The way to obtain environmentally friendly diesel fuel sulfur crudes
(57) Abstract:The invention relates to petrochemical technology, in particular to methods of producing low-sulfur diesel fuel, and can be used in the refining and petrochemical industries. Describes how to obtain clean diesel fuel by distillation emitting kerosene and diesel fractions, catalytic Hydrotreating last at elevated temperature and hydrogen pressure, using layers loaded aluminoborosilicate (AKM) and alumnirelations (AMN) catalysts, characterized in that the refining of oil to produce kerosene and diesel fractions (160-190)-300oWith and (300-310)-390oWith, then mixing them in the ratio of 70:30-30:70 wt.%, the resulting mixture is subjected to Hydrotreating in the presence of densely located along the raw layers of catalysts: alumnirelations (AMN) catalyst spherical shape with a diameter of 2.8-4.2 mm and two layers aluminoborosilicate (AKM) catalyst made in the form of a trefoil with a diameter of 1.8 to 2.6 and 1.3-1.8 mm, respectively, when the mass ratio of the layers(1,0-1,5) :10: (30-35), moreover, the catalysts previously Obernai 0,4-1,0 wt. % with a step rise in temperature up to 160-200, 220-240 and 300-340oC with a dwell time at each temperature for 2 hours, the Hydrotreating of the feedstock is carried out at a temperature of 330-370oC, a pressure of 2.5 to 4.0 MPa, the space velocity of the raw material of 3.0-4.5 h-1and the resulting hydrogenation product is subjected to stabilize the temperature of the top of the column 115-160oWith, the bottom 250-320oC, at pressures of 0.1-1.2 MPa to obtain the desired fuel fraction (160-190)-380oC. Technical result is an increase in the depth of Hydrotreating diesel fuel, increasing its output, as well as simplification of the process. table 1. The invention relates to methods of producing environmentally friendly diesel fuel sulfur crudes and can be used in the refining and petrochemical industries.Known methods of producing low-sulfur diesel fuel:
by using an effective catalyst for Hydrotreating TH-86, providing a residual sulfur content of the target fuel up to 0.02 wt.% /Refining and petrochemicals, 1995, N11, S. 15./,
by hydrodesulphurization unit straight-run fraction with a sulfur content not higher than 1.3 wt.% and 95% of which boils at a temperature not exceeding 360oC privy media. The sulfur content of the hydrotreated fuel to 0.1% wt /Refining and petrochemicals 1997, N1, S. 21-22/,
by Hydrotreating of the feedstock in the presence of three layers of catalysts: aluminoborosilicate (AKM), alumnirelations (AMN) and aluminoborosilicate (AOM) at a mass ratio of catalyst layers 0,5-1,0 : 4,0-4,5 : 5,0-8,0, moreover, the catalysts subjected to preliminary acarnania by loading of elemental sulfur on top of each layer (3). SU 1801116, 07.03.93)
The disadvantages of the above methods are: high temperature, which is achieved satisfactory gidroobesserivaniya activity of the catalytic system (above 360oC) and the resulting low output hydrotreated diesel fuel (93,5 estimates 95.2 wt.%).The closest in technical essence and the achieved result of the present invention is a method of obtaining low-sulfur diesel fuel produced by Hydrotreating diesel fractions at elevated temperature and pressure in the presence of a layer aluminoborosilicate catalyst, characterized in that use layer aluminoborosilicate catalyst with a diameter of 3.2-4.0 mm in a mixture with elemental sulfur is a catalyst with a diameter of 2.0-3.2 mm and alumnirelations catalyst, taken in the mass ratio 1:1:1.3 to 8.0 and pre-activated in the environment of hydrogen containing gas at 350-400oC (EN, 2005765, 12.12.91).The disadvantages of this method are the following factors:
- use when the catalyst loading additional reagent is sulfur. The application of this technology leads to technical difficulties in catalyst loading, cost of production of low-sulfur diesel fuel,
- used in the middle layer of the loading of the zeolite catalyst, which is produced by a different technology than the catalysts of the upper and lower layer. The use of the zeolite catalyst leads to increased degradation of raw materials, resulting in reduced yield of the target fuel. In addition, the catalysts of this type is particularly sensitive to the poisoning of nitrogen-containing compounds of the raw materials, so the use of diesel fuels containing heavy components, leads to rapid deactivation of the catalytic system,
the Hydrotreating process to ensure the required degree of removal from raw materials is carried out at an elevated pressure of 4 MPa. Most of Hydrotreating works by using vodorodsoderzhashchee of the invention is to increase the depth of the diesel hydrotreater unit, the increase in its output, as well as the simplification of the production of environmentally friendly fuel by conducting hydrodesulphurization unit in mild process conditions.This goal is achieved in the following way. The oil is subjected to atmospheric distillation emitting fractions (160-190)-300oC and (300-310)-390oC. Further their compounding in a mass ratio of 70:30-30:70. The resulting mixture is sent to a Hydrotreating unit with a serial arrangement of reactors, which use special devices in layers tightly downloaded two catalyst: in the upper layer aluminumalloy catalyst spherical shape with a diameter of 2.8-4.2 mm and two layers aluminoborosilicate catalyst, made in the shape of a trefoil with a diameter of 1.8 to 2.6 and 1.3-1.8 mm, respectively, when the mass ratio of the layers(1,0-1,5):10:(30-35).To improve the activity of the catalyst spend his special processing of straight-run diesel fraction with an end boiling point not exceeding 340oC, with a sulfur content of 0.4 to 1.0 wt. percent, at step rise of temperature up to 160-200, 220-240 and 300-340oC with a dwell time at each temperature for 2 hours.The diesel fuel hydrotreatment is carried out at a pressure, the hydrogenation product is fed to stabilize at the temperature of the top of the column 115-160oC, bottom 260-320oC, at pressures of 0.1-1.2 MPa to obtain the desired fuel fraction (160-190)-380oC.The proposed method of obtaining fuel at the expense of catalyst preparation, special download, the selection ratio of the fractions of the fuel allows to significantly simplify the process of obtaining clean fuel, to provide the necessary cleaning from sulfur, to expand the limits of the fractional composition of the original fuel by involving fractions with higher end boiling (up to 390oC) and thereby to increase the output of low-sulfur diesel fuel. The table presents data on the main parameters of the process of the present invention and prototype.The following are specific examples of execution of the invention.Example 1 (prototype).The Hydrotreating diesel fraction is subjected 180-360oC, containing 1.6 wt. % sulfur. As aluminoborosilicate catalyst (upper layer) using a catalyst with NiO content of 4.1 wt.%, MoO3-15,4%. The middle layer is a zeolite-containing catalyst with a total content of hydrogenating metals 17 wt.%, high zeolite (DCM)-5 wt.% Bottom layer - aluminumalloy the catalyst of the brand DT-005H (assy upper and middle catalyst. Activation of the catalyst is elemental sulfur in the environment of the hydrogen-containing gas at a temperature of 350-400oC. the Ratio between the layers of catalysts 1,0:1,0: 1,3. The Hydrotreating is conducted at a pressure of 4 MPa, a temperature of 360oC. the Residual sulfur content in the hydrogenation product is 0.02 wt.%
Example 2.The oil is subjected to distillation at atmospheric setting with the release of factions (160-190)-300oC (Stripping K-3/2) and (300-310)-390oC (Stripping To-3/3), mix them in a mass ratio of 30:70. The obtained distillate diesel fuel with a sulfur content of 1.6 wt.% sent to the hydrotreatment reactor, loaded successively along the raw catalysts AMN with a diameter of 2.8 mm, AKM - diameter 1.8 and 1.3 mm with a ratio of catalysts 1:10:30.As the ACME of catalyst (middle and bottom layers) used industrial catalyst containing oxides, wt.%: molybdenum - 5,3, cobalt - 1,7, aluminium - the rest is up to 100.The catalyst pre username straight-run diesel fraction with a lightweight end of the boil (338oC) at step raising the temperature to 160, 220 and 300oC with a dwell time at each temperature for 2 hours.The process parameters and characteristics fractie between layers of catalysts - 1,5:10:35 (example 3) and 1,25:10:32 (example 4), respectively. Other parameters and characteristics of the fractions in the table.Examples 5-6.Carry out the method according to example 4 when changing the diameter of the granules of the catalyst and the following ratio between the layers of catalysts - 1,25:10:32. The reduced diameter lower than specified in the invention leads to a decrease in strength of the catalyst and the pressure increase in the reactor (example 5). Increasing the sulfur content in the finished fuel. Increasing the diameter of the granules leads to a decrease gidroobesserivaniya the activity of the catalyst by reducing its total activity (example 6).Examples 7-8.Carry out the method according to example 4, when the change in the ratio between catalyst for the limits specified in the invention, namely to 0.9:9:28 (example 7) and 1,2:11:36 (example 8). In both cases decreases the activity of catalysts. The sulfur content in the hydrotreated diesel fuel increases.Example 9.The method is carried out according to example 4. Acarnania catalyst spend a diesel fuel with a higher end boiling (354oC). This increases the coke formation on the catalyst, antisemitist in example 4. Acarnania catalyst spend a diesel fuel with a sulfur content of 0.35%. When this cycle of activation of the catalyst is increased, the partial pressure of H2S in the reactor is reduced, leading to less complete acarnania catalyst and reduce its activity. The sulfur content of the hydrotreated fuel increases.Example 11.The method is carried out according to example 4. Acarnania catalyst is conducted without the speed of temperature rise with time of 2 hours at each temperature. This results in intense heat, and more rapid coking of the catalyst, which leads to the decrease of its activity and the increase in sulfur in the target fuel.Examples 12-13.The method is carried out according to example 4. Conditions of stabilization of the modified hydrogenated feed is cut. When the temperature of the top and bottom of the column stabilization, as well as the pressure increases the time of ottowa H2S and hydrotreated fuel does not stand the test corrosion (example 12). With increasing temperature stabilize the top of the column above 320oC (325oC) and pressure reduction part of the fraction of diesel fuel went along with gasoline fractions. Hydrotreated fuel had higher which is (example 13).Example 14-15.The method is carried out according to example 4. The hydrotreatment was served raw materials with lower fractions of (160-190)-300oC and the higher fraction (300-310)-390oC.Reduction in fuel fractions (190-200)-300oC leads to deterioration of desulfurization of diesel fuel and increasing sulfur content in the target product (example 14).The increase of heavy fractions in diesel fuel increases the freezing temperature of the target fuel (example 15).Low content in the mixture of heavy fractions of the atmospheric distillation reduces the yield of the target product. The way to obtain environmentally friendly diesel fuel by distillation emitting kerosene and diesel fractions, catalytic Hydrotreating last at elevated temperature and hydrogen pressure, using layers loaded aluminoborosilicate (AKM) and alumnirelations (AMN) catalysts, characterized in that the refining of oil allocate fractions (160 - 190) - 300oC and (300 - 310) - 390oC, then mix them in a mass ratio of 70 : 30 to 30 : 70, the resulting mixture is subjected to Hydrotreating in the presence of densely Packed on x is IU trefoil diameter of 1.8 - 2.6 and 1.3 - 1.8 mm, respectively, when the mass ratio of the layers(1,0 - 1,5) : 10 : (30 - 35), moreover, the catalysts previously sarnaut straight-run diesel fraction with a lightweight end boiling point not exceeding 340oC and a sulfur content of 0.4 to 1.0 wt.% at step raising the temperature to 160 - 200, 220 - 240 and 300 -340oC, with a dwell time at each temperature for 2 hours, the Hydrotreating of the feedstock is carried out at a temperature of 330 - 370oC, a pressure of 2.5 to 4.0 MPa, the space velocity of the raw material of 3.0 - 4.5 h-1and the resulting hydrogenation product is subjected to stabilize the temperature of the top of the column 115 - 160oC, bottom - 250 - 320oC, at pressures of 0.1 - 1.2 MPa to obtain the desired fuel fraction (160 - 190) - 380oC.
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.