Method of producing high octane gasoline fractions
(57) Abstract:Usage: in the petrochemical industry, in particular in the processing of hydrocarbon raw materials. The inventive method involves contacting the hydrocarbon ( boiling point up to 200 to 220°C ) in an environment of hydrogen containing gas with a catalyst containing zeolites, including zeolite with structure of ZSM-5 or ZSM-11, the metals of the second, third, fourth, eighth group, and/or compounds of metals of the first - fourth group in the presence of carbon monoxide (2+and/or carbon dioxide (4+). The process is carried out at 280 460°C., a pressure of 0.3 to 10.0 MPa, mass flow rate of feed of 0.2 to 10.0 wt. h/wt. h per hour space velocity of hydrogen containing gas 1000 22100 about. PM/about.h. per hour, a molar ratio of hydrogen and the mixture monoxide and carbon dioxide, equal to 1 to 20, and the molar ratio of carbon monoxide to the dioxide, equal to 0.02 1000. When using raw materials containing paraffins and naphthenes, the process is carried out at 350 to 440°C., a pressure of 1 to 10 MPa, feedstock containing olefins, at 300 and 400°C., a pressure of 0.5 to 6 MPa. 7 C.p. f-crystals, 6 PL. The invention relates to a catalytic process for the production of unleaded high-octane gasoline fractions from the hydrocarbon is adnie faction, wikipaedia at the temperature of boiling gasoline (up to 200-220aboutC) and gaseous registereda faction.Known methods for producing gasoline fractions and their high-octane components of hydrocarbons in the environment of the hydrogen-containing gas, for example [1-3] According to the methods of conversion of various hydrocarbons WITH2-C12carried out in the temperature intervals of the reaction 200-700aboutWith the speed of feed of 0.1-400 h-1when the molar ratio of N2/Plevo - Dorogi to 20 on the catalysts containing zeolites of type ZSM, including modified by various elements. The main disadvantages of these methods or relatively low yields or low octane gasolines produced.The closest in technical essence is a way to hydroprene hydrocarbons  According to the selected prototype high-octane gasoline fraction obtained by contacting the hydrocarbons WITH1-C12at a temperature of 250-700aboutC, a pressure of 0.1-10 MPa, the space velocity of the raw material of 0.5-10 h-1and the molar ratio of N2/hydrocarbons 50 with a catalyst based on zeolites, including ZSM. The catalyst may contain IU torida 1-80, metal is 0.1-30 wt. The main disadvantages of the prototype are relatively low-octane gasoline fractions obtained.The invention consists in contacting the hydrocarbon feedstock with zeolite catalyst at elevated temperature and pressure in the environment of the hydrogen-containing gas in the presence of carbon monoxide II and/or carbon monoxide IV (CO, CO2). The reaction products separated from gaseous and liquid (gasoline) fractions. Stage contacting is carried out in temperature ranges of reactions 280-460aboutC, a pressure of 0.3 to 10 MPa, mass flow rate of feed of hydrocarbons from 0.2 to 10 h-1, volumetric feed rate of the hydrogen-containing gas 1000-22100 h-1and the molar ratios of H2/CO+CO21-20 and CO/CO2=-0-1000.As raw materials is possible using liquid hydrocarbon fractions, wikipaedia in the temperature range of the boiling point of gasoline (up to 200-220aboutS), and/or gaseous registergui fractions. Optimal processing of paraffin-naphthene raw material (a process called "Sinar") are the reaction temperature 350-440aboutC and a pressure of 4-10 MPa, and for processing registertimer (C2-C5) raw materials (protonirovannogo or modified elements I, II, III, VI and VIII groups of the zeolite, 0-70% of oxides of elements I, II, III, VI groups and 0-30% of a binder. As zeolite using zeolites with structure of ZSM-5 or ZSM-11 General formula aNa2O bAl2O3the bot dSiO2(where enOmone or more oxides of elements I-VIII groups, and the coefficients a, b, c and d depend on the method of preparation of the zeolite, or zeolite type Y or mordenite or beta; zeolites (after synthesis) can be modified by items I, II, III, VI and VIII groups; zeolites, including modified, prepared by the known methods. The composition of the catalyst of oxides of elements I, II, III, VI groups described General formula (aCuO+bZnO+cAl2O3+dCr2O3+eW2O5), where a=0-60, b=24-67, C=0-10, d=0-33, e=0-1 wt.The main advantages of the proposed method are higher octane number gasolines produced.The main distinctive feature of the invention, the implementation stage contacting of the feedstock with the catalyst in the presence of carbon monoxide II and/or carbon monoxide IV.Industrial applicability of the invention is illustrated as follows: example 1 prototype examples 2-6 equivalents of the prototype and is shown for comparison, examples 7-33 the proposed method.P IS SUB>5+0,1) is subjected to contacting with the catalyst in the environment of hydrogen at a molar ratio of N2/CH=3, a temperature of 300aboutWith and the weight of the feed rate of the raw material 1 h-1. The catalyst contains, by weight, 80. zeolite H-ZSM-5 and 20% AlF3. In the contact formed 75% of hydrocarbon gases and 25% gasoline5+containing 52% of aromatic hydrocarbons.P R I m m e R 2. Straight-run gasoline fraction 40-150aboutWith octane PTS= 62 MM and the composition is shown in table. 3, is subjected to contacting with the catalyst 1 (composition shown in table. 2) in the environment of hydrogen at the reaction temperature Tp=380aboutC, pressure P=8.0 MPa, the mass feed rate of the raw material g=1.5 h-1and flow rate of gas (hydrogen) W=2300 h-1. The reaction products separated from the allocation of 17.5 wt. hydrocarbon gases and 82.5% gasoline PTS=69,3 MM and composition is shown in table. 3.P R I m e R 3. Analogous to example 2. Model hydrocarbon fraction 68-146aboutWith the estimated octane OCHp=46 MM and the composition is shown in table. 4, is subjected to contacting with the catalyst 1 (composition shown in table. 2) at Tp= 380aboutC, P=8.0 MPa, g=1.4 CH-1and W=3000 h-1. Prva, are given in table. 4.P R I m e R s 4-6. Analogous to example 2. Hydrocarbons hexene-1 is subjected to contacting with the catalyst in the environment of hydrogen at the reaction temperature Tp, the pressure P, the mass feed rate of the raw material g and the volumetric rate of gas supply W. Products contact share with gaseous and liquid (gasoline) fractions. The process conditions are given in table. 1, the compositions of the catalysts in table. 2, the compositions obtained gasoline fractions in the table. 5.Examples 7-33 the proposed method.P R I m e R 7. Straight-run gasoline fraction 40-150aboutWith octane PTS=62 MM and the composition is shown in table. 3, is subjected to contacting with the catalyst 1 in the presence of CO and CO2in the environment of the hydrogen-containing gas composition, vol. H267,1; 30,0; CO20,3; CH4+N22,6. The process of contacting is carried out at a reaction temperature Tp=380aboutC, pressure P=8.0 MPa, the mass feed rate of the raw material g=1.5 h-1, space velocity gas W=2300 h-1and the molar ratio of N2/CO+CO22.2 and CO/CO2100. Hydrocarbon reaction products separated with the separation of 19.4 wt. hydrocarbon gases and 80.6% gasoline fraction with a logical example 7. In example 9 the molar ratio of N2/CO+CO220, and the ratio of CO/CO226. The process conditions are given in table. 1, the compositions of the catalysts in table. 2. outputs, composition and octane number of the gasoline obtained in table. 3.P R I m e R 10. Similar to example 7. The contacting with the catalyst 4 (composition shown in table. 2) in the environment of hydrogen gas (H250,3% about. WITH 48,9; CO20,05; N2-0,75) is subjected to model hydrocarbon fraction WITH6-C9with the estimated octane OCHp=-8 and composition is shown in table. 3, the contacting is carried out at Tp= 420aboutC, P= 4.0 MPa, g=1.4 CH-1W=1540 h-1N2/CO+CO21,0 and CO/CO21000. Hydrocarbon reaction products separated with the separation of 30.5 wt. hydrocarbon gases and 69.5% gasoline-OCHp= 38 and composition is shown in table. 3.P R I m e R 11. Similar to example 7. The contacting with the catalyst 1 (composition shown in table. 2) in the environment of hydrogen gas (H267,1 about. WITH 30,0; CO20,3; CH4+N22,6) subjecting a hydrocarbon fraction 63-125aboutWith octane OCHp= 48 MM and the composition is shown in table. 4. The contacting is carried out at Tp=380
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