A method of reducing the total acid number of crude oil
(57) Abstract:Usage: petrochemistry. Essence: spend processing oil hydrogen-containing processing gas containing hydrogen sulfide, in the presence of the Hydrotreating catalyst. The contacting is carried out at 200-370oWith, 239-13900 kPa, the concentration of hydrogen sulfide in the hydrogen-containing processing gas of 0.05-25 mol. %. The technical result - the reduction of total acid number of crude oil. 8 C. p. F.-ly, 4 PL. , 2 Il. The invention relates to a method of catalytic reduction of total acid number of acidic crude oil.Because of the demands of the market becomes more economically attractive treatment vysokochistykh crude oils such as naphthenic acid oil. It is well known that the treatment of acidic materials can cause a variety of problems associated with the oil and other acidic corrosion. Was offered a number of ways to reduce the total acid number (ACC), which represents the number of milligrams of potassium hydroxide required to neutralize the acids in one gram of crude oil.One approach is a chemical neutralization of acidic components from different bases. In this venture the salts and additional stages of processing. Another approach is to use corrosion resistant metal treatment plants. This, however, causes significant costs and may be economically unsound for existing installations. The next approach is to add corrosion inhibitors to crude oil. This has the negative effect of corrosion inhibitors on subsequent nodes, for example, reduces the life or efficiency of the catalyst. Moreover, even with extensive monitoring and verification are difficult to obtain confirmation of the widespread and complete corrosion protection. Another possibility is to reduce the acid content of the mixture of sour crude oil having a low acid content. Limited stocks of such discotekas oil make this approach more difficult.In U.S. patent 3617501 declared an integrated method of cleaning a solid oil. The first stage is a Catholic Hydrotreating solid oil to remove sulfur, nitrogen, metals and other impurities. In U.S. patent 2921023 provides a way to work with improved catalytic activity during the mild Hydrotreating to remove naphthenic acids in high-boiling fractions of crude oil. Kata is the oil. In U.S. patent 2734019 described method of treatment of naphthenic lubricating oil fraction by contacting with the catalyst is cobalt molybdate on alumina, which does not contain silicon oxide, in the presence of hydrogen to reduce the concentration of sulfur, nitrogen and naphthenic acids. U.S. patent 3876532 relates to a method of very mild Hydrotreating direct middle distillates to reduce the total acid number or content of mercaptans in the distillate without a significant reduction in sulfur content using a catalyst, which was previously decontaminated during more severe Hydrotreating.It would be desirable to reduce the acidity of crude oil without the addition of neutralizing or corrosion agents, and without turning the oil into the threads of the oil.This invention relates to a method of reducing the total acid number of sour crude oil, which comprises contacting the crude oil with a Hydrotreating catalyst at a temperature of from about 200 to 370oC in the presence of a hydrogen-containing processing gas containing hydrogen sulfide with a total pressure from about 239 to 13900 kPa, where the molar concentration of hydrogen sulfide in natural gas processing castanette.In Fig. 2 graphically shows the effect of added hydrogen sulfide to reduce OKC.Sour crude oil usually contains naphthenic acid and other acids and has OKC from 1 to 8. Discovered that is OCC in sour oil can be significantly reduced by Hydrotreating of crude oil or topped crude in the presence of hydrogen gas, containing hydrogen sulfide. The Hydrotreating catalysts are usually used to saturate the olefins and/or aromatics and reduce the content of nitrogen and/or sulfur in the streams fed or recycled oil products. Such catalysts, however, can also reduce the acidity of crude oil by reducing the content of naphthenic acids.The Hydrotreating catalysts are catalysts that contain metals of group VI (on the basis of the periodic table, published in Fisher Scientific) and base metals of group VIII. These metals or mixtures of metals are usually present in the form of oxides or sulfides on a refractory carrier metals. Examples of such catalysts are the oxides of cobalt and molybdenum on a carrier such as alumina. Other examples include oxides of cobalt/Nickel/molybdenum or oxides nor the comfort of solifidianism. Preferred catalysts include cobalt/molybdenum (1-5% in the form of oxide, 5-25% Mo oxide), Nickel/molybdenum (1-5% Ni oxide, 5-25% Mo oxide), and Nickel/tungsten (1-5% Ni oxide, 5-30% Wo oxide) on alumina. Especially preferred are Nickel/molybdenum, cobalt/molybdenum catalysts.Appropriate refractory carriers metals are oxides of metals such as silicon oxide, aluminum oxide, titanium oxide or mixtures thereof. To minimize reactions of hydrocracking and/or hydroisomerization, preferred low acidity of the metal oxide media. Particularly preferred carriers are porous alumina, such as gamma or beta-alumina having an average pore size from about 50 to 300 , the surface area of from about 100 to 400 m2/g and a pore volume from about 0.25 to 1.5 cm3/,The reaction conditions for contacting the acidic crude oil with a Hydrotreating catalysts include a temperature from about 200 to 370oC, preferably from about 232 to 316oC, most preferably from about 246 to 288oC, and hourly space velocity of fluid (COSI) from 0.1 to 10, preferably from 0.3 is(from 20 to 2000 psig), preferably from about 446 to 3550 kPa (about 50 to 500 psig). The flow ratio of hydrogen: crude oil is in the range from 3.56 to 889,94 (from 20 to 5000 scf/B), preferably from 5,34 to 266,98 (from 30 to 1500 scf/B), most preferably from 8,90 to 88,99 (from 50 to 500 scf/B).It was found that the addition of hydrogen sulfide to the hydrogen-containing processing gas significantly improves the degree of reduction of OKC sour oil. Apparently, the introduction of hydrogen sulfide in the processing gas improves the activity of the Hydrotreating catalyst. The amount of hydrogen sulfide in the hydrogen-containing gas can vary in the range from 0.05 to 25 mol. %, preferably from 1 to 15, most preferably from 2 to 10. The hydrogen sulfide can be added to hydrogen gas. In another embodiment, as the gas Hydrotreating can be used acidic hydrogen-containing refinery stream of gas, such as flue gas Hydrotreating high pressure.In a typical refining process, crude oil is first subjected to desalting. Crude oil may then be heated and heated as directed in the column pre-flash evaporation to remove most of the products having a boiling point less than primer the well. Thus, here we use crude oil, including potenciano oil and stripped oil.In this way decrease the acidity vyskocilova oil use a heat exchanger and/or the furnace and zone catalytic processing before the atmospheric column. In the heat exchanger and/or the oven is pre-heated crude oil. The heated oil is then directed to the area of catalytic processing, which includes the reactor and the catalyst. The reactor preferably is a standard flow-through reactor with a catalyst bed, however, you can use reactors of different design, in particular, the fluidized bed reactor, a slurry reactor, and others.The method according to this invention is further illustrated in Fig. 1. Crude oil, which may be preheated, is directed through line 8 to the column pre-flash evaporation. Top zipper containing gas and the liquid phase, for example, light naphtha, removed from the column pre-flash evaporation on line 14. The remaining crude oil is directed through line 16 to the heater 20. In another embodiment, the crude oil can be sent directly to the heater 20 through the line 10. The heated crude oil from the heat is replaced in the case, if the reactor for the receipt of crude oil 24 has a sufficient temperature in order to satisfy the temperature requirements of the reactor 24. In the reactor 24 crude oil is in contact with stationary hot catalyst 28 in the presence of hydrogen-containing gas containing hydrogen sulfide is added through line 26. Crude oil is fed from the top through the catalyst layer 28 and is directed along the line 30 in the atmospheric column 32. Atmospheric column 32 operates in the usual way, producing the top ring, which is removed through line 34, various distillate fractions such as heavy nakikiramay naphtha, gas oil, heavy gas oil and purified from hydrogen sulfide gas, which, as shown, together are removed through line 36. Oil, not containing light fraction, is removed through line 38 for further processing in a vacuum distillation column (not shown).In the reactor 24 OCC crude oil is reduced by the catalytic conversion of components representing naphthenic acids with lower molecular weight contained in the crude oil to obtain CO, CO2H2And non-hydrocarbon products. Reaction conditions in the reactor 24 are such that the saturation of the aromatic ring is e conditions, besides insufficient to accelerate the reactions of hydrocracking or hydroisomerization. In the presence of hydrogen may be some conversion of reactive sulfur, that is, nativename sulfur in H2S.The invention is further illustrated by the following examples without limiting the scope of invention.Example 1.This example illustrates the reduction of the presence of naphthenic acids in vyskocilova oil. In the pilot installation was downloaded Hydrotreating catalyst, and the catalyst was sliderule the usual way, using straight distilled water as a carrier containing dimethyl disulfide as a source of sulfur. Studied two different commercially available Ni/Mo catalyst Hydrotreating. Catalyst a is a conventional Ni/Mo catalyst with high metal content, typically used in the pre-treatment liquid feedstock to the catalytic cracking installation, and the catalyst is a catalyst with wide pores with a low content of metals commonly used in hydrodemetallization. As supplied oil used vysokochistoi crude oil, with OKC 3,7 (mg KOH/ml). The crude oil was treated under the conditions shown in table. 1.Fig. 2 is a graph showing the measured OKC products in the conditions of the experiment, Pavlina kinetic rate constants of the first order, calculated to reduce OKC and correlated with the activity of the catalyst And in the absence of H2S.Despite the fact that the catalyst with a low content of metals has an activity substantially lower than the catalyst And, in relation to reducing OCC, the activity of both catalysts is increased by 30-50%, when the processing gas is about 4. % H2S.This result is opposite to the result obtained for conventional hydrodesulphurization reactions (SDS) and hydrodenitrification (GAM) in the Hydrotreating, where it was observed that the hydrogen sulfide slows down as the reaction of the SDS and the PAU. Thus, the influence of additives of hydrogen sulfide to the hydrogen-containing gas is unexpected.Example 2.Repeating the procedure of example 1, except that used the new catalysts. The catalyst With high metal content With/Mo usually used in desulfurization of distillate. Catalyst D with a high content of metals With/Mo used in the Hydrotreating VAT residue. Table. 3 and 4 is similar to table. 1 and 2 in example 1.Similar to the results presented in table. 2, the activity of both catalysts is increased by 50 to 95%, when the gas for processing is 4 mol. % H
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