The method of obtaining petroleum fuels with improved environmental characteristics
(57) Abstract:We propose a method of extracting petroleum fuels with improved environmental characteristics in the presence of alumina catalysts, pre-activated elementary sulfur, characterized in that the package alumina catalysts is at least 50% aluminoborosilicate catalyst containing molybdenum oxide 12 to 18 wt.%, oxide of cobalt, 3 to 6 wt.%, obtained by mixing with a suspension of cobalt molybdate in the hydrogen peroxide solution, aluminium hydroxide, treated with nitric acid in two steps - the first part of the aluminium hydroxide is treated with concentrated nitric acid for 0.5 - 2.0 hours at 20 - 80oC and a molar ratio of the aluminum hydroxide: nitric acid(1: 0,64) - (1: 1,92), and then the obtained product of the interaction of aluminium hydroxide with nitric acid is mixed with the rest of aluminium hydroxide at 20 - 80oC and the mass ratio of the product : aluminium hydroxide in terms of alumina (1.5 to 3.0) : 100, followed by forming, drying and calcination of the obtained product, the second component of the catalytic system is aluminumalloy catalyst. 3 CCI.Known methods of Hydrotreating of petroleum distillates in the medium of hydrogen using Ecumenical and aluminoborosilicate catalysts [1-3]
The closest in technical essence and the achieved effect is way hydrodesulphurization unit of hydrocarbons in the presence of pre-solifidian catalysts containing Nickel and molybdenum, cobalt and molybdenum 
The disadvantage of this method is insufficient hydrofining produced during the hydrotreatment of petroleum fractions.The purpose of the invention obtaining the hydrogenated feed is separated middle distillate fractions with sulfur content not more than 0.05 wt. aromatic hydrocarbons of not more than 20 wt.This goal is achieved by a method of obtaining petroleum fuels with improved environmental characteristics by hydrodesulphurization unit of hydrocarbons in the presence of alumina catalysts, pre-activated elementary sulfur, provided that the process is conducted in the presence of aluminoborosilicate catalyst composition, wt. molybdenum oxide 12,0 18,0, cobalt oxide 3,0 6,0 obtained by mixing with a suspension of cobalt molybdate in solution of hydrogen peroxide of haste aluminium hydroxide with concentrated nitric acid for 0.5 to 2.0 hours at 20 80oC, molar ratio of the aluminum hydroxide nitric acid (1 0,64) (1 1,92) in the first stage and the mixing product of the interaction of aluminium hydroxide with nitric acid with the rest of aluminium hydroxide at 20 80oC, the mass ratio of the product aluminium hydroxide in terms of alumina (1.5 to 3.0) 100 in the second stage, followed by shaping, drying and calcining the resulting product, or in the presence of a catalytic system containing at least 50 wt. aluminoborosilicate catalyst of specified composition and received the agreed way and alumnirelations catalyst.The hallmark of the invention is that the process is conducted in the presence of aluminoborosilicate catalyst composition, wt. molybdenum oxide 12,0 18,0, cobalt oxide 3,0 6,0 obtained by mixing with a suspension of cobalt molybdate in the hydrogen peroxide solution, aluminium hydroxide, pre-treated with nitric acid in two stages - the initial processing parts of aluminium hydroxide with concentrated nitric acid for 0.5 to 2.0 hours at 20 80oC, molar ratio of the aluminum hydroxide nitric acid (1 0,64) (1 1,92) in the first stage and smashin the 80 and 20oC, the mass ratio of the product aluminium hydroxide in terms of alumina (1.5 to 3.0) 100 in the second stage, followed by shaping, drying and calcining the resulting product, or in the presence of a catalytic system containing at least 50 wt. aluminoborosilicate catalyst of specified composition and received the agreed way and alumnirelations catalyst.Used in the Hydrotreating process aluminoborosilicate catalyst obtained as described above, increases the degree of conversion of sulfur-containing compounds and saturation of aromatic hydrocarbons by obtaining aluminum oxide with a specific acid-basic properties and distribution of active ingredients that contribute to getting on the catalyst surface the optimal number of active sites responsible for the reactions of hydrodesulphurization unit and dearomatization.The use of a catalytic system consisting of allocability alumonickelsilicate catalysts, valid when the content in the raw material is high (above 25 wt.) aromatic hydrocarbons, since the use of such a catalytic system creates a synergistic effect is Ogii unknown.Examples.Tests of the invention were conducted on three samples of raw materials, the main characteristics of which are given in table. 1.Tests were conducted on samples aluminoborosilicate catalysts synthesized in accordance with the proposed formula of the invention listed in table. 2. When using the catalytic system was applied aluminumalloy catalyst containing molybdenum oxide 18 wt. Nickel oxide 6 wt. The Hydrotreating process was carried out at 360oC, hydrogen pressure of 3.0 MPa.Direct catalytic composition of the package with the indication used for Hydrotreating raw settings Hydrotreating and quality of the obtained hydrogenated feed is separated in examples 1 to 7 shown in table. 3. In this same table shows the sulfur content in the resulting product, as well as similar data for carrying out the process in a known manner (example 7). Examples 1, 2 and 6 are made in accordance with the proposed invention. Examples 3, 4 and 5 shows how the beyond.Implementation of a prototype in the form of raw materials such results does not. Change ratio Ecumenical and aluminoborosilicate catalysts, technology prigot"ptx2">The method of obtaining petroleum fuels with improved environmental characteristics by hydrodesulphurization unit of hydrocarbons in the presence of alumina catalysts, pre-activated elemental sulfur, wherein the process is conducted in the presence of aluminoborosilicate catalyst composition, wt.Molybdenum oxide 12 18
The cobalt oxide 3 6
obtained by mixing with a suspension of cobalt molybdate in the hydrogen peroxide solution, aluminium hydroxide, pre-treated with nitric acid in two stages: initial processing parts of aluminium hydroxide with concentrated nitric acid for 0.5 to 2.0 hours at 20 80oWith a molar ratio of the aluminum hydroxide nitric acid 1 0,64 1,92 in the first stage and the mixing product of the interaction of aluminium hydroxide with nitric acid with the rest of aluminium hydroxide at 20 80oWith, the mass ratio of the product: aluminium hydroxide in terms of aluminum oxide 1,5 3,0 100 at the second stage, followed by molding, drying, and annealing the resulting product in the presence of a catalytic system containing at least 50 wt. aluminosilicates catalyst is
FIELD: production of hydrorefining catalyst.
SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.
EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.
10 cl, 8 ex, 4 dwg
FIELD: petroleum processing catalysts.
SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.
EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.
40 cl, 2 tbl, 19 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.
EFFECT: enhanced hydrodesulfurization and hydrogenation activities allowing involvement of feedstock with high contents of sulfur and unsaturated hydrocarbons, in particular in production of environmentally acceptable motor fuels.
3 cl, 4 tbl, 13 ex
FIELD: petroleum refining industry.
SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.
EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.
7 cl, 2 tbl, 2 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.
EFFECT: improved performance characteristics of catalyst.
2 cl, 3 tbl, 10 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic system is prepared by consecutively charging into reactor alumino-cobalt and alumino-nickel-molybdenum catalysts containing 12.0-25.0% molybdenum oxide, 3,0-6.0% nickel oxide, and 3.0-6.9% cobalt oxide provided that alumino-cobalt and alumino-nickel-molybdenum catalysts are charged at ratio between 1.0:0.1 and 0.1:1.0, preparation of catalysts employs mixture of aluminum hydroxide and/or oxide powders, to which acids are added to pH 1-5. More specifically, aluminum hydroxide powder mixture utilized is a product of thermochemical activation of gibbsite and pseudoboehmite AlOOH and content of pseudoboehmite in mixture is at least 70%, and aluminum oxide powder mixture utilized comprises powders of γ-Al2O3 with particle size up to 50 μm and up to 50-200 μm taken at ratio from 5:1 to 2:5, or γ-Al2O3 powders with particle size up to 50 μm, 50-200 μm, and up to 200-400 μm taken at ratio between 1:8:1 and 3:6:1.
EFFECT: method of preparing catalytic systems for large-scale high-sulfur hydrocarbon feedstock hydrofining processes is provided allowing production of products with desired levels of residual sulfur and polycyclic aromatic hydrocarbons.
4 tbl, 3 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.
EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.
5 cl, 6 tbl, 12 ex
FIELD: petroleum processing catalysts.
SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.
EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.
FIELD: production of catalytic compositions.
SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.
EFFECT: enhanced efficiency.
29 cl, 8 ex
FIELD: petroleum processing.
SUBSTANCE: invention, in particular, relates to petroleum fraction hydrofining process utilizing presulfided catalysts. Hydrofining process is described involving contacting petroleum fractions with presulfided catalyst containing alumina-carried cobalt, molybdenum, phosphorus, and boron, said process being conducted at 320-340°C, pressure 3.0-5.0 MPa, volumetric feed supply rate 1.0-6.0 h-1, normalized volumetric hydrogen-containing gas-to-feed ratio (500-1000):1 in presence of catalyst sulfided outside of reactor. Sulfidizing of catalyst is accomplished with hydrogen sulfide at 80-500°C and volumetric hydrogen sulfide flow rate 0.02-6.0 h-1. Chemical composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O3 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and aluminum oxide - the balance.
EFFECT: simplified process.
2 cl, 1 tbl, 3 ex