The way to obtain environmentally friendly diesel fuel
(57) Abstract:The invention relates to the refining of crude oil and, in particular, to the Hydrotreating of petroleum distillates. When hydrogenation refining 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 - 10-15
Oxide of Nickel and cobalt - 2-5
Phosphate of aluminum is 1.5-10
Iron phosphate is 0.5 to 2.0
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, iron and coke deposits.For HC the weave of crude oil. There is a method of Hydrotreating of 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 80,0 and diesel fraction at least 90
The closest to the proposed invention is a method 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 1.68 wt. the nitrogen of 0.14 wt. coking ability to 0.7 wt. the total content of vanadium, Nickel and iron 3.8 g/t) is carried out at a pressure of 5 MPa, a temperature of 360-400oC and various space velocities of hydroptherapy and Hydrotreating.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 is not less than 89,0 and diesel fractions up to 96
The aim of the invention is to improve the processing of crude oil, including preliminary hydroptherapy catalyst containing molybdenum trioxide, Nickel oxide or cobalt, aluminum oxide, aluminum phosphate and iron phosphate at a molar ratio of aluminum phosphate to phosphate from 3:1 to 5:1 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
Phosphate of aluminium 1,5-10,0
Iron phosphate is 0.5-2,00
The major difference of the proposed method is the use of being hydroptherapy catalyst additionally containing aluminum phosphate and iron phosphate at a molar ratio from 3:1 to 5:1, the modifying oxide of aluminum 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/luminia, the modified zeolite or pjatiokisi phosphorus and iron phosphate or oxide of cerium, europium and zirconium or titanium oxide promoted with metals IV or VIII group.Comparison of the proposed method with the prototype shows that it is used in the catalyst composition of hydroptherapy phosphate of aluminum, which meets the criterion of "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 1.5 to 10.0 phosphate of aluminum and from 0.5 to 2.0 phosphate at a molar ratio of from 3 to 5 unknown and selected by the authors due to the fact that the combination in one catalyst of aluminum phosphate and iron phosphate 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 increases the degree of purification of the target product, improve the techno-eco is the criteria of "significant differences".Example 1. Raw diesel distillate (FR. 180-360oC) straight-in a mixture with diesel distillate Orenburg gas condensate has the following characteristics: a density of 860 kg/m3the sulfur 18000 ppm, a content of aromatic hydrocarbons 20% of the nitrogen content of 300 ppm. Hydroptherapy diesel distillate is carried out at a temperature of 340oC, a pressure of 4 MPa, space velocity of 3.0 HR-1the circulation of the hydrogen-containing gas 300 nm3/m3.The molar ratio of aluminum phosphate to phosphate 3. The ratio of catalysts I and II stage 1:20. In table. 1 shows the results of the hydrotreatment on offer (example 1) and by a known method.Example 2. As raw materials use of vacuum gasoil 350-540 oWith West-Siberian oil containing 19000 ppm sulfur, 1300 ppm of nitrogen, including 400 ppm primary, 1 g/t metals (V+Ni) and having a coking ability to 0.97 wt. Hydroperiod vacuum gasoil performed at a pressure of 5.0 MPa, a temperature of 370oC, flow rate of feed of 1.0 h-1the circulation of the hydrogen-containing gas 500 nm3/m3the catalysts taken in the ratio of 1:8 and having the following composition, wt. (see tab. 2).The molar ratio of the Foz method (example 2). The comparison shows that in the case of application of the method with the described catalyst degree of Hydrotreating to remove sulfur and nitrogen compounds above.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, including the main 600 ppm, cocking behavior 1,0 wt. the metal content (V+Ni) 10 g/T. Hydroperiod feedstock is carried out at a pressure of 5.0 MPa, a temperature of 380oC, flow rate of feed of 1.0 h-1and circulation of hydrogen containing gas 500 nm3/m3when the mass ratio of catalyst 1:1 and having the following composition, wt. (see tab. 3). The molar ratio of aluminum phosphate to phosphate 5. In table. 3 shows the results of the experiences described and the known methods. In case of application of the proposed method with the described system catalysts degree of desulfurization is 92,8 the degree of diazotoluene 36,2 Obtained hydrogenation product to meet demand for low-sulfur raw materials for the catalytic cracking of the residual sulfur (not more than 300 ppm), the concentration of heavy metals (not what the use of the proposed method with the known method, shows that the degree of purification increases in the case of Hydrotreating diesel fraction, especially aromatic and nitrogen compounds (it is necessary to improve the stability of diesel fuel), and the result is an environmentally friendly diesel fuel with sulfur content below 500 ppm and aromatic hydrocarbons below about 20. which corresponds to THE 38.1011348-90 in environmental diesel fuel, vacuum gas oil 350-540 oC 5.5 (example 2); and when the Hydrotreating a mixture of vacuum gas oil fuel oil (example 3) you can get a product that meets the requirements of raw material for installation type D-43-107 or CT-1. The degree of Hydrotreating and diazotoluene above. The application of this method in relation to the installation of the L-24-5 will allow you to get environmentally friendly diesel fuel and according to preliminary data, the economic effect from implementation of this invention will be about $ 500,000 per year. The way to obtain environmentally friendly diesel fuel in two stages by means of preliminary preparation of the feedstock in the first stage at elevated temperature and pressure in the presence of a catalyst containing molybdenum trioxide, Nickel oxide or cobalt, aluminum oxide, and Hydrotreating floor is a, containing molybdenum trioxide and the oxide of Nickel or cobalt, characterized in that in the first stage using the catalyst additionally containing aluminum phosphate and iron phosphate with a molar ratio of aluminum phosphate to phosphate 3 5 in the following ratio, wt.The molybdenum trioxide 10 15
Oxide of Nickel or cobalt 2 5
Phosphate of aluminium 1,5 10,0
Iron phosphate 0,5 2,0
and the method is carried out at a mass loading of the catalysts of the first and second stages of 1:1 to 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
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