Method of producing high octane gasoline
(57) Abstract:Applications: petrochemical industry. The essence of the invention: stable gas condensate is subjected to a single evaporation to form a liquid residue in an amount not less than the amount of actual pitches in the original condensate. The condensation is then subjected to fractionation. The fraction of 58°C QC the end of the boil, is processed in the presence of a catalyst containing a zeolite of type pentasil. Gasoline fraction processing products mixed with fractions of stable gas condensate. 1 Il. table 2. The invention relates to gas processing and petrochemical industries, in particular the production of high octane gasoline from gas condensate.A known method of producing motor fuels from gas condensate by allocating to 30-70% straight-run gasoline fraction with a low octane number and fraction of diesel and fuel oil and the subsequent elevation of gasoline fraction with the aim of producing high-octane gasoline (Gritsenko, A. I. Gas industry, 1981, No. 11, S. 8-9).The closest in technical essence and the achieved result to the invention is a method of processing the Oia fuel and oils 1988, No. 5, S. 6-7). According to this method, the raw material straight-run fraction of the initial boiling point -170aboutC, isolated from stable gas condensate, fractionary emitting straight-run gasoline fractions start boiling -58aboutC; 58-140aboutWith or 62-170aboutC. Fraction 58-140aboutWith or 62-170aboutWith evaporated, overheat and subjected to catalytic processing in a reactor in the presence of high catalyst at a temperature of 300-450about(380-450aboutC) and a pressure of 1-5 MPa (1-2 MPa). The reaction products sephirot, stabilize. The rectification allocate target high-octane gasoline fraction, which compounder with straight-run gasoline fraction start boiling -58aboutC.In the specified method is not used at the stage catalytic conversion of fraction, wikipaedia at a temperature of 170aboutSince, due to the additional coking of the catalyst (see, for example, Aghabalyan L., and others Zeoforming new technology high octane fuels on small modular plants// Promising processes and catalysts for oil refining and petrochemistry: Sat. the scientific. Tr. / Granie Tsniiteneftehim, 1990 vol. 43 C. 75-84). Involvement in the processing of this fraction would increase gasoline is about coking of the catalyst when used on stage catalytic conversion of gas-condensate fractions, wikipaedia at a temperature of 140-170aboutWith and more. Involvement in catalytic processing faction 58aboutWith the end of the boil can increase the potential of the gasoline fraction in the condensate 10-12% and, respectively, the output of gasoline at 6-8% compared to the fraction 58-170aboutC.The delivered result is achieved by the method of producing high octane gasoline from stable gas condensate by fractionation with getting straight-run fractions, one of them on the catalytic wall in the presence of a catalyst containing a zeolite of type pentasil, at elevated temperature and pressure, separation, stabilization, fractionation of the products of processing of obtaining gasoline fraction and offset it with a straight-run fraction of stable gas condensate, in which the fractionation of stable gas condensate is subjected to a single evaporation with the separation of liquid residue in an amount not less than the amount of actual pitches in the original condensate, and catalytic processing serves faction 58aboutWith the end of the boil.Actual pitch is defined as the residue after evaporation of condensate in a stream of steam at a temperature of 180aboutFaction 58aboutWith the end of the boil overheat and served on catalytic processing in the presence of a zeolite catalyst of the type pentasil with a ratio of SiO2/Al2O3at least 12 at a temperature of 300-450aboutC and a pressure of 0.5 to 5 MPa.The resulting reaction products are cooled, sephirot, stabilize and subjected to rectification with a target allocation of gasoline fraction, for example, the beginning of the boil -185aboutWith the obtained gasoline fraction compounding with straight-run fractions of the condensate, for example, the fraction of the beginning of the boil -58aboutWith, and the residue after distillation of the reaction products directed to the selection of valuable aromatic hydrocarbons10+for example, durene, naphthalene and other Light hydrocarbons fraction1-C4obtained by stabilizing the gasoline fraction, is used as fuel.Differences between the proposed method consist in the use of on-stage catalytic conversion of fractions 58aboutWith the end of the boil stable gas condensate subjected to single evaporation from removing the actual resins in the form of liquid residue.The amount of liquid residue will determine, based on the technological requirements, We have established, the actual resin chemical composition are asphalt-maloperation hydrocarbons are the primary source of coke on the catalyst. After their removal from the raw materials of the catalyst also works consistently and with the same koksoobrazovaniya as using fractions 58-170aboutSince, according to the prototype. Normal alkanes and naphthenes, (C6-C11) remaining in distillate (FR. 58aboutWith the end of the boil) after a single evaporation and fractionation, are converted to conversion close to 100% and the lighter alkanes (C1-C5and arena WITH6+.The method is carried out according to the following schematic diagram (see drawing).Stable gas condensate is subjected to a single evaporation in the evaporator separator 1 with the release of vapor phase and liquid residue containing the actual resin. The liquid residue is used as a component of diesel or fuel oil. Vapour phase serves to distillation column 2, where the top is separated straight-run gasoline fraction start boiling -58aboutAnd cube fraction 58aboutWith the end of the boil. CBM product of the column 2 is evaporated in the heat exchanger 3, overheat in the furnace 4 and is subjected to katal is paratore 7. Vapour phase separator 7, containing hydrocarbons WITH1-C4use as fuel, and the liquid phase is directed to the stabilization of the column 8. The distillate of the column 8 is used for the propane-butane fraction and CBM product is directed to the separation in a distillation column 9. From the top of column 9 select your target gasoline fraction, and CBM product sent for extraction of aromatic hydrocarbons FROM10+. The obtained gasoline fraction compounding with a light straight run fraction. Start boiling -58aboutWith in the vessel 10.P R I m e R 1 (the prototype). Stable gas condensate of Vuktyl field containing the actual resin in the amount of 523 mg/100 cm3(0.8% wt. ), (see tab. 1, 2) fractionary emitting 50% wt. light gasoline fractions start boiling -58aboutWith octane number (PTS) 75 by the research method (IM), 35 wt. faction 58-140aboutAnd 15 wt. / faction 140aboutWith the end of the boil.Fraction 58-140aboutAfter evaporation in the heat exchanger and overheating in the oven served in a reactor, where it condenses at a temperature of 380aboutC, a pressure of 1 MPa and a space velocity of liquid feedstock 2H-1with catalyst, sostojashie is you reaction directed to the separation unit, stabilization and rectification. Get on the fraction 58-140aboutWith 40% by weight of hydrocarbon gases WITH1-C4that is 57.5 wt. target gasoline fraction start boiling -185aboutWith about 2.5% fraction 185aboutK. K. and 0.02 wt. Cox.The obtained gasoline fraction compounding with a light straight run fraction start boiling -58aboutC. the Yield of gasoline from PTS=78 IM is 70% by weight of stable gas condensate. The duration of operation of the catalyst without reducing the activity of 120 hoursP R I m m e R 2. Stable gas condensate composition of example 1 (see tab. 1, 2 and hell.) subjected to a single evaporation at a temperature of 120aboutWith the evaporator-separator 1 with allocation of 97 wt. distillate-faction start boiling -195aboutAnd 3 wt. the liquid residue that is used as a component of the boiler or diesel fuel. From the fraction boiling -195aboutWith rectification column 2 separate top 51,5% mass fraction start boiling -58aboutAnd the cube of 48.5 wt. faction 58-195aboutWith that evaporated in the heat exchanger 3, overheat circuit 4 and then subjected to catalytic processing in the reactor 5 through the conditions of example 1.The reaction products are cooled in the heat exchanger 6 and separated in the separator 7. Steam is on the stabilization of the column 8. Top of the column 8 are selected fraction WITH3-C4and CBM product is directed to the separation in the reaction column 9. Top of the column 9 select your target gasoline fraction start boiling -185aboutAnd cube fraction 185aboutWith the end of the boil. Get on the fraction 58-195aboutWith: 36 wt. hydrocarbon gases WITH1-C4, 60,3 wt. target gasoline fraction start boiling -185aboutWith about 3.7 wt. faction 185aboutWith the end of the boil, containing aromatic hydrocarbons WITH10+composition (wt.): the durene 40, naphthalene 20; arena WITH10+40, and coke 0.02 wt.The obtained gasoline fraction compounding with a light straight run fraction start boiling -58aboutWith in the vessel 10. The output of gasoline PTS=79 (IM) is to 78.3 wt. Indicators derived gasoline meet the requirements of GOST 2084-77 for gasoline grades a-76.The duration of operation of the catalyst without reducing the activity of 120 hoursP R I m e R 3. Stable gas condensate (see tab. 1, 2) containing the actual resin in the amount of 1800 mg/100 cm3(2.6 wt.) subjected to a single evaporation in the evaporator 1 at a temperature of 120aboutWith the allocation of 95 wt. faction start boiling 200aboutWith 5 wt. the liquid residue. From the faction start key is BOM 59 wt. faction 58-200aboutWith, which is subjected to the processing conditions of example 2. The output of gasoline with an octane rating 78 (IM) is 75 wt. the output of coke -0,02 wt. The duration of operation of the catalyst without reducing the activity of 120 hoursP R I m e R 4 (for comparison). Stable gas condensate processed at the conditions of example 2, but without preliminary single evaporation. The output of coke 0.06 wt. the duration of the catalyst without lowering activity 48 hours METHOD of producing high OCTANE GASOLINE from stable gas condensate by fractionation with getting straight-run fractions, one of them on catalytic processing in the presence of a catalyst containing a zeolite of type pentasil, at elevated temperature and pressure, separation, stabilization, fractionation of the products of processing of obtaining gasoline fraction and mixing it with straight-run fraction of stable gas condensate, characterized in that stable gas condensate before fractionation previously subjected to a single evaporation with the separation of liquid residue in an amount not less than the amount of actual pitches in the original condensation and catalytic who
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