The method of hydrotreating a wide condensate fraction
Usage: petrochemistry. Essence: conduct sequential contacting of the feedstock with the catalyst in the environment of the hydrogen-containing gas at elevated temperature and pressure, and the first stage is carried out in contact with low catalyst containing oxides of Nickel, cobalt and molybdenum, in the form of Raschig rings, the second low-level aluminumaluminium catalyst in the form of extrudates, the third high-level radioactive aluminoborosilicate catalyst in the shape of shamrocks. Effect: improved product quality, reduced pressure drop in the reactor and increase the turnaround of the reactor. 1 C.p. f-crystals, 1 table. The invention relates to a method of Hydrotreating a wide condensate fraction containing mercaptans and other sulfur compounds, and may find application in the oil and petrochemical industry.It is known that the increase of pressure drop in the reactor entails a forced shutdown for repairs and cleaning and is one of the most common problems faced by manufacturers. As shown by studies conducted on the lips of the population in the Hydrotreating reactor is the formation of a solid crust sediments in the upper layers of the catalyst. The composition of these sediments consists of mechanical impurities and corrosion products equipment introduced into the reactor with the flow of raw materials and coke formed during hydrotreatment. The formation of a solid crust of sediment leads to a decrease of free volume between the particles in the catalyst layer and, consequently, to the increase of pressure drop in height of the reactor. To resolve this problem in Russia and abroad, in addition to the pre-filtering of the raw materials Hydrotreating, use layer-by-layer loading of the catalyst in the Hydrotreating reactor so that the upper layers were the catalyst with large free volume of the layer of trapping unwanted impurities, providing a lower degree of Hydrotreating compared with the next layer. This feature stems from the fact that excessive activity of the catalyst in the upper layers can lead to undesirable polymerization, the formation of resins, and eventually coke from various compounds included in the composition of raw materials (for example, olefins, mercaptans, and so on).In the world practice Hydrotreating is used as alumonickelsilicate (AMN), and aluminoborosilicate (AKM) catalysts, if AMN predpochtitelen, that at moderately high sulfur content in the product and at moderately low pressure catalyst AKM finds the best performance compared with the catalyst of AMN [Mayo S., Brevard E., Gerritsen L., Plantago F. Oil and gas technology. - M. , 2001, 3, S. 91-93]. Thus, when carrying out Hydrotreating plays an important role in the composition of the catalyst and the fraction of free volume between the particles in the catalyst bed. The shape of the catalyst particles is the main factor determining the free volume of the catalyst layer. The more the outer surface of the particles, the more free volume of the layer. For catalyst particles of different forms free layer volume will increase in a row: spherical particles, extrudates, rings, hollow granules, tablets with holes.A method of obtaining environmentally friendly diesel fuel (RF patent 2044031, IPC 6 With 10 G 65/12), on which straight-run petroleum fraction or a mixture thereof with a fraction of the products of catalytic cracking, wikipaedia when 150-365oWith, is subjected to Hydrotreating in the first stage of the process in the presence of a catalyst. The catalyst contains molybdenum oxide - 7,0-18.0 wt. %, cobalt oxide or Nickel-2.0 to 9.5 wt.% and the aluminum oxide - rest. The guide is split). The second stage catalyst contains, in wt. %: platinum and/or palladium and 0.2-2 or a mixture of platinum and/or palladium and rhenium from 0.25 to 2.25 (including rhenium 0,05-0,25); chlorine 0.1 to 1.5, or a mixture of chlorine and fluorine 0,15-1,5; heat-resistant carrier - rest.The disadvantage of this method is that the catalyst of the second stage, containing in its composition VIII noble metals gr. and rare earth element VII gr. the periodic system of elements and require promotion halides, provide a high degree of purification from sulfur, nitrogen and oxygen-containing compounds, but has a higher cost compared with the catalysts of new generation, which contain oxides of molybdenum, cobalt, Nickel and aluminum.Closest to the proposed invention prototype is a method of Hydrotreating petroleum fractions (RF patent 1815993, IPC 6 With 10 G 65/04). According to this method, the feedstock in the first stage of the process is in contact with the catalyst at elevated temperature and pressure. The catalyst is a hollow cylindrical granules with an external diameter of 10-15 mm and inner 3-5 mm. It contains the oxide of Nickel 2.0 to 3.0 wt.%, molybdenum oxide - 3,0-4,0 wt.% and the aluminum oxide - rest. In the second stage of the process used Catala This method does not use expensive catalysts, containing precious metals and rare earth elements of the periodic system. Step-by-step Hydrotreating using alumonickelsilicate catalysts can improve the quality of the product. In addition, the shape of the catalyst and its composition provides reduced pressure drop in the reactor.The increase in pressure drop in the reactor is also solved by using the first stage Hydrotreating catalyst in the form of a hollow cylindrical granules, resulting in the upper catalyst layer has a large free volume for retention of undesirable impurities.The disadvantage of the prototype is that when the Hydrotreating of petroleum fractions using only alumonickelsilicate catalysts in the form of a hollow cylindrical granules, which limits the effect of the cleaning process. The task of improving the quality of the product in the prototype could not be fully resolved without the use of catalysts AKM.The task of the invention is to improve product quality and reduce pressure drop in the Hydrotreating reactor through the use of aluminoborosilicate and alumnirelations catalysts with different forms of particles, as well as through the application is achieved as follows. Straight wide condensate fraction is subjected to Hydrotreating sequentially on three layers of catalyst in the presence of hydrogen-containing gas at elevated temperature and pressure. As the catalyst for the first stage of use of the catalyst in the form of Raschig rings 15x15 mm diameter inner hole of 6 mm In the composition of the catalyst include Nickel oxide and cobalt (metals of group VIII) of 0.8 to 1.5 wt.% (total), molybdenum oxide is 3.5 to 4.5 wt.%, alumina - rest. In the second stage using the catalyst in the form of extrudates with a diameter of 3-4 mm composition: Nickel oxide and 1.5 - 2.5 wt.%, molybdenum oxide is 6.0-7.0 wt.%, alumina - rest. At the third stage of use of the catalyst in the form of shamrocks with a diameter of 1.2-1.5 mm composition: cobalt oxide to 4.0-5.0 wt.%, molybdenum oxide - 18,0-19.0 wt.%, alumina - rest. The mass ratio of the first, second and third layers of the catalysts is from 1:1,2:7,8 to 1:1,3:8,5.Low catalyst of the first stage of the process has a relatively large free volume of the catalyst layer for retaining unwanted impurities and softly hydroabrasive feedstock. In this case, thanks to the optimal composition of the catalyst are as reaction nasyshenost AMN mainly reactions proceed hydrodesulphurization unit and the saturation of arenes and on the third stage of the process on a highly active catalyst AKM is the greatest purification from sulfur compounds.Example.As an example, the results of tests conducted on the asnr.The original straight-wide gas-condensate fraction, wikipaedia within NK-350oWith and containing 0.6 to 0.8 wt.% total sulfur and 0.2 wt.% and more mercaptan sulfur was subjected to Hydrotreating. The parameters of the technological mode of Hydrotreating temperature in the reactor 310-350oWith; the pressure in the reactor is 3.2 to 3.7 MPa; the ratio of hydrogen gas: raw materials - 200-250 nm3/m3raw materials; the volumetric feed rate to the reactor - 4,5-5,0 h-1. Data turnaround runs Hydrotreating with different catalyst loading are presented in the table.The table shows that under the common scheme of loading of the catalyst, when the distribution plate into the reactor above the catalyst bed load layer porcelain balls (option I), the pressure drop in the reactor after 1968 hours exceeds its allowable value and 0.69 MPa. The increase in pressure drop in the reactor for a period of mileage should not exceed 0.3 MPa. This means that this scheme download catalysis loading scheme, when instead of porcelain balls were loaded inert ring process (option II), increased significantly overhaul mileage installation, and pressure drop through 4512 of hours the reactor was 0.5 MPa. This fact allows us to conclude that the inert ring process due to its shape creates a larger free volume of the catalyst layer for retaining unwanted impurities and thereby provide more effective protection for the next catalyst layer compared to inert porcelain balls.When the layer loading of the catalyst in the Hydrotreating reactor, when the protective layer was applied low catalyst (option III), the increase in pressure drop in the reactor per 1 million tons of recycled raw materials amounted to 0.44 MPa, which is 0.06 MPa lower than the scheme with inert rings process (option II). Option III and option IV (see table) differ from each other by the composition of the catalyst used in the second stage of the process. From the table it is seen that the most favorable conditions for equipment operation under other equal conditions provides a diagram of the layered charge of catalyst (option IV). When the layer loading is markedly reduced the increase in differential pressure is systematic processing of research results, held on the hydrotreatment of asnr, allowed us to calculate the duration of operation of the plant to an acceptable value of the differential pressure in the Hydrotreating reactor according to the height of the catalyst layer. For option I, this value was only 1000 hours, for options II and III is approximately 2300 h, and for option IV - approximately 8,000 hours (i.e. 1 year!).The table shows that the greatest degree of Hydrotreating occurs when the layer-by-layer catalyst loading (options III and IV), the degree of desulfurization in the fourth embodiment, 4.8 wt.% compared to option I, 10.5%, compared with option II and 2.6 wt.% compared with option III.Thus, this method allows you by using layer-by-layer loading of the catalyst in the Hydrotreating reactor significantly increases the turnaround mileage installation by reducing the differential pressure across the height of the catalyst layer, to increase the degree of Hydrotreating, i.e. to improve the quality of the product.
Claims1. The method of Hydrotreating a wide condensate fraction by contacting the feedstock in the layers of the catalysts in the presence of hydrogen-containing gas at elevated temperature, characterized in that h is isoactive catalyst in the form of Raschig rings, containing oxides of Nickel and cobalt in total, 0.8-1.5 wt.%, molybdenum oxide 3.5 to 4.5 wt.%, alumina rest, the second layer of low catalyst in the form of extrudates containing Nickel oxide 1.5 to 2.5 wt. %, molybdenum oxide 6-7 wt.%, alumina rest, and the third is a highly active catalyst in the shape of shamrocks, containing cobalt oxide 4,0-5,0 wt. %, molybdenum oxide is 18.0-19.0 wt.%, alumina rest, and the mass ratio of the first, second and third layers of the catalysts is from 1:1,2:7,8 to 1:1,3:8,5.2. The method according to p. 1, wherein the process is carried out at a temperature in the beginning of the process 310-350oWith the pressure of 3.2 to 3.7 MPa, the ratio of the hydrogen-containing gas:raw 200-250 nm3/m3raw materials and space velocity of the raw material on the third layer of the catalyst of 4.5-5.0 h-1.
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