How hydroperiod of crude oil
(57) Abstract:The invention relates to the refining of crude oil and, in particular, to the Hydrotreating of petroleum distillates. When hydroperoxidation processing distillates and mixtures thereof with the remnants happens piling and deactivation of catalysts, ORGANOMETALLIC compounds and deposition of coke. To increase the service life of the catalyst and increase their activity proposed 2-stage method of Hydrotreating, where under hydroptherapy serves the catalyst in the following ratio, wt. %:
The molybdenum trioxide - 10,0-15,0
Oxide of Nickel or cobalt - 2,0-5,0
Oxide titanium (H2TiO3:TiOSO4)=2:1 to 1:2 - 0,05-2,0
Iron phosphate is 0.5 - 2,00
Alumina - Rest
table 4. The invention relates to a method for hydrogenation refining of crude oil in the presence of a catalyst and hydrogen and can be used in the oil industry.When hydrogenation refining of petroleum distillates and mixtures thereof with the remnants happens piling and deactivation of catalysts, ORGANOMETALLIC compounds of vanadium, Nickel, teleseminar two-stage methods hydroperiod of crude oil. A method of obtaining petroleum fractions /1/ in which to increase the stability and lifetime of the catalyst in the Hydrotreating process is carried out in two stages with the preliminary preparation of raw materials. The depth of vacuum gasoil hydrodesulphurization unit in such a process is not less than 84-87
There is also known a method of hydroperiod /2/, which is carried out with the prior hydropedological raw materials at two different catalysts hydroptherapy and Hydrotreating.The process of hydroperiod preliminary hydropedological vacuum gasoil 350-560oC (sulfur 1.9 wt. the nitrogen of 0.14 wt. coking ability of 0.52 wt. the total content of vanadium and Nickel 3 g/t) performed at a pressure of 3-10 MPa, a temperature of 330-420oC flow rate in zone hydroptherapy raw materials 2-15 h-1and Hydrotreating zone 1-10 h-1when the ratio of the catalysts in the area of training and Hydrotreating 1:1 to 1:20, the circulation of the hydrogen-containing gas 300-1000 nm3/m3of raw materials.As catalysts for Hydrotreating use catalysts based on aluminum oxide-modified additives and promoted with metals of IV-VIII groups.The depth of vacuum gasoil hydrodesulphurization unit in such a process some the result is a two-step method hydroperiod /3/, performed preliminary hydropedological raw materials at two different catalysts hydroptherapy and Hydrotreating.The process of hydroperiod preliminary hydropedological vacuum gasoil 350-560oC (sulfur 19000 ppm nitrogen 1300 ppm, coking ability of 0.52 wt. the total content of vanadium and Nickel 3 g/t) are, for example, at a pressure of 5 MPa, a temperature of 360oC flow rate in zone hydroptherapy raw materials 1-2 h-1and Hydrotreating zone 1-10 h-1when the ratio of the catalysts in the area of training and Hydrotreating 2-1, the circulation of the hydrogen-containing gas 500 nm3/m3raw materials in the presence of catalysts hydroptherapy and Hydrotreating containing oxides of molybdenum, Nickel or cobalt, aluminum and silicon.The depth of vacuum gasoil hydrodesulphurization unit in such a process is not less than 93,5
The aim of the present invention is to increase the degree of purification of the feedstock.This goal is achieved by the described method hydroperiod of crude oil, including preliminary hydroptherapy catalyst containing oxides of molybdenum, Nickel or cobalt, aluminum, iron phosphate, titanium oxide in the form of sosnowego sulfate titanium, taken in a molar ratio from 2:1 to 1:2 and stage Hydrotreating when the ratio of the catalysts is from 1:1 to 1:20 at elevated temperature and pressure with a ratio of catalyst components of hydroptherapy, wt.The molybdenum trioxide 10,0-15,0
Oxide of Nickel or cobalt 2,0-5,0
Oxide titanium (H2TiO3:TiOSO4)=2:1 to 1:2 0,05-2,0
Iron phosphate is 0.5-2,00
The major difference of the proposed method is the use of being hydroptherapy of the above catalyst composition in which titanium oxide is formed using a mixture matutinovic acid at a molar ratio from 2: 1 to 1:2, modifier alumina and allowing increasing the level of treatment, and the effectiveness of the proposed method.The process is performed at a pressure of 3-10 MPa, a temperature of 330-420oC, flow rate in the zone of hydroptherapy raw materials 2-15 h-1and in the Hydrotreating zone 1-10 h-1when the ratio of the catalysts in the area of hydroptherapy and Hydrotreating from 1:1 to 1:20, the circulation of the hydrogen-containing gas 300-1000 nm3/m3of raw materials.As catalysts for Hydrotreating use catalysts based on aluminum oxide, modifica is Ethan, promoted by metals IV or VIII group.Comparison of the proposed method with the prototype shows that it is used in the catalyst composition of hydroptherapy titanium dioxide produced using metatitanate acid and basic titanium sulfate in a molar ratio of 2:1 to 1:2, which corresponds to the criterion "novelty".A comparison of the proposed technical solutions with other known in the art solutions shows that the use of under hydroptherapy catalyst containing from 0.05 to 2.0 titanium oxide obtained with the use of acid and basic sulfate in a molar ratio from 2: 1 to 1:2 is unknown and selected by the authors due to the fact that the combination in one catalyst titanium dioxide produced using metatitanate acid and basic titanium sulfate along with Ni, Co, Mo and alumina, as shown by the authors, not only increases gidroobesserivaniya activity but also significantly increases the activity of removal of nitrogen compounds, especially for removing basic nitrogen, which has a positive impact on the subsequent stage of Hydrotreating and thereby ensures high stability of the catalyst and S="ptx2">Thus, the claimed technical solution meets the criterion of "substantial differences".Example 1. Raw diesel distillate (diesel fraction 180-350oC), straight-run in a mixture with secondary distillate oil has the following characteristics: a density of 860 kg/m3the sulfur 13000 ppm; nitrogen content of 300 ppm. Hydroptherapy diesel distillate at a temperature of 340oC, space velocity of the raw materials 3.5 h-1the circulation of the hydrogen-containing gas 200 nm3/m3of raw materials. Catalyst hydroptherapy prepared as follows. To 250 aluminium hydroxide with a humidity of 85 wt. add phosphoric acid with a concentration of 60 to pH values obtained mass of 6.5. To the resulting mass with stirring, add 0.15 g of aqueous slurry of phosphate of iron with a dry matter concentration of 62 (0.2 g pulp mixture of metatitanate acid and basic titanium sulfate (1:1) in aqueous solution of TiCl4with the concentration of TiO260), then add nitric acid with a concentration of 70 to pH of 3.0. The resulting mass is maintained with stirring and at a temperature of 60oC for 0.3 hours, then add aqueous ammonia with a concentration of 12 to pH values of 6.5 and evaporated mass 5 h Obtained granules carrier impregnated with a mixed solution of Nickel nitrate and para-molybdate of ammonium in the 15-dimensional solution of ammonia, dried at a temperature of 120 oC 3 h and calcined at a temperature of 400oC 5 o'clockThe mass ratio of the catalysts I and II stage 1:20. In table. 1 the data on quality product hydroperiod (hydrogenator) received the described and known ways. The latter is performed on similar raw materials (diesel fraction) at a temperature of 340 oC, space velocity of the raw materials 3.5 h-1the circulation of the hydrogen-containing gas 300 nm3/m3of raw materials.Example 2. As raw materials use of vacuum gasoil 350-500oC West Siberian oil containing 18000 ppm sulfur, 1300 ppm of nitrogen, including 400 ppm primary, 1 g/t metals (V+Ni), with coking ability of 0.27 wt. Hydroperiod vacuum gasoil performed at a pressure of 5.0 MPa, a temperature of 340oC, flow rate of the raw material 1,0 h-1the circulation of the hydrogen-containing gas 500 nm3/m3on the catalysts, taken in a mass ratio of 1:8 and having the following composition, wt. (see PL. 2).In table. 2 shows the data on quality product hydroperiod obtained described and known ways. Last conducted using as raw vacuum gas oil 350oC-540oC when asego gas 500 nm3/m3of raw materials.Example 3. As raw materials use of vacuum gasoil 350-500oC in a mixture with oil. Used mixture has the following characteristics: sulfur content 19000 ppm nitrogen total 1350 ppm, primary 600 ppm, cocking behavior 1,0 wt. the metal content of V+Ni 10 g/T. Hydroperiod feedstock is carried out at a pressure of 5.0 MPa, a temperature of 360oC, flow rate of feed of 1.0 h-1and circulation of hydrogen containing gas 500 nm3/m3when the mass ratio of catalyst 1:1 having the following composition, wt. (see tab.4).From the data table. 4 it follows that the desulfurization is 91,5 Rel. the degree of diazotoluene 36,2
The resulting hydrogenation product meets the requirements for low-sulfur raw materials for the catalytic cracking of the residual sulfur (not more than 1300 ppm), heavy metal content (not more than 3 g/t) coking ability (not exceeding 0,5-0,0).Thus, comparison of data obtained using the described method with the known method, shows that the degree of purification increases in the case of a diesel fraction 0.3 Rel. (example 1), vacuum gas oil 350-500oC 4.7 Rel. (example 2). Using the mixture of vaskovo cracking type G-43-107. How hydroperiod crude oil in two stages by pre-hydroptherapy feedstock in the first stage in the presence of a catalyst containing molybdenum trioxide, Nickel oxide or cobalt, aluminum oxide, and Hydrotreating of the products obtained in the second stage in the presence of the oxide catalyst is carried out at elevated temperature and pressure, characterized in that in the first stage using a catalyst, optionally containing patikis phosphorus, iron phosphate and oxide of titanium derived from a mixture of metatitanate acid and basic titanium sulfate, taken in a molar ratio of 1 2 2 1, in the following ratio, wt.The molybdenum trioxide 10 15
Oxide of Nickel or cobalt 2 5
Patikis phosphorus 1 5
Iron phosphate 0,05 0,1
Oxide titanium of 0.05 to 2.0
and the method is carried out at a mass ratio of the catalysts of the first and second stages 1 1 1:20.
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
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