Method of refining
(57) Abstract:We propose a method of reformirovania oil by thermal treatment of the desalted oil on the package Ecumenical and/or aluminoborosilicate catalysts loaded in a mixture with elemental sulfur in the environment of hydrogen at elevated temperature and pressure, characterized in that before thermal treatment desalted oil is heated to 40-50oC and mixed with oxygen-containing compounds, taken in the amount of about 1-7. %; contacting the resulting mixture with the catalyst package is carried out at a temperature 330-410oC, a pressure of 20-150 MPa, followed by fractionation of the resulting product. table 2. The invention relates to the refining and petrochemical industry, in particular, to methods for processing of oil and gas condensate.Known methods of refining [1, 2] which includes the preliminary fractionation desalted and dewatered oil and subsequent processing of each of the oil fractions, require significant amounts of complex technological equipment, a large amount of different catalysts, Hydrotreating, reforming, catalytic cracking, and drive the x metals.The main task of processing the oil has traditionally been the allocation fractions of petroleum products, wikipaedia at certain temperatures. The process of such selection is based on the gradual destruction of the original oil lighter fractions by heating up. The process is known as rectification process (or distillation) of oil.The process of rectification (i.e., the separation of oil components of the hydrocarbon fraction by heating) defined the whole modern way of refining of crude oil.Since the most valuable light oil fractions, in the first place were traditionally developed oil with a high content of light distillates. With the development of transport and the chemical industry consumption of petroleum products, and especially bright, sharply increased, which led to the exhaustion of deposits of oils with a high content of light petroleum products.In connection with the reduction of selecting light of new varieties of crude oil on the one hand and the increasing demand on the other, widely developed processes for deep processing of oil.Deep processing of oil is currently underway for residual oil, sostoyalas oil currently on the best refineries, according to approximately 85% of this Practically means, the result of this processing 85% of the original oil turns into a light oil. The remainder is either remains in the form of heavy residues, or converted into hydrocarbon gases.The problem of deepening refining is becoming increasingly important because of the tendency to deterioration of the oil quality is still growing. Deep processing of oil currently represents a serious problem. This is primarily due to technical difficulties deeper processing of oil: low degree of transformation of serosoderjaschei compounds in the Hydrotreating, increased gas formation in catalytic cracking processes, etc.One of the ways of solving the problem of increasing the output of light oil products, decreasing the material and obtain low-sulfur fuel oil and coke in the processing of high-sulfur heavy oil is changing the approach to refining.Currently, the methods of separate hydrofining of petroleum fractions: gasoline, kerosene, diesel fractions. There are publications on the Hydrotreating of the heavy oil feedstock [3-6]
However, currently known approaches to hydroblock solution to the technical essence and the achieved result is a method of Hydrotreating a hydrocarbon feedstock, in particular vacuum gasoil go deasphalting residual oil  However, this method also does not allow for hydrofining oil or gas condensate at the stage of preliminary processing, i.e. before fractionation, when composed of a wax substance.The aim of the invention is to increase the output of light oil products and receipt of petroleum products with improved environmental characteristics.This goal is achieved by thermal treatment of demineralized feedstock in the presence of Ecumenical and/or aluminoborosilicate catalyst in the environment of hydrogen at elevated temperature and pressure, provided that before thermal processing of the feedstock is pre-heated to 40-50oC and mixed with a lower aliphatic alcohol, taken in the amount of 1,0-7,0 about. and the treatment is carried out in the presence of catalysts loaded in a mixture of elemental sulfur at a temperature 330-410oC, the pressure of 204,150 ATI with subsequent fractionation of the resulting product.A distinctive feature of the proposed method is that before thermocatalytic is that taken in the amount of 1,0-7,0 about. and the treatment is carried out in the presence of catalysts loaded in a mixture with elemental sulfur at a temperature 330-410oC, a pressure of 20-150 MPa, followed by fractionation of the resulting product.The basis of the proposed method of refining is the process of hydrofining oil with subsequent separation into fractions. During hydrofining oil flow processes Hydrotreating, light cracking in the environment of hydrogen. The result is the obtaining of oil with low content of sulphur, nitrogen and heavy metals. In addition, significantly increased the yield of liquid light hydrocarbons.Preliminary preparation desalted and dewatered oil by mixing and heated to 40-50oC with a specified number of lower aliphatic alcohols modifies the micellar structure of oil and facilitates what is happening in the hydrofining mixture of light cracking, which increases the yield of light fractions with a lower content of sulfur compounds.In the known methods of refining the application of the described technology is unknown. Therefore, this solution meets the criteria of "novelties is mi physico-chemical characteristics:
density 8620 kg/m3,
the viscosity at 20oFrom 23.1 mm2/s
content, wt.paraffin 2,95
coking ability of 5.9%
output fractions, about.70-180oC 12
99 ml of oil specified composition was mixed with 1 ml of ethanol and heated to a temperature of 40oC.The resulting mixture was subjected to hydrofining at a temperature of 330oC, hydrogen pressure of 20 MPa at lookbetteronline.com catalyst.Conducted fractionation obtained hydrogenated feed is cut, the results of which are given in table. 2.The parameters of the process, the raw materials used catalyst are given in table. 1. The quality of the product according to examples 2-6 are shown in table. 2. The sequence of operations used to test a sample of oil when running examples 2 to 6 is similar to example 1.When carrying out examples 1-5 (table. 1) contacting the mixture is carried out with the catalyst loaded in the reactor in a mixture with elemental sulfur.As seen from the above table. 1 and 2 data, the proposed method can significantly improve whoolesale feedstock in the presence of Ecumenical and/or aluminoborosilicate catalyst in the environment of hydrogen at elevated temperature and pressure, characterized in that before thermal processing of the feedstock is pre-heated to 40 50oWith and mix with a lower aliphatic alcohol, taken in quantities of 1 to 7. and the treatment is carried out in the presence of catalysts loaded in a mixture with elemental sulfur at 330 410oC, 20 to 150 MPa, followed by fractionation of the resulting product.
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