The method of hydrotreating petroleum fractions
(57) Abstract:
The invention relates to the refining, in particular to a method of Hydrotreating petroleum fractions. We propose a method of Hydrotreating petroleum fractions, comprising contacting the feedstock at elevated temperature and pressure with a catalyst containing, wt.%: Nickel oxide 2,5-4,0; molybdenum oxide 8,0-11,0; phosphorus oxide of 0.5 to 1.3; boron oxide of 0.3-1.0 and pre-processed sequentially elementary sulfur in a quantity of 1.0 to 2.5% by weight of catalyst at a temperature of 120-140oAnd hydrogen sulfide-containing gas at a temperature of 150-250oC. the Method provides a residual sulfur content in the product 0,030-0,045%. 1 C.p. f-crystals. The invention relates to methods of Hydrotreating distillate oil fractions and can be used in the oil industry.The known process hydrodesulphurization unit in the reactor, containing two layers of catalyst.The hydrodesulphurization unit oil fractions is carried out in a reactor in which two layers of catalyst are arranged successively at different levels. First, the raw material is in contact with a catalyst containing 8-20% metals VI-VIII groups of the Periodic system (Co-Mo, Ni-Mo, Ni-W is achieved (Ti) in an amount of 2.5-8%The Hydrotreating is carried out at 343-427oC, partial pressure P 70-210 al, three-dimensional velocity Vc0,2-1,25 h-1the circulation rate of hydrogen 360-1780 nm3/m3raw materials and the molar ratio of hydrogen:feedstock equal 4-80:1. By passing the feedstock over apromotional catalyst, the degree of removal of sulfur and metals reaches > 80% [1]
The disadvantage of this method is that at a pressure of less than 45 MPa and a flow rate more than 2.0 h-1is not provides the hydrogenated feed is cut with a sulfur content less than 0.05% in order To obtain a desired depth of the sulfur removal process is carried out at high pressure and low flow rate.Known Hydrotreating process, which is conducted in flow-through mode in two series-connected areas. The Hydrotreating catalyst in area 1 contains, 2-4 Ni; Mo 8-15; P 1-4. Catalyst II zone contains Co and/or Ni 2-4; Mo 8-15 and P is 0.5. As the carrier used Al2ABOUT3. This process also does not provide a sufficient degree of hydrodesulphurization unit.Also known process hydrobromide vacuum gas oil, which is carried out on the catalyst containing NiO 1-8; NGO35-30; P2ABOUT56-38 and Al2O3
Molybdenum oxide 8,0 11,0
The phosphorus oxide 0,5 1,3
The boron oxide 0,3 1,0
Alumina Rest
and pre-processed sequentially elementary sulfur in a quantity of 1.0 to 2.5% by weight of a catalyst at a temperature of 120 140oAnd hydrogen sulfide-containing gas at a temperature of 150 250oC.2. The method according to p. 1, wherein the Hydrotreating is carried out at a temperature of 335 375oC, a pressure of 3.5 to 4.5 MPa, the space velocity of the raw material 2,5 4,0 h-1the ratio of the circulation of the hydrogen-containing gas 200 300 nl/l of raw materials.
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: 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 catalysts.
SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.
EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.
8 cl, 1 tbl, 7 ex
FIELD: isomerization and disproportionation catalysts.
SUBSTANCE: invention relates to crystalline α-chromium oxide, chromium-containing catalytic compositions, method for preparation thereof, and to a process of fluorine distribution in hydrocarbon and/or halogenated hydrocarbon in presence of indicated catalytic compositions. In claimed α-chromium oxide, about 0.05 to about 2 atomic % chromium in the lattice of α-chromium oxide is substituted by nickel atoms and, optionally, further chromium atoms in the lattice are substituted by trivalent cobalt atoms, the total amount of nickel and trivalent cobalt atoms in the α-chromium oxide lattice not exceeding 6 atomic %. Claimed α-chromium oxide is prepared via coprecipitation of solid substance by introducing ammonium hydroxide, this method being supplemented by introducing an excess of ammonium nitrate into precipitated mixture before dehydration step and calcination step at 375 to 1000°C in presence of oxygen. Chromium-containing catalytic compositions containing crystalline nickel-substituted α-chromium oxide as chromium-containing component optionally treated with fluorination agent are also claimed. Composition preparation procedure comprises: (a) coprecipitation of solid substance by introducing ammonium hydroxide into aqueous solution of soluble bivalent nickel salt, soluble trivalent chromium salt, and optionally soluble bi- or trivalent cobalt salt, wherein solution contains at least three moles nitrate per mole chromium and has concentration of nickel from about 0.05 to about 2 mol % based on total content of nickel, chromium, and cobalt (if present) in solution and total concentration of nickel and cobalt (if present) not higher than 6 mol % on the same basis; (b) collecting coprecipitated solid substance obtained in step (a); (c) drying collected solid substance; and (d) calcination of dried solid substance at 375 to 1000°C in presence of oxygen.
EFFECT: increased activity of catalytic composition in above-indicated processes.
15 cl, 8 dwg, 13 ex
FIELD: petroleum processing.
SUBSTANCE: invention relates to preparation of protective-layer catalysts for hydrofining of petroleum fractions in petroleum processing industry. Invention provides catalyst containing oxides of molybdenum, nickel and/or cobalt, silicon, and aluminum, which catalyst is molded in the form of hollow cylindrical granules. Starting composition for preparation of alumina-based carrier includes structuring additive, 5.0-8.5%, kaolin, 2.0-5.0%, and alumino-nickel-molybdenum and/or alumino-cobalt-molybdenum catalyst, 10-20%. Thus prepared alumina-supported contains 0.5-4.0% nickel oxide and/or cobalt oxide and 0.8-3.0% silicon oxide.
EFFECT: increased degree of hydrogenation of unsaturated hydrocarbons, prevented coking of basic catalyst, and reduced pressure gradient.
3 cl, 4 ex
FIELD: chemistry.
SUBSTANCE: principle refers to catalyst and method of complex purification of waste gases of different production, heat and power utilities, automobile transport, which works on natural gas (methane). Described is a method of complex purification of effluent gases from nitrogen oxides, carbon oxide and hydrocarbons and it involves passing the effluent gases at temperatures 455-600°C through a layer of mechanical mixture of nickel chromium oxide industrial catalyst a copper zink nickel industrial catalyst in a volume composition of 1:1 to 20:1 respectively. To the effluent gases, methane up to a volume composition of CH4/O2 0.07-0.15 can be added before passing it through the catalyst layer. Nickel chromium oxide industrial catalyst contains NiO 38-42 %; ZnO 28-32 %; NiO 4-6 % and not less than Al2O3 17 % masses.
EFFECT: increasing of the purifying index of effluent gases.
3 cl, 4 ex
FIELD: chemistry.
SUBSTANCE: claimed invention relates to catalysts of hydration, method of their production and use for hydration such as selective hydration of acetylene admixtures in non-purified olefinic and diolefiniuc flows. Described is a selective catalyst of hydration for selective hydration of acetylene admixtures in non-purified olefinic and diolefinic flows, containing only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, applied on carrier, which is alumunium oxide with the following physical characteristics: BET surface area from 30 to approximately 100 m2/g, total volume of pores on nitrogen from 0.4 to approximately 0.9 cm3/g and the average pore diameter from approximately 110 to 450 Å , where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Described are the method of catalyst production, which includes impregnation of carrier represented by aluminium oxide and having the aforesaid physical characteristics, with soluble salts of only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, from one or more solutions, obtaining impregnated carrier, where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Also described is the method of selective hydration of acetylene compounds, which includes contact of original raw material containing acetylene compounds and other unsaturated compounds, with the described above catalyst.
EFFECT: increased degree of 1,3-butadien extraction with full or nearly full conversion of C4-acetylenes.
25 cl, 1 dwg, 1 tbl, 2 ex
FIELD: technological processes.
SUBSTANCE: invention is referred to technological processes, namely to ways of realisation of chemical processes, in particular, to area of the general and specific catalysis. The method of catalytic element manufacturing, including preparation of catalytically active coating by spraying of a powder composition on the metal carrier using high-speed cold gas-dynamic method is described. The powder composition contains in wt %: aluminium 30-50, nickel 30-45, oxide of transition metals 1-6, oxides of rare-earth metals in the sum 1-6, alpha oxide of aluminium 5-25, aluminum hydroxide - the rest. Simultaneously with spraying of the same powder composition an erosive handling of the metal carrier surface is performed. At temperature not exceeding 100°C spray a powder composition on distance of 40-70 mm from the metal carrier at speed of a composition stream of 450-600 km/s with 50-200 microns coating.
EFFECT: increase of mechanical strength of a catalytic element, high activity of catalytically active coating.
1 cl, 1 ex
FIELD: chemistry.
SUBSTANCE: description is given of a catalytic composition with general formula, in consideration of oxides: (X)b(M)c(Z)d(O)e (I), in which X represents at least one group VIII base metal, M represents at least one group VIB metal, Z represents one or more elements, chosen from aluminium, silicon, magnesium, titanium, zirconium, boron and zinc, O represents oxygen, one of b and c represents an integer 1, and d, e and one of b and c represents each a number bigger than 0, such that the molar ratio b:c ranges from 0.5:1 to 5:1, molar ratio d:c ranges from 0.1:1 to 50:1, and molar ratio e:c ranges from 3.6:1 to 108:1. The method of obtaining the composition involves heating a composition with general formula (NH4)a(X)b(M)c(Z)d(O)e (II), in which a represents a number bigger than 0, and X, M, Z, O, b, c, d and e are such that, they are bigger, at temperature ranging from 100 to 600°C, where the composition with formula II is in suspension form or is extracted from a suspension, optionally after maturing at temperature ranging from 20 to 95°C for a period of not less than 10 min. The above mentioned suspension is obtained by precipitation at temperature and within a period of time, sufficient for obtaining formula II composition, of at least one compound of a group VIII base metal at least one compound of a group VIB metal at least one refractory oxide material and alkaline compound in protonic liquid. At least one of the metal compounds is partially in solid state and partially in dissolved state. Description is given of volumetric metal oxide catalytic composition, obtained using the method given above, and a composition with general formula I, which can be obtained using a precipitation method, in which a refractory oxide material in quantity ranging from 15 to 40 wt % is precipitated at least with one compound of a group VIII base metal, and at least with one compound of a group VIB metal, as well as the method of obtaining it. Description is also given of the use of compositions, moulded or sulphided when necessary, in hydro-processing.
EFFECT: increased activity of catalytic compositions.
14 cl, 10 tbl, 24 ex
