. Therefore, for catalysts with high density of this invention, it is important to have effective relationships platinum group metals to tin, which maintain acceptable characteristics of the reforming process and makes it possible to work with high catalyst density, allowing you to work with a moving bed of catalyst with a high limit of traction in the conversion of hydrocarbons.
Presents x-rays of the catalysts of the previous examples are obtained standard x-ray methods on the powder. Radiographs showed that the catalysts of similar material, opened in US 6,514,904, which is included here as reference. Peaks were characterized by relative intensity of halogen with exceptiona is th peaks, compared to the standard gamma alumina. The intensity ratio of peaks at the respective values of two-theta Bragg angle 34,0:32,5 and 46,0:45,5 were equal to 1.0 and 1.1 for the standard gamma aluminum oxide and 1.4 and 1.0 for the catalysts of the present invention.
1. The catalyst for conversion of hydrocarbons comprising a platinum group metal, tin and the substrate, having an average bulk density greater than 0.6 g/cm3and preferably greater than 0.65 g/cm3in which the mass ratio of platinum group metal to tin is less than 0.9, and preferably less than 0,85, where the platinum group metal is platinum in an amount of from 0.01 to 2.0 wt.% in the calculation of the element, and where the above-mentioned catalyst has an associated tin in specific clusters of tin and platinum group metals in the amount of at least 33 wt.% and effective molar ratio of the associated tin to platinum in the above clusters is at least 0,65 analysis of mössbauer spectroscopy.
2. The catalyst according to claim 1, where component substrate is a binder, which represents an inorganic oxide selected from the group consisting of aluminum oxide, magnesium oxide, zirconium dioxide, chromium oxide, titanium oxide, boron oxide, thorium oxide, phosphate, zinc oxide, silicon oxide and their mixtures, preferably alumina.
3. The catalyst according to claim 2, where the binder is an inorganic oxide is alumina, with the x-ray intensity ratio of peaks at values of two-theta Bragg angle 34,0:32,5 at least 1.2 and the ratio of the intensities of the peaks at values of two-theta Bragg angle 46,0:45,5, not more than 1.1.
4. Catalyst according to any one of claims 1 to 3, further comprising a metal promoter selected from the group consisting of germanium, rhenium, gallium, cerium, lanthanum, europium, indium, phosphorus, Nickel, iron, tungsten, molybdenum, zinc, cadmium and mixtures thereof, where the metal promoter ranges from 0.01 to 5.0 wt.% in the calculation of the element.
5. Catalyst according to any one of claims 1 to 3, optionally containing halogen in an amount of from 0.1 to 10 wt.%.
6. Catalyst according to any one of claims 1 to 3, where the alumina has a surface area of from 140 to 210 m2/g, preferably from 150 to 180 m2/year
7. Catalyst according to any one of claims 1 to 3, where the volumetric mass ratio of platinum group metal to tin is less than 0,85.
8. A method of converting hydrocarbons comprising contacting a hydrocarbon feedstock with a catalyst according to any one of claims 1 to 7 when the conversion of hydrocarbons, the converted hydrocarbon, where the catalyst comprises a platinum group metal, tin and the substrate having the average volume of the bacterial density is greater than 0.6 g/cm3where the mass ratio of platinum group metal to tin is less than 0.9.
9. The method of claim 8, where the hydrocarbon feedstock is the raw number of naphtha and how is the process of catalytic reforming process.
10. The method of claim 8, where the method is dehydration, and the catalyst additionally contains an alkaline or alkaline earth metal dispersed in the shaped catalyst in an amount of from 0.01 to 5.0 wt.% in the calculation of the element.
SUBSTANCE: catalyst for reforming of benzene fractions contains carrier represents compound: xAl2O3·yZrO2·zTiO2 with molar values of coefficients: x=(9.2-9.7)·10-1; y=(8.1-49.0)·10-3; z=(0.63-6.3)·10-3 and also platinum, rhenium and/or iridium and chlorine with following weight ratio of components: platinum 0.1-1.0; rhenium and/or iridium 0.1-1.0; chlorine 0.5-2.5; carrier to 100.
EFFECT: high activity and stability at high volume speed of raw material feeding and low pressure.
2 cl, 1 tbl, 10 ex
SUBSTANCE: method of hydro-processing a hydrocarbon material consists of: a) a hydrocarbon (HC) and hydrogen are mixed in the necessary ratio by supplying both streams in a jet-pump, and the supply of the HC is carried out at the starting part of the pump with pressure, which provides the necessary technological volume flow and pressure of the mixture, b) the mixture from stage a) are moved to the hydro-processing reactor, c) the flow of the mixture exiting from the hydro-processing reactor are cooled to a temperature below the critical temperature (Tc) of the lightest component of the HC, but higher than the heaviest component in the gas phase and is divided in two streams, liquid and gas, d) the gas stream is separated, by sequentially reducing its temperature, at the same time separating from it the condensed components, which are present in every stage of the highest critical temperature, further hydrogen is cleaned using the method of short-cycle adsorption and are submitted to the inlet of the jet-pump, closing its recirculation or a gaseous stream is directed to the reactor for additional hydro-processing only afterwards to its separation, cleaning using the method of short-cycle adsorption and returning hydrogen to the contours of its recirculation, e) the liquid stream is cleansed off liquefied gases, subsequently choking the pressure of the flow.
EFFECT: reduction in capital-output ratio, energy consumption and parasitic dissolving of gases in liquids.
FIELD: petroleum processing.
SUBSTANCE: invention relates to low-capacity hydrocarbon feedstock (petroleum, stabilized gas condensate, and the like) processing plants involving liquid-phase oxidative catalytic cracking, dehydrogenation, isomerization, and aromatization in heterogeneous catalyst bed. More particularly, invention concerns plant for liquid-phase oxidative catalytic cracking of hydrocarbon feedstock consisting of feed vessel to prepare feedstock connected via pipelines provided with shutoff means, through reactor producing gasoline fraction, to reactor producing diesel fuel fraction and black oil fuel, to heat-exchangers wherein gasoline vapor-gas fractions and diesel fuel are condensed and black oil fuel is cooled, to liquid fraction storage tanks, and to pumps supplying hydrocarbon feedstock and those removing gasoline, diesel fuel, and black oil fuel from the plant. Feed vessel for preparing feedstock incorporates grate throughout its surface and distribution system, through which air is supplied to activate hydrocarbon feedstock. Structures of gasoline and diesel fuel production reactors are of the same type, contain electrical heaters to heat hydrocarbon feedstock in lower reactor zone and contain three fixed beds. To dispose middle bed of heterogeneous catalysts, there is a mounted block in the form of two-way heat-exchanger wherein tube space is filled with catalyst granules, through which hydrocarbon feedstock from the tube plate enters as descending flow lower catalyst bed, while vapor-gas phase enters as ascending flow upper catalyst bed.
EFFECT: simplified structure, reduced metal usage, increased reliability and economical efficiency of plant, prevented thermal decomposition of hydrocarbon feedstock and cocking on catalyst surface, and enabled switch of plant to process different types of hydrocarbon stock without assembling operations.
2 cl, 1 dwg
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: chief matter of invention consists in performing preliminary reforming plant preparation stage wherein nitrogen/air mix circulates through empty reforming reactors and zeolite-containing bed at elevated temperature rising from 350 to 520°C: at 350-500°C only through empty reforming reactors and at 500-520°C also through zeolite-containing bed. Preferably, oxygen-to-nitrogen molar ratio in gas mix is (1-3):50 and circulation of gas mix is carried out for at least 1 h.
EFFECT: reduced preliminary plant preparation time, shortened start-up period, and increased yield of stable high-octane number reformate.
3 cl, 3 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: process comprises catalytic reforming of straight-run hydrofined gasoline fraction, rectification of reforming products to produce first fraction having dry point temperature 110°C and below and second fraction having boiling start temperature 110°C and below, contact of the first fraction first with aluminoplatinum catalyst containing, wt %: 0.35-0.40% platinum 0.35-0.40, 0.36-0.42% rhenium 0.36-0.42, 0.25-0.30% cadmium 0.25-0.30, chlorine 0.35-0.40, and balancing amount of alumina at temperature 200-250°C and pressure up to 4 MPa and then with isomerization catalyst containing, wt %: platinum 0.30-0.35, zirconium oxide 70-80, alumina 10-25, sulfate ion 6-12, sodium oxide 0.02-0.03, iron 0.03-0.04, and chlorine 0.03-1.32 at temperature 185-200°C and pressure 3-3.5 MPa, and mixing of contact product with second fraction.
EFFECT: increased octane number of desired product at insignificant increase in content of aromatic hydrocarbons.
2 tbl, 5 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: straight-run hydrofined gasoline fraction is subjected to catalytic reforming. Gasoline portion of reaction mixture, prior to feeding into the last reactor, is separated into top, median, and residual fractions boiling in following ranges: boiling start-(85-95)°C, (85-95)-(150-155)°Cm and (150-155)°C-dry point, respectively. Median fraction is brought into contact with alumino-platinum catalyst in last reactor and top and residual fractions are combined with last reactor product.
EFFECT: increased yield of desired product.
1 tbl, 4 ex
SUBSTANCE: method of producing chlorine involves oxidation of hydrogen chloride at 270 to 370°C with molecular oxygen in the presence of a vanadium anhydride based catalyst. Components of the catalyst are lithium and potassium chlorides with the following ratio in wt % of the total mass of catalyst: KCl - 4 to 52, LiCl to 3-43, V2O5 - 15 to 85.
EFFECT: increased rate of oxidation of hydrogen chloride and reduced operating temperature.
SUBSTANCE: aqueous suspension containing earth metal salt, powdered metal chloride and powdered transition metal oxide is made; aqueous suspension is made by dispersing in water the earth metal salt chosen from the group including barium and/or calcium and probably strontium or their combination. Water is added in powdered metal chloride, where powdered metal chloride is chosen from the group including Sn, Mg, Na, Li, Ba. Further powdered transition metal oxide is added being titanium oxide, to water; then plastic binder is added to until paste is formed; paste is dried up paste to powder; powder is heated up at raising temperature following preset temperature profile. Heated powder is baked to produce perovskite catalyst. Suspension contains mixed Ba and/or Ca and/or Sr (0.95mole) + TiO2 + metal chloride chosen from the group Sn, Mg, Na, Li, Ba in amount 0.05 mole.
EFFECT: simplified technology of catalyst producing.
19 cl, 14 ex, 2 tbl, 8 dwg
FIELD: chemistry, pharmaceutics.
SUBSTANCE: invention relates to method of obtaining catalyst of dehydrating 4,5,6,7-tetrahydroindole into indole. Described is catalyst of dehydrating 4,5,6,7-tetrahydroindole into indole containing nickel sulphide applied on aluminium oxide, catalyst being dopated with sodium and chlorine ions and contains 0.30-2.00% of nickel, 0.20-1.50% of sulphur, 0.10-0.20% of sodium, 0.20-1.00% of chlorine. Also described is method of obtaining catalyst which lies in impregnation of aluminium oxide with nickel salt with further processing with metal sulphide at room temperature in water medium in presence of hydrochloric acid and surface-active substance. Catalyst is isolated by filtration without further washing, dopating of catalyst takes place, and dopants are fixed by means of thermal processing.
EFFECT: increase of mechanical strength and activity of catalyst, as well as increase of its service life.
4 cl, 1 dwg, 10 ex
FIELD: petroleum processing and catalysts.
SUBSTANCE: invention relates to bismuth- and phosphorus-containing catalyst carriers, petroleum reforming catalysts prepared on these carriers, to methods for preparing both carriers and catalysts, and to petroleum reforming process using these catalysts. Described are catalyst carrier containing γ-alumina particles wherein bismuth and phosphorus are distributed essentially uniformly in catalytically efficient concentrations and a method for preparation thereof comprising (a) preparing solution containing bismuth precursor and solution containing phosphorus precursor; (b) preparing γ-alumina/alumina sol mixture; (c) mixing mixture of step (b) with solutions prepared in step (a) to produce carrier precursor containing essentially uniformly distributed phosphorus and bismuth; (d) molding; and (e) drying and calcination. Invention also describes petroleum reforming catalyst containing above-defined carrier and catalytically efficient amount of platinum, chlorine, and optionally rhenium; method of preparation thereof; and petroleum reforming process after hydrofining, which involves contacting petroleum with above-defined catalyst in presence of hydrogen at elevated temperature and pressure.
EFFECT: reduced catalyst coking velocity and achieved high stable activity of catalyst.
25 cl, 6 dwg, 4 tbl, 10 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention concerns catalytic process for obtaining isooctane fractions via alkylation of isobutane with butylene fractions. Process involves catalytic complex having following composition: MexOy*aAn-*bCnClmH2n+2-m, wherein Me represents group III-IV metal, x=1-2, y=2-3, and An- anion of oxygen-containing acid selected from sulfuric, phosphoric, molybdenic, and tungstenic acid, or mixture thereof in any proportions; a=0.01-0,2, b=0.01-0.1; bCnClmH2n+2-m is polychlorine-substituted hydrocarbon with n=1-10 and m=1-22, dispersed on porous support and containing hydrogenation component. Alkylation process is carried out at temperature not exceeding 150°C, mass flow rate of starting mixture not higher than 3 g/g cat*h, pressure not higher than 40 atm, and in presence of 10 mol % hydrogen.
EFFECT: increased catalyst stability and selectivity.
5 cl, 3 tbl, 20 ex
FIELD: organic chemistry.
SUBSTANCE: invention relates to method for production of derivatives of general formula , wherein R is C2H5, C3H7, C4H9. Claimed method includes reaction of aniline with aliphatic aldehydes in presence of catalyst. Method is characterized in that as catalyst crystallohydrate of lanthanide trichloride (LnCl3.6H2O, Ln = Pr, Nd, Eu) and triisobutylaluminum (iso-Bu3Al)in LnCl3.6H2O:(iso-Bu3Al) molar ratio of 1:12 are used. Process is carried out in air, under atmospheric pressure and room temperature in toluene for 25 min. quinoline and derivatives thereof are useful in synthesis of cyan dyes, as extractants, sorbents and corrosion inhibitors.
EFFECT: simplified method with increased yield.
1 cl, 1 tbl, 7 ex
FIELD: organic chemistry.
SUBSTANCE: invention relates to method for production of derivatives of general formula , wherein R is C2H5, C3H7, C4H9. Claimed method includes reaction of aniline with aliphatic aldehydes of general formula RCH2CHO, wherein R is as defined above in presence of catalyst. Method is characterized in that as catalyst crystallohydrate of lanthanide trichloride (LnCl3.6H2O, Ln = Pr, Nd, Eu) is used. Process is carried out in C6H5NH2:RCH2CHO:LnCl3.6H2O molar ratio of 45:100:1.2, in air, under atmospheric pressure and room temperature in ethanol for 25 min. Quinoline and derivatives thereof are useful in synthesis of cyan dyes, as extractants, sorbents and corrosion inhibitors.
EFFECT: simplified method with increased yield.
1 cl, 1 tbl, 7 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.
EFFECT: improved conversion method.
61 cl, 8 tbl, 32 ex
SUBSTANCE: invention relates to a catalyst system and a method of reducing nitrogen oxide emissions. The described catalyst system for reducing NOx contains: a catalyst having a support which contains at least one compound selected from a group consisting of aluminium oxide, titanium dioxide, zirconium dioxide, cerium oxide, silicon carbide and mixtures thereof, a catalytic metal oxide containing at least one of gallium oxide or silver oxide and at least one activating metal selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium or mixtures thereof; and a gas stream containing oxygen ranging from approximately 1 mol % to approximately 12 mol % and an organic reducing agent selected from a group consisting of alcohol, carbonate or combinations thereof, where the said organic reducing agent and the said NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to approximately 24:1. A catalyst system for reducing NOx which contains the following is described: a catalyst consisting of (i) metal oxide support which contains aluminium oxide, (ii) at least one of the following oxides: gallium oxide or silver oxide, present in amount ranging from approximately 5 mol % to approximately 31 mol %; and (iii) an activating metal or a combination of activating metals, present in amount ranging from approximately 1 mol % to approximately 22 mol % and selected from a group consisting of silver, cobalt, molybdenum, tungsten, indium and molybdenum, indium and cobalt, and indium and tungsten; and a gas stream containing (A) water in range from approximately 1 mol % to approximately 12 mol %; (B) oxygen in the range from approximately 1 mol % to approximately 15 mol %; and (C) an organic reducing agent containing oxygen and selected from a group consisting of methanol, ethanol, butyl alcohol, propyl alcohol, dimethyl carbonate or combinations thereof; where the said organic reducing agent and NOx are present in molar ratio carbon: NOx ranging from approximately 0.5:1 to 24:1. Also described are methods of reducing NOx which involve the following steps: providing a gas mixture and bringing the said gas mixture into contact with above described catalysts for reducing NOx (versions).
EFFECT: reduced ill effects of air contamination caused by by-products of incomplete high-temperature combustion of organic substances.
21 cl, 34 ex, 4 tbl