The method of obtaining of raw materials of high-sulphur crude oil
(57) Abstract:We propose a method of obtaining of raw materials of high-sulphur crude oil by contacting desalted and dehydrated oil from Ecumenical and/or aluminoborosilicate catalysts in the environment of hydrogen at elevated temperature and pressure, characterized in that as an additive to the desalted and dehydrated sour crude oil on the catalyst is fed in an amount of 1-20%. a mixture of one of the organic alcohols with long hydrocarbon chain C1-C4 with water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume 70-120A at a temperature of 370-400oAnd pressure 35-70 MPa and subsequent processing in the usual way at the refinery. table 1. The invention relates to the refining and petrochemical industries, in particular, to a method of refining.Known methods of refining [1-2] which includes a preliminary fractionation desalted and dewatered oil and subsequent processing of the narrow oil fractions leads to the formation of significant quantities of residual oil with a high content of sulfur, heavy metals and hard PNA processing. These oils are high-sulphur oil Canada, Venezuela, Egypt and others.One of the ways of solving the tasks involved in the processing of so-called "off-grade" oils and production of crude oil in the processing of high-sulfur heavy oil is advance preparation by Hydrotreating.Currently, the methods of separate hydrofining of petroleum fractions: gasoline, kerosene, diesel fraction. There are publications on the Hydrotreating of the heavy oil feedstock [3-6]
However, currently known approaches to separate hydrofining petroleum fractions not applicable for hydrobromide oil in General.The closest solution to the technical essence and the achieved result is a method of Hydrotreating a hydrocarbon feedstock, in particular vacuum gasoil or deasphalting residual oil  However, this method also does not allow for hydrofining oil at the stage of preliminary processing, i.e. before fractionation, when composed of a wax substance.The purpose of the proposed invention is the floor of the refinery.This goal is achieved by contacting desalted to dehydrated oil from Ecumenical and/or aluminoborosilicate catalysts in the environment of hydrogen at elevated temperature and pressure, provided that desalted and dehydrated oil is pre-mixed with 1-20% about. mixtures of one of the aliphatic saturated C1-C4 alcohols and water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume 70-120A at a temperature of 370-400oC and a pressure of 3.5 to 7.0 MPa.A distinctive feature of the proposed method is that the catalyst is supplied desalted and dehydrated oil is pre-mixed with 1-20% about. mixtures of one of the aliphatic saturated C1-C4 alcohols and water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume 70-120A at a temperature of 370-400oC and a pressure of 35-70 MPa.The basis of the proposed method of refining is the process of hydrofining oil c and subsequent processing of the received sweet crude oil according to the usual scheme refinery. During hydrofining oil flow processes Hydrotreating light the metals.An important advantage of the proposed method is the possibility of profitable processing of heavy and sour crude oils, the processing of which by the usual options is difficult and requires dilution other varieties with high levels of light and lower sulfur content.The process hydrofining oil in a mixture with the additive which is a mixture of the alcohol with the specified length of the hydrocarbon chains and water in a certain ratio under given technological parameters allows the hydrofining process dehydrated and desalted oil prior to its division into individual fractions, which can significantly reduce the sulphur content in refined oil and then process it in the usual way.In the known methods of refining the application of the described technology is unknown. Therefore, this solution meets the criteria of "novelty" and "significant difference".The proposed method is illustrated by the following examples.Example 1. The raw material used oil with the following physical-chemical characteristics:
density, 8960 kg/cubic mthe viscosity at 20oWith, 18,6 KVM is Shemot, 6,3;
99 ml of oil specified composition was mixed with 1ml of additives consisting of 0.95 ml of methanol and 0.05 ml of water.The resulting mixture was subjected to hydrofining at a temperature of 370oC, hydrogen pressure of 35 MPa at lookbetteronline.com catalyst with a predominant pore 70A.Conducted fractionation of the feedstock and the resulting hydrogenated feed is cut showed that the amount of light distillates (gasoline and kerosene, gas oil fractions) when such processing is increased by 5%vol.As can be seen from the data in table 1, the proposed method at the first stage of refining to get from high-sulphur raw material raw material reforming and Hydrotreating diesel fractions with relatively low sulfur content. In addition, at the same time, sweet crude oil.The same table lists the parameters of the process, the raw materials used catalyst, as well as the quality of the obtained hydrogenated feed is separated in examples 2-6. The sequence of operations used to test a sample of oil when running examples 2 to 6 is similar to example 1. The method of obtaining of raw materials of high-sulphur crude oil by kami in the environment of hydrogen at elevated temperature and pressure, wherein the desalted and dehydrated oil is pre-mixed with about 1-20. mixtures of one of the aliphatic saturated alcohols WITH1-C4and water, taken in an amount not less than 5% by volume of the additive, and the contacting is carried out with a catalyst having a pore volume at a temperature of 370-400oC and a pressure of 3.5 to 7.0 MPa.
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