Microspheric zeolite catalyst for the conversion of aliphatic hydrocarbons, c2- c10
(57) Abstract:The inventive catalyst contains high-silica zeolite of the type pentasil in the hydrogen form with a ratio Si/Al=12 - 30 25 - 35 wt%, binder - zirconium oxide 5 to 10 wt%, (BF ZrO2), the promoter is zinc oxide, 1 to 2 wt% (ZnO, ) phosphate Zirconia 25 - 30 wt.%(CF Zr3(PO4)4) and alumina rest (BF Al2O3). The content of compounds of zirconium in the catalyst does not exceed 35 wt.%. In the apparatus with stirrer and heating load condensate and water pellet of aluminum hydroxide. Mix and add an aqueous solution of nitric acid Zirconia and an aqueous solution of zinc nitrate, stirred for 1 h Type zeolite CBM - III in the ammonium form. After stirring gradually add the aqueous solution of orthophosphoric acid. The temperature was raised to 90 To 60 °C and the suspension is incubated 3 hours is Subjected to spray drying at 190 to 220°C. Calcined granules in a muffle furnace at 550°C 5 h 4 table. The invention relates to compositions resulting zeolite-containing catalyst for the conversion of aliphatic hydrocarbons2-C10contained in the low-octane gas condensate or straight-run gasoline and Shir the liquids.In aromatization reactions of olefins WITH2-C4and paraffins WITH2-C10high activity is exhibited by zeolites groups of pentelow - ZSM - 5, ZSM - 11, DCM, WHC and others. The zeolite is usually used in the hydrogen form (the content of Na2O less than 0.1 wt.%) [1, 2] and as a binder is alumina - Al2O3. The content of zeolite in the catalyst varies widely - from 1 to 99 wt.%. In addition, the catalyst may contain promoters that increase output arenes is one or more metals II, III or VIII groups of the Periodic system is typically Zn, Cd, Ga, Pt or Pd in an amount of 0.1-10 wt.%, preferably 0.1 to 2%.Known  the catalyst dehydrocyclization aliphatic hydrocarbons2-C5comprising 40-60 wt. % of phosphorus-containing alumina (P/Al = 0,01-1). 0.1 to 5 wt. % gallium and crystalline aluminosilicate with SiO2/Al2O31 2 (ZSM - 5). The catalyst is prepared as follows. In a mixture of freshly prepared Hydrosol Al2O3and zeolite injected mixture glioblastomas agent is hexamethylenetetramine and source of P (usually phosphoric acid or its salts) and get a homogeneous mass which is dispersed in the oil. The catalyst particles, remove the wear on the catalyst impregnated or mixed with the zeolite and the Hydrosol Al2O3. Introduction to the catalyst dehydrocyclization phosphorus-containing aluminum oxide provides improved resistance to the formation of coke.Known introduction of salts of zirconium in the bifunctional catalyst. The catalyst for the isomerization of n-paraffins in the patent  contains a 49.9-97 wt.% zeolite (mordenite or fogasa), a 49.9 - 1 wt.% metal oxide (Al2O3the binding agent), 0.1 to 1% of the mass. Pt or Pd and 0.1-1 wt.% Zn (but not less than noble metal). The zeolite is impregnated with a solution of Zn salt prior to its mixing with the binder, the compounds of Pt (Pd) is applied by impregnation on the calcined catalyst. The use of bimetallic couples Zn and Pt or Zn and Pd increase the activity and selectivity of the catalyst for isomerization of n-paraffins.It is known that salts of Zr have a weak acidic properties and can be used as catalysts. Patented catalyst for the conversion of methanol or dimethyl ether to olefins WITH2-C6 containing 1-60 wt.% (preferably 5-20%) partially hydrated zirconium sulfate Zr(SO4)2on-Al2O3, SiO2or ZrO2.In the patent  proposed the closest to the proposed invention the composition bi the pore size (ZSM - 5, ZSM - 23, ) and binder (Al2O3, SiO2or aluminosilicate) in any proportion, as well as noble metal). Introduction to the catalyst components containing complex cation zirconium (hydroxychloride Zr or Al3Zr(OH)9Cl4improves the hydrothermal stability of the catalyst and the dispersion of the noble metal. The compound containing a complex cation Zr, mixed with the zeolite or with a binder at any stage of the preparation of the catalyst. It is assumed that during annealing the pellets of the catalyst complexes of Zr into ZrO2. Is an example of the preparation of the catalyst of the following composition (wt.%): zeolite ZSM - 5-65, Al2O3- 32,5; ZrO2- 2,5; Pd - 0,39. Zeolite is stirred with Pd(NH3)4Cl2dissolved in water, containing products of reaction of equimolar amounts of glycine and Al3Zr(OH)9Cl4add Al2O3and a lot ekstragiruyut. Bulk density of the calcined catalyst was 0.63 g/cm3the density of 2.65 g/cm3.Catalysts used in fluid-the process should have a bulk density 0,80-0,85 g/cm3to avoid uncontrolled release of catalyst from the reaction products, when acceptable to the practical is Oh resistant to abrasion. These qualities are provided by the composition of the catalyst and the technology of its preparation. When this catalyst should contain the maximum number of active component is a zeolite, components with high specific gravity and sufficient plastic component.The increase of the content in the catalyst ZrO2up to 20 wt.%, permitted in  , is insufficient to obtain a catalyst with the desired bulk weight, and leads to the decrease of the specific surface of the catalyst and the specific pore volume.In accordance with the invention catalysts for the conversion of aliphatic hydrocarbons2-C10in a high-octane component of gasoline, is enriched in aromatic hydrocarbons, contains the group zeolite with Si/Al= = 12-30 in the hydrogen form, aluminum oxide and zirconium oxide as a binder, zinc oxide as promoter and zirconium phosphate in the following ratio, wt.%: Zeolite 25-35 ZrO25-10 Zr(PO4)425-30 ZnO 1-2 Al2O3Else
The content of compounds of zirconium in the catalyst does not exceed 35 wt.%.The proposed composition of the catalyst differs from the known to the introduction of a new comp the number of Zirconia ZrO(NO3) 2H2O and phosphoric acid, H3PO4. Thus, the claimed solution meets the criterion of "novelty."Known zeolite-containing catalysts include phosphorus-containing alumina  or zirconium dioxide . However, their use in these cases, in combination with other components do not provide compositions such properties that they are sharing in the inventive solution, namely the increase in the activity of the catalyst with suitable for practical purposes, the bulk weight 0,80-0,85 g/cm3.The observed effect is explained by the fact that in the conditions of preparation of the catalyst of phosphoric acid reacts with nitric acid zirconium with the formation of phosphates of zirconium conditional composition Zr3(PO4)4that possess catalytic activity in reactions acid-base type and are involved in the conversion of aliphatic hydrocarbons WITH2-C10. Therefore, when close physical characteristics of the zeolite catalyst containing zirconium oxide and zirconium phosphate is more active than the catalyst containing only zirconium oxide. This is manifested in higher stemperature process or reduce the content of zeolite in the catalyst. Thus, the catalyst of the proposed composition has new properties and meets the criterion of "inventive step".The catalyst is prepared as follows. In steel apparatus with stirrer and heating receive aqueous suspension of the catalyst mass of a given composition. For this, the device loads the estimated amount of condensation and water pellet of aluminum hydroxide and after stirring the aqueous solution of nitric acid Zirconia ZrO(NO3)22H2O and an aqueous solution of zinc nitrate Zn(NO3)26H2O. the resulting suspension is stirred for 1 hour. Then in a mixer add the estimated amount of the zeolite CBM-III in ammonium form (degree of relative crystallinity, x-ray, 100%. Si/Al = 15,7. - static capacity for water vapor of 0.08 cm3/g pairs heptane 0,24 cm3/g). After 30 minutes stirring the resulting suspension into it gradually add the estimated amount of the aqueous ortho-phosphoric acid (H3PO4. The temperature in the apparatus is increased up to 50-60aboutAnd the suspension is maintained at this temperature and stirring for 3 hours After that, the suspension is drained and sent for spraying onto the laboratory is kasperesky granules are calcined in a muffle furnace at 550aboutWith over 5 hours of Calcined pellets scatter on the screens and separate the fraction of 20-150 μm, and the fraction of 20-50 μm 70 wt.%.The following examples illustrate the preparation of catalysts according to the alleged invention and for comparison and the results of their testing in the reactions of conversion of hydrocarbons WITH2-C10containing aliphatic hydrocarbons - low-octane gas condensate and gasoline fractions of light hydrocarbons in a high-octane component of gasoline.P R I m e R 1. To prepare a homogeneous aqueous slurry of a catalyst mass of a given composition in a mixer load 20 l of condensate and 1400 g of water pellet of aluminum hydroxide (SPT = =80 wt.%) and get a homogeneous suspension. Then, the device loads the solution 523,7 g nitrate Zirconia ZrO(NO3)2x x2H2O in 2 liters of condensate and solution to 74.2 g of zinc nitrate Zn(NO3)26H2O in 1 liter of condensate. After stirring for 1 h in a mixer add 412 g of zeolite NH4CBM-III (SPT - 15 wt.%) and after 30 minutes of stirring the solution to 150.1 g of N3PO4in 5 l of condensate. The resulting mass is stirred until a homogenous mixture for 3 h at 50-60aboutWith, drained and eg is aboutC for 5 hours, the Catalyst has the following composition, wt.%: Zeolite CBM-III 35 ZrO210 Zr(PO4)225 ZnO 2 Al2O328
The catalysts according to examples 2-6 were prepared similarly to the catalyst of example 1. The number of the blend components and the composition calcined at 550aboutSince the catalysts are given in table. 1. The composition of the catalyst mass does not account for water condensation, the flow of which is to prepare the catalysts according to examples 1-6, the following: obtaining a water suspension of aluminum hydroxide - 20 l; obtaining solutions of nitric acid zirconyl - 2 l, nitrate zinc - 1 l, phosphoric acid - 5 lThe weight of the catalysts prepared according to examples 1-6 0,80-0,85 g/cm3.Samples of the resulting catalysts were tested in the pilot unit.The raw material passes through the heating furnace and heated to 250aboutComes with under a distribution grid of the reactor where the conversion of raw materials into a product enriched arenas. The process is carried out in a turbulent fluidized bed of partially spent catalyst at a pressure of 0.3-0.4 MPa, a temperature of 360-530aboutC, space velocity of the raw material 500 h-1and ratio of catalyst circulation 3-6 maticevski.The reactor is equipped with independent electric heating zones. The temperature control on the height of the reactor is carried out using a chromel-aluminievyh thermocouple readings are recorded multi-point potentiometer PSC-4.Charged to the reactor of 1 liter of the catalyst. Prior to testing, the catalyst is heated in a stream of nitrogen to 250-560aboutWith depending on the feedstock. In the case of turning registertimer gas heat withdrawn partially removed water refrigerator.Turbulent fluidized bed of catalyst is achieved by maintaining the linear velocity of the vapor of the raw material of 0.15-0.25 m/s (based on the cross-section of the reactor).The reaction products rise to the top of the reactor, separated from the catalyst particles in the cyclone and filter and fed into the separator, where the separated liquid phase is unstable condensate and gas. The condensate after stabilization and gaseous products analyze.To maintain a constant catalyst activity part of it through a pipeline to bring in the regenerator. Regeneration is performed by air (volumetric feed rate of 600 h-1) if 600aboutC.The duration of the catalyst in the reactor 1 h, the duration is 49-142aboutWith a density of 0,702 g/cm3with an octane number by the motor method 59,8 and wide fraction of light hydrocarbons (NGL) Nizhnevartovsk condensate and onefineday gas similar in composition to the greasy gas catalytic cracking. The composition of raw materials are given in table. 2.Are given in table. 3 the results of the tests of catalysts indicate that samples containing 25-30 wt.% Zr3(PO4)4more active in the conversion of hydrocarbon feedstocks into high-octane component of gasoline. When turning retinotomies gas increases the conversion of olefins and the yield of liquid product. Similar activity is achieved on the catalyst comparison with the temperature increase on the 15aboutWith and on the catalyst according to example 4, containing 10 wt.% less zeolite than the catalyst of comparison. During the transformation of broad fraction of light hydrocarbons, the catalysts prepared in accordance with the claimed invention, have a higher yield of liquid products and a higher content of aromatic hydrocarbons. Liquid products obtained from gas-condensate gasoline on the catalysts according to examples 1-5, enriched with aromatic hydrocarbons, and you have more the scientists at the transformation of different kinds of raw materials for the catalyst prepared according to example 3, in accordance with the claimed invention. MICROSPHERIC ZEOLITE CATALYST FOR THE CONVERSION OF ALIPHATIC HYDROCARBONS, C2-C10in high-octane component of gasoline containing high-silica zeolite of the type pentasil in the hydrogen form with a ratio Si/Al = 12-30, aluminum oxide, binder - zirconium oxide, the promoter is zinc oxide, characterized in that it further contains zirconium phosphate with the following content, wt.%:
High-silica zeolite 25 - 35
Zirconium oxide 5 - 10
The zirconium phosphate 25 - 30
Zinc oxide 1 - 2
the content of compounds of zirconium in the catalyst does not exceed 35 wt.%.
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
SUBSTANCE: proposed zeolites have AAI of at least 1,2. Method of obtaining zeolite includes removal of tetraethyl ammonium standard agent at temperature not above 550°C under conditions when zeolite has AAI of at least 1, 2 after removal of standard specimen. Zeolite is selected from group consisting of beta-zeolite, TEA-mordenite and TEA-ZSM-12. Proposed zeolites are effective for aromatic alkylation processes.
EFFECT: enhanced efficiency.
8 cl, 8 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention proposes a method for synthesis of linear alkylbenzenes involving the alkylation reaction of benzene with (C8-C20)-alpha-olefin at temperature 100-4500C and under pressure 0.2-5 MPa on catalyst of micro-mesoporous structure with part of micropores from 0.03 to 0.90 and part of mesopores from 0.97 to 0.10. Catalyst comprises microporous crystalline silicates of zeolite structure and having the composition of anionic carcass of the formula: T2O3(10-1000)SiO2 wherein T means elements chosen from group consisting of p-element of group III or d-elements of groups IV-VIII, or their mixtures. Catalyst of micro-mesoporous structure comprises, in particular, microporous crystalline silicate of zeolite structure of the following type: FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL and MTW. Invention provides increasing yield of linear alkylbenzenes and with high selectivity by sum of linear alkylbenzenes and 2-phenyl isomer and in retaining catalytic stability of catalyst.
EFFECT: improved method of synthesis.
6 cl, 2 tbl, 2 dwg, 29 ex