The method of processing of gas condensate
(57) Abstract:Usage: petrochemistry. Essence: from the condensate separated from the gas. Unstable gas condensate is subjected to contacting with a zeolite-containing catalyst at 250 - 430oC, a pressure of 0.1 to 1.5 MPa. Produce is subjected to rectification to give the fuel fractions. Use preferably the catalyst composition, % wt: zeolite Y with a molar ratio of SiO2/Al2O3from 4.0 to 8.0 - 0,05 - 5,0, high-silica zeolite with a molar ratio of SiO2/Al2O3from 20,0 to 100.0 - 0,05 - 85,0, matrix - rest. The finishing is carried out at flow rate of feed of 0.5 - 3.5 m3/m3including the Rectification is carried out in the presence of gaseous products of the process of refining and/or gas rectification. 3 C.p. f-crystals, 2 tab., 1 Il. The invention relates to the refining and petrochemical industries, namely the processing of gas condensate from the production of motor fuels and fuel formed by mixing the individual fractions isolated from the condensate.Known methods of processing hydrocarbon material extracted from wells include two stages. The first stage of processing on promyslovosti installations. The second stage processing of the prepared raw material for refineries, including primary and secondary processing (I. A. Gurevich "Technology of oil and gas processing", h I, M. Chemistry, 1972, S. 153 198).Secondary processing of hydrocarbons in the fuel are such basic processes as the processes of reforming of straight-run gasoline, naphtha fractions, the cracking of oil fractions, wikipaedia more than 200oC (Cm. A. I. Vladimirov "catalytic reforming", M. 1993, s 8 26). There are various schemes of the organization of secondary processes (reforming) using a variety of hydrocarbons and catalytic systems.For example, there is a method of improving the quality naphtha fractions, including fractionation of the feedstock naphtha light fraction and heavy fraction. The heavy fraction is subjected to reforming to aromatics and octane number.Part of the flow of the reformer is mixed with the light fraction and subjected to reforming over zeolite catalyst ZS M-5. Receive a stream of hydrocarbon enriched in aromatics, which can be divided into fractions. (Patent Velicer. N 2034351, C 10 F 59/00, 1980).The known is SUP>oC by multi-stage catalytic reforming followed by distillation of the obtained liquid products, and the rectification of liquid products of reforming are emitting head of the faction wikipeida from the initial boiling point of up to 130 - 160oC and the residual, wikipeida from 130 160oC until the end of the boil and then mix in a certain ratio. (Ed. mon. N 1766945, C 10 G 35/04, 16.10.1989).In the known methods of producing high octane gasoline, performed at the factory, as a source of raw materials used hydrocarbon fraction, the receipt of which from gas-and-oil raw materials involves many technological operations, which complicates the process as a whole.Closest to the proposed method to the technical essence and the achieved result is a method of processing gas in motor fuel, separating gas from condensate multistage separation in the oil fields and the subsequent processing of the raw gas condensate and volatile factory settings. Processing of unstable condensate includes:
remove from condensation of the methane-ethane fraction (separation at a temperature of 30oC);
destructive processing of condensate, including preliminary deep Hydrotreating stabilization section of hydrogenated feed and subsequent fractionation (distillation) with the release of factions since the beginning of the boil 62oC 62 85oC, 85 180oC. Fraction 62 85oC and 85 - 180oC is subjected to catalytic improvement in equipment of the type L-35-II/1000, followed by distillation and producing high-octane gasoline. The reforming process is carried out at a temperature of 450 530oC, a pressure of 1.5 to 3.0 MPa, and space velocities of 1.2 to 1.5 h-1("Technology of processing of sulfurous gas and condensate" edited Vakulin Century. And. Orenburg, 1990, S. 103 129).The disadvantage of the prototype is a complex technology of processing of gas condensate in motor fuel, due to the commercial preparation of the condensate for transport to the factory and complex processing factory, including the stage of stabilization, fractionation, Hydrotreating of the obtained fractions, catalytic refining and distillation. In addition, as a rule, released by condensate stabilization and fractionation of light hydrocarbons is fed to the processing and lost (burned), which reduces the yield of the target topsite provides the possibility of processing in the area of gas condensate production, with the production of motor fuels, while a simplification of the process, and increase output of high-quality fuel fractions due to involvement in the processing of additional quantities of light hydrocarbons and regulate the output of gasoline, kerosene and diesel fractions.The problem is solved by the proposed method for processing of gas condensate, including the separation of gas from liquid phase and recycling of unstable condensate in motor fuels using catalytic refining and distillation, the distinctive feature of which is that beautification is subjected directly to the unstable condensate in the presence of a zeolite catalyst at a temperature of 250 430oC, a pressure of 0.1 to 1.5 MPa, after which the produce is subjected to rectification with the selection of the target fuel fractions.Preferably the process of gentrification should be conducted using a zeolite-containing catalyst having the following composition, wt. zeolite Y with a molar ratio of SiO2/Al2O3equal to from 4.0 to 8.0, 0,05 5,0, servicecompany zeolite with a molar ratio of SiO2/Al2O3equal to from 20 to 100, 0,05 85,0, matrix - OYA 0.5 to 3.5 m3/m3h), and the process of rectification in the presence of gaseous products formed during catalytic sweetening and/or gas rectification.The combination of these features allows to significantly simplify the technology of processing of gas condensate and implement it directly on the fields; to increase the output of motor fuels by engaging in the process of processing the fraction of light hydrocarbons dissolved in the unstable condensate and get these products with high consumer properties (see data table 2); to regulate the ratio of the outputs of petrol, diesel and kerosene fractions, by regulating the temperature conditions of the process and composition of the used catalyst.The drawing shows a schematic diagram of an installation for the production of motor fuels by the proposed technology.The installation includes a separator 1 for separating gas from the condensate, the finishing reactor 2, the rectifying column 3.The method is as follows: the gas from the well into the separator 1 (or system separators, high and low pressure), where the separation of raw gas from condense light hydrocarbon into the reactor 2, where at a temperature of 250
430oC, a pressure of 0.1 to 1.5 MPa, the space velocity of the raw material of 0.5 to 3.5 m3/(m3h) in the presence of the zeolite catalyst is in the process of gentrification.As the zeolite catalyst can be used any known catalysts containing zeolites sverkhvysokochastotnye type pentasil or zeolite type Y, which introduced various inorganic binder clay, alyumooksid, silica, metroselect and so on (see for example, A. S. N 1594768, B 01 J 29/08, 1983 A. S. N 1594767, B 01 J 29/08, 1983 A. S. N 1396334, B 01 J 29/12, 1982, A. S. N 1396333, B 01 J 29/12, 1984 Pat. G B N 2034351, C 10 G 59/00, 1980; EP N 0032414, C 10 G 59/02, 1981; JP N 54-23362, C 10 G 37/10, 1979, and so on).The best results were obtained on the catalyst comprising a mixture of the two zeolites zeolite of type Y with a molar ratio of SiO2/Al2O3equal to 4,0oC8,0, in the amount of 0.05 to 5.0 wt.%. and sverkhvysokochastotnogo zeolite with a molar ratio of SiO2/Al2O3equal to 20 to 100, in the amount of 0,05 85,0, matrix else.Zeolite Y and servicecompany zeolite included in the catalyst composition may be used in rare-earth ion-exchange form, and/or H-shape, and/or Zn-forms. The/SUB>, amorphous aluminosilicates, zirconosilicate, etc. In the process of finishing the formation of the catalyzate isoparaffin and aromatic hydrocarbons, which contribute to higher octane and cetane numbers of motor fuels. The resulting produce (liquid reaction products) are then fed into the distillation column 3, where the selection of the following oils: gasoline N. K. 120oC 120 140oC or 120 160oC, or 120 180oC or 120 - 200oC, or N. K. 200oC and kerosene-diesel fraction 200 - 350oC. the Process of rectification, it is advisable to conduct in the presence of gaseous products formed during catalytic sweetening and/or gas rectification, which perform the role of inert gases. Then depending on seasonal needs fuels get summer and winter varieties of automotive and diesel fuels by mixing gasoline and diesel fractions in a certain ratio.Characteristics used unstable condensates obtained from the Department of gascondensate raw gas are presented in table 1.The following examples illustrate the method, but not ohranyayuschie it.Zeolite Y and servicecompany zeolite in the Na-forms are mixed with a matrix, is formed in the form of extrudates, pellets, pastilles and then carry out ion exchange of cations Na+on rare and/or cations of Zn+2and/or H+, washed with water, dried and calcined (examples 3, 8, 13 to 16).Example 1. An aqueous solution of aluminum sulfate concentrations of 20 kg/m3on Al2O3and containing 80 kg/m3H2SO4, an aqueous solution of sodium silicate concentration of 130 kg/m3on SiO2and containing 65 kg/m3NaOH, aqueous suspension of zeolite NaY and sverkhvysokochastotnogo zeolite concentration, respectively, 1.4 and 140,0 kg/m3mixed at the temperature of 15oC C the formation of hydrogel with a pH of 8.5. Then the hydrogel was processed with an aqueous solution of ammonium sulfate concentration of 10 kg/m3when temperature 50oC for 24 hours, washed with distilled water at 50oC for 24 hours, dried at 170oC and calcined at 550oC in air for 12 hours. Get a catalyst of the following composition: zeolite Y in N vokalnym ratio of SiO2/Al2O3100 5% rest of the matrix is amorphous aluminosilicate.Example 2. Catalytic improvement of unstable condensate is carried out at 250oC and space velocity of the feedstock 0.75 m3/(m3h) and a pressure of 1.5 MPa by using a catalyst having the composition, wt. zeolite Y in rare form with a molar ratio of SiO2/Al2O3equal 5,2 5,0% zeolite servicecompany in the protonated form with a molar ratio equal to 40 25% rest of the matrix pseudoboehmite.Example 3. Catalytic improvement of unstable condensate is carried out at 430oC, space velocity of the raw materials 3.5 m3/(m3h) and a pressure of 0.1 MPa by using a catalyst having the composition, wt. zeolite Y in the H form with a molar ratio of SiO2/Al2O3equal to 8.0, 0.05% zeolite servicecompany in the protonated form with a molar ratio of SiO2/Al2O3100, 5% rest of the matrix is amorphous aluminosilicate.Example 4. Catalytic improvement of unstable condensate is carried out at 275oC, space velocity of the raw material 2.5 m3/(m3h) and a pressure of 0.5 MPa using a catalyst having the composition, vysokokremnievykh in Zn-shaped with a molar ratio of SiO2/Al2O3equal to 20, 50% rest of the matrix - g-Al2O3.Example 5. Catalytic improvement of unstable condensate is carried out at 350oC, space velocity of the raw material 1.5 m3/(m3h) and a pressure of 0.2 MPa using a catalyst having the composition, wt. zeolite Y in Zn-shaped with a molar ratio of SiO2/Al2O3; equal to 4.8, 1,0% servicecompany zeolite in the H form with a molar ratio of SiO2O3equal to 60, 0.5% of the rest of the matrix is amorphous zirconosilicate.Example 6. Catalytic improvement of unstable condensate is carried out at 400oC, space velocity of the raw material 2.0 m3/(m3h) and a pressure of 0.1 MPa by using a catalyst having the composition, wt. zeolite Y in the H form with a molar ratio of SiO2/Al2O3equal to 5.1, 1.5% zeolite servicecompany in rare form with a molar ratio of SiO2/Al2O360, 30% of the rest of the matrix - a-Al2O3.Example 7. Catalytic improvement of unstable condensate is carried out at 300oC, flow rate of feed of 1.0 m3(m3h) and a pressure of 1.0 MPa when using the catalysate is th 7,2, 5.0% zeolite servicecompany in Zn-shaped with a molar ratio of SiO2/Al2O3100, 0.05% of the rest of the matrix is amorphous magnicient.Example 8. Catalytic beautification gas condensate is carried out at 375oC, space velocity of the raw material 1.5 m3/(m3h) and a pressure of 0.1 MPa by using a catalyst having the composition, wt. zeolite Y in the H form with a molar ratio of SiO2/Al2O3equal to 4.8, 1.0% zeolite servicecompany in the protonated form with a molar ratio of SiO2/Al2O3equal to 45, 85% of the rest of the matrix boehmite.Example 9. Catalytic improvement of unstable condensate is carried out at 250oC, flow rate of feed of 1.0 m3/(m3h) and a pressure of 0.1 MPa by using a catalyst having the composition, wt. the zeolite in the H-and rare forms with a molar ratio of SiO2/Al2O3equal to 5.1, 3.5% of the zeolite servicecompany in the protonated form with a molar ratio of SiO2O3equal to 65, 20% rest of the matrix g-Al2O3.Example 10. The catalyst as in example 9. Catalytic improvement of unstable condensate is carried out at 350oC, flow rate is political colouration of unstable condensate is carried out at 430oC, flow rate of feed of 1.0 m3/(m3h) and a pressure of 0.1 MPa.Example 12. The catalyst as in example 9. Catalytic improvement of unstable condensate osushestvliayut at 375oC, flow rate of 1.5 m3/(m3h) and a pressure of 0.5 MPa.Example 13. Catalytic improvement of unstable condensate is carried out at 400oC, space velocity of the raw material 1.5 m3/(m3h) and a pressure of 0.25 MPa by using a catalyst having the composition, wt. zeolite Y in the N - and rare forms with a molar ratio of SiO2/Al2O3equal to 70, 1.5% of the rest of the matrix is amorphous zirconosilicate.Example 14. The catalyst as in example 13. Catalytic improvement of unstable condensate is carried out at 400oC, flow rate of feed of 1.0 m3/(m3h) and a pressure of 0.1 MPa.Example 15. The catalyst as in example 13. Catalytic improvement of unstable condensate is carried out at 375oC, flow rate of feed of 1.0 m3/(m3h) and a pressure of 1.5 MPa.Example 16. Catalytic improvement of unstable condensate is carried out at 430oC, flow rate under the t Y in the N - and rare forms with a molar ratio of SiO2/Al2O3equal to 5.1, 25% rest of the matrix is amorphous zirconosilicate.Example 17. Catalytic improvement of unstable condensate is carried out at 375oC, space velocity of the raw material 1.5 m3/(m3h) and a pressure of 0.2 MPa using a catalyst having the composition, wt. zeolite servicecompany in N - and rare forms with a molar ratio of SiO2/Al2O3equal to 70, 5.0% of the rest of the matrix is amorphous magnicient.The obtained samples catalyzate in the process of elevating unstable condensate (examples 2 to 17) is subjected to distillation in the presence of gaseous products formed during the processing of unstable condensate and/or rectification. Temperature catalyzate at the entrance of the distillation column is 270 320oC and a pressure of 0.12 to 0.20 MPa.The results of the experiments are presented in table 2.Thus the advantage of the proposed method is:
possibility of production wells in the area of operation, which will give an opportunity to save costs for the preparation of well production to transportation, transportation and delivery of motor fuels in place is piracy (respectively AIDS);
the increase in the output of motor fuels at the expense of involvement in the processing of light hydrocarbons;
obtaining high-octane gasoline with an octane rating of up to 85 98 and diesel fuels with pentanoyl number 45 54 with the output up to 93.7% wtthe ability to adjust the output of gasoline and diesel fractions depending on the needs in a particular type of fuel. 1. The method of processing of gas condensate, including the separation of gas from liquid phase, processing the received unstable condensate in motor fuels using catalytic refining and distillation, characterized in that the improvement is subjected directly to the unstable condensate in the presence of the zeolite catalyst at 250 430oC, 0.1 to 1.5 MPa, after which the produce is subjected to rectification with the selection of the target fuel fractions.2. The method according to p. 1, characterized in that the finishing is carried out in the presence of a zeolite-containing catalyst composition, wt.The zeolite of type V with a molar ratio of SiO2/Al2O34 8 - 0,05 5,0
High-silica zeolite with a molar ratio of SiO2/Al2O320 100 0,05 85,0
3. Spas 3.5 m3/m3h4. The method according to p. 1, characterized in that the rectification catalyzate carried out in the presence of gaseous products formed during the catalytic refining, and/or gas rectification.
FIELD: petrochemical processes.
SUBSTANCE: high-octane fuels and propane-butane fraction are obtained via conversion of hydrocarbon feedstock on contact with hot catalyst placed in reactor, into which diluting gas is supplied at elevated pressure. Catalyst is Pentasil-type zeolite with general formula xM2/nO,xAl2O3,ySiO2,zMe2/mO wherein M represents hydrogen and/or metal cation, Me group II or VII metal, n is M cation valence, m is Me metal valence, x, y, z are numbers of moles of Al2O3, SiO2, and Me2/mO, respectively, and y/x and y/z ratios lie within a range of 5 to 1000. Metal oxide Me2/mO is formed during calcination, in presence of oxygen, of Me-containing insoluble compound obtained in zeolite reaction mixture.
EFFECT: increased octane number of gasoline fractions with propane-butane fraction as chief component of gas products, and prolonged inter-regeneration time of catalyst.
11 cl, 4 dwg, 3 tbl, 16 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: hydrocarbon feed is converted in presence of porous catalyst at 250-500°C and pressure not higher than 2.5 MPa, feed uptake being not higher than 10 h-1. Hydrocarbon feed utilized are various-origin hydrocarbon distillates with dry point not higher than 400°C. Catalyst is selected from various aluminosilicate-type zeolites, gallosilicates, galloaluminosilicate, ferrosilicates, ferroaluminosilicates, chromosilicates, and chromoaluminosilicates with different elements incorporated into structure in synthesis stage. Resulting C1-C5-hydrocarbons are separated from gasoline and diesel fuel in separator and passed to second reactor filled with porous catalyst, wherein C1-C5-hydrocarbons are converted into concentrate of aromatic hydrocarbons with summary content of aromatics at least 95 wt %. In other embodiments of invention, products leaving second reactor are separated into gas and high-octane fraction. The latter is combined with straight-run gasoline fraction distilled from initial hydrocarbon feedstock.
EFFECT: increased average production of liquid products.
18 cl, 3 dwg, 9 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.
EFFECT: facilitated reduction of benzene and unsaturated hydrocarbons in gasoline fractions and other hydrocarbon fuel mixtures.
3 cl, 1 tbl, 13 ex
FIELD: petrochemical processes.
SUBSTANCE: feedstock is brought into contact with catalyst based on Pentasil family zeolite in at least two zones differing from each other in conditions of conversion of aliphatic hydrocarbons into aromatic hydrocarbons, first in low-temperature conversion zone to covert more active feedstock components to produce aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom and, then, contacting the rest of hydrocarbons produced in low-temperature conversion zone with catalyst in high-temperature conversion zone, wherein less active component(s) is converted into aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom.
EFFECT: enabled production of aromatic hydrocarbons under optimal conditions from feedstock containing aliphatic C1-C4-hydrocarbons with no necessity of separating the latter.
4 cl, 1 dwg, 1 tbl
FIELD: petrochemical processes.
SUBSTANCE: hydrocarbon feedstock, containing narrow and wide hydrocarbon fractions boiling within a range from boiling point to 205°C and C1-C4-alcohols and/or dimethyl ether, which are blended in a system, to which they are supplied separately (by two pumps) at volume ratio (20.0-90.0):(10-80), respectively, is brought into contact with zeolite-containing catalyst at 380-420°C, pressure 0.2-5.0 MPa, and liquid feedstock volume flow rate 0.5-2.0·h-1, whereupon reaction products are liberated from water produced in the reaction. Above-mentioned zeolite-containing catalyst is comprised of (i) Pentasil-type zeolite with silica ratio (SiO2/Al2O3) 25-100 in amount 65-70% including residual amount of sodium ions equivalent to 0.05-0.1% sodium oxide, (ii) modifiers: zinc oxide (0.5-3.0%), rare-earth element oxides (0.1-3.0%), cobalt oxide (0.05-2.5%) or copper chromite (0.1-0.3%), and (iii) binder: alumina or silica in balancing amount.
EFFECT: increased octane number of gasoline.
2 tbl, 9 ex
FIELD: petrochemical processes.
SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.
EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.
12 cl, 3 tbl, 22 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.
EFFECT: increased yield of isoparaffin hydrocarbons.
7 cl, 2 tbl, 7 ex
SUBSTANCE: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.
EFFECT: increase in catalyst activity and gasoline octane number, accompanied by increase in yield.
4 cl, 3 tbl, 4 ex
SUBSTANCE: invention describes zeolite-containing catalyst for transformation of aliphatic hydrocarbons C2-C12 to a mix of aromatic hydrocarbons or high-octane gasoline component containing zeolite ZSM-5 with silicate module SiO2/Al2O3=60-80 mol/mol and 0.02-0.05 wt % of residual sodium oxide content, zeolite structural element, promoter and binding component, with zirconium or zirconium and nickel oxides as zeolite structural component, and zinc oxide as promoter, at the following component ratio (wt %): zeolite 65.00-80.00; ZrO2 1.59-4.00; NiO 0-1.00; ZnO 0-5.00; Na2O 0.02-0.05, the rest being binding component. Also, a method for obtaining zeolite-containing catalyst is described, which involves mixing reagents, hydrothermal synthesis, flushing, drying and calcinations of sediment. The reaction mix of water solutions of aluminum, zirconium and nickel salts, sodium hydroxide, silicagel and/or aqueous silicate acid, inoculating zeolite crystals with ZSM-5 structure in Na or H-form, and structure-former, such as n-butanol, is placed in an autoclave, where hydrothermal synthesis is performed at 160-190°C for 10-20 hours with continuous stirring; the hydrothermal synthesis over, Na-form pulp of the zeolite is filtered; the obtained sediment is flushed with domestic water and transferred to salt ion exchange by processing by water ammonium chloride solution with heating and stirring of the pulp; the pulp obtained from salt ion exchange is filtered and flushed with demineralised water with residual sodium oxide content of 0.02-0.05 wt % on the basis of dried and calcinated product; flushed sediment of ammonium zeolite form proceeds to zinc promoter introduction and preparation of catalyst mass by mixing of ammonium zeolite form modified by zinc and active aluminum hydroxide; obtained catalyst mass is extruded and granulated; the granules are dried at 100-110°C and calcinated at 550-650°C; calcinated granules of zeolite-containing catalyst are sorted, ready fraction of zeolite-containing catalyst is separated, while the granule fraction under 2.5 mm is milled into homogenous powder and returned to the stage of catalyst mass preparation. The invention also describes method of transformation of aliphatic hydrocarbons to high-octane gasoline component or a mix of aromatic hydrocarbons (variants), involving heating and passing raw material (gasoline oil fraction direct sublimation vapours or gas mix of saturated C2-C4 hydrocarbons) through stationary layer of the aforesaid catalyst.
EFFECT: reduced number of components and synthesis stages of zeolite-containing catalyst; increased transformation degree of raw material; improved quality and yield of target products with the said catalyst.
4 cl, 8 tbl, 12 ex
SUBSTANCE: invention refers to production method of high-octane gasoline fractions and/or aromatic hydrocarbons C6-C10 as follows, hydrocarbon materials is heated, evaporated and overheated to process temperature, thereafter providing its contact at temperature 320-480°C and excess pressure with periodically recyclable catalyst containing zeolite of composition ZSM-5 or ZSM-11. Then it is cooled. Contact products are partially condensed, separated into gaseous and liquid fractions by separation. Liquid products of separation are supplied as power primarily to the first distillation column for separation of hydrocarbon gases and liquid stable fraction. The latter is supplied to the second distillation column for separation of high-octane gasoline fraction, or aromatic hydrocarbon fraction, and heavy charge fraction. Gaseous fraction resulted from separation of contact products is supplied to the first distillation column, specifically to intermediate section between infeed and external reflux inlet. External reflux is liquid distillate of the first distillation column.
EFFECT: reduction of power inputs, i.e. quantities of heat and cooling agent, required for reaction products separation.
5 cl, 2 ex