The method of obtaining low-sulfur petroleum fractions and products
(57) Abstract:Usage: petrochemistry. The essence of the crude oil is subjected to hydrocide in the presence of packet alumina catalysts containing 20-100%. aluminoborosilicate catalyst obtained on the basis of three-hydrate of aluminum containing oxides, wt.%, no more: of silicon - 0,2, iron - 0,04, potassium and sodium - 0.6, moisture - 12,0. The process is carried out at 350-400oC. 1 table. The invention relates to the refining, in particular to methods of Hydrotreating petroleum fractions.There is a method of Hydrotreating a petroleum distillate in an environment of hydrogen at elevated temperature and pressure with the use of Ecumenical or aluminoborosilicate catalysts 
The closest in technical essence and the achieved effect is a method of obtaining low-sulfur diesel fuel at elevated temperature and pressure in the presence of the oxide layer aluminoborosilicate catalyst with a diameter of 3.2-4.0 mm in a mixture with elemental sulfur, then in the presence of consecutive layers of oxide zeolite catalyst with a diameter of 2.0 to 3.0 mm and the oxide alumnirelations produce the containing gas at 350-400oC 
The disadvantage of this method is insufficient hydrodesulphurization unit diesel fuels in terms of existing hydrotreatment units, as well as the complexity of operation of three-layer package of the catalyst, which differ from each other in composition of the active components. The operation of the catalytic package is only possible when regeneration is not less than 1 time in 8-10 months and the subsequent overload. When uploading this catalytic system in terms of existing industrial installations is inevitable mixture of catalysts. Therefore, to make further loading is necessary to use a fresh batch of catalyst, significantly, about 5 times, reduces the overall lifetime of the catalysts.The aim of the invention is to increase the depth of hydrofining petroleum fractions in terms of existing industrial installations Hydrotreating.This goal is achieved by obtaining low-sulfur petroleum fractions and products with sulfur content of no more than: gasoline 0,001% wt. diesel fuels: 0.2% wt. vacuum gasoil feedstock for catalytic cracking of 0.6% wt. by Hydrotreating of crude oil at elevated temperature and Yes rasego gas elemental sulfur or a raw material at a temperature of 350-400oC provided that use package alumina catalysts containing 20-100%. aluminoborosilicate catalyst obtained on the basis of trihydride ammonium containing oxides, wt. no more: silicon 0,2; iron 0,04; potassium and sodium 0,6; water 12,0.Under the package catalysts refers to a catalytic system consisting of one or more types and brands of catalysts.The hallmark of the invention is that use package alumina catalysts containing 20-100%. aluminoborosilicate catalyst obtained on the basis of trihydride ammonium containing oxides, wt. no more: silicon 0,2; iron 0,04; potassium and sodium 0,6; water - 12,0.The use of the catalytic composition of the package is not less than 80% aluminoborosilicate catalyst obtained on the basis of three-hydrate of aluminum given quality, significantly increases the catalytic activity of the package due to the optimum dispersion of the crystal structure and acid-basic properties of the obtained aluminum oxide.In the known methods of obtaining small-scale oil with the application of the described technology is unknown.Thus, S="ptx2">Tests of the invention were conducted on three types of materials:
fraction 70-180oC with a sulfur content of 1.2 wt.diesel fraction 180-360oC with a sulfur content of 2.0 wt.%vacuum gas oil with a sulphur content of 2.2 wt.%The test was subjected to three samples of the catalyst:
1. TH-70 (TU 38.1011111-91) with the content of molybdenum trioxide 14,0% wt. the cobalt oxide 4.5% by weight. the raw material used trihydrate aluminum content wt. oxides: silicon 0,16, iron 0,038, potassium and sodium - 0,53; moisture 11,8 obtained from Pikalyovo alumina.2. TH-86 (TU 38.40132-88) with the content of molybdenum trioxide to 13.8 wt. the cobalt oxide of 4.2 wt. the raw material used trihydrate aluminum content wt. oxides: silicon 0,16, iron 0,038, potassium and sodium - 0,53, moisture 11,8 obtained from Pikalyovo alumina.3. DT K (TU 38.301-13-91) with the content of molybdenum trioxide 15% wt. the cobalt oxide 4.5% by weight. the raw material used trihydrate aluminum content, wt. oxides: silicon 0,25, iron 0,05, potassium and sodium 0,75, moisture 13,0 obtained from Achinsk alumina.Direct catalytic composition of the package with the indication used for Hydrotreating raw settings Hydrotreating and kachadurian sulfur in the resulting product, and also similar data for carrying out the process in a known manner (example 6).Examples 1-3 are executed in accordance with the proposed claims for different types of raw materials. Examples 4 and 5 shows how the beyond.From the table it is seen that the proposed method allows to obtain the desired depth of Hydrotreating. Implementation of a prototype on the same raw materials such results does not. The change in the ratio of the used catalyst downward share aluminoborosilicate catalyst made of alumina deposits Pikalyovo, leads to a reduction in the depth of Hydrotreating. The method of obtaining low-sulfur petroleum fractions and products with sulphur content not more wt.Gasoline 0,15
Diesel fuels 0,2
Vacuum gasoil feedstock for catalytic cracking 0,6
by Hydrotreating of crude oil at elevated temperature and pressure in the presence of packet alumina catalysts, pre-activated in the environment of the hydrogen-containing gas to elemental sulfur or raw materials with 350 400o, Characterized in that use package alumina catalysts containing 20 to about 100. lumocolor CLASS="ptx2">Silicon 0,2
Potassium and sodium 0,6
Water 12.0 p
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