Method of purification of liquid hydrocarbons from sulfur compounds
(57) Abstract:The invention relates to petrochemistry and oil refining and can be used in the processes hydrodesulphurization unit of hydrocarbon fractions. Cleaning liquid hydrocarbons is carried out in the presence of hydrogen in aluminium oxide-platinum catalyst, pre-activated with hydrogen at 80 - 300oC and high pressure. This method allows to obtain a hydrocarbon feedstock with a high degree of purification from sulfur compounds. The invention relates to methods for cleaning hydrocarbons from sulfur compounds and can be used for desulfurization paraffinic, olefinic and aromatic hydrocarbons.Known method of hydrodesulfurization and hydrogenation distillate hydrocarbon complex bimetallic catalyst consisting of various catalytic zones. In the composition of the catalyst 1 zone comprises active components containing precious metals such as cobalt, Nickel, molybdenum, tungsten. Catalyst 2 zone contains the active component of the platinum group metal. Moreover, it is interesting to note that purification from sulfur occurs mainly in the first reaction zone, and platinum katalia diesel fuel in two stages, using the first stage lookbetteronline catalyst, and the second stage catalyst platinum source. The disadvantage of this method is the use of advanced secondary treatment and use of high temperatures .There is a method of Hydrotreating sulfur kerosene to improve his raketoopasnyh characteristics . The method consists in the treatment of this fraction with hydrogen at the maximum allowable for this catalyst temperature ( < 400oC) a catalyst comprising an inorganic carrier containing aluminum oxide, 0.1 to 1.5 wt.% halogen component, a platinum component, a rhodium and tin component. The disadvantage of this method is the necessity of using high temperatures.The closest in technical essence and the achieved effect is a method of desulfurization of crude benzene, light and heavy oil and shale oils and other hydrocarbons . The method consists in passing the vapors of these hydrocarbons in a stream of hydrogen at atmospheric pressure and a temperature of 300-350oC over a catalyst selected from the group of Nickel deposited on alumina, platinum or palavered removed by ordinary methods.To obtain hydrocarbons with a high degree of Hydrotreating at lower temperatures, we propose a method of purification of liquid hydrocarbons from sulphur at 80-300oC on aluminium oxide-platinum catalyst, pre-activated with hydrogen. As aluminium oxide-platinum catalyst used aluminium oxide-platinum catalyst for isomerization.Distinctive features of the invention are the use of aluminium oxide-platinum catalyst, pre-activated with hydrogen, and the process of purification at 80-300oC.When comparing essential features of the invention with those prototypes and analogues, it is possible to draw a conclusion on the conformity of the proposed technical solution the criteria of "novelty" and "inventive step", since the use of pre-activated hydrogen aluminium oxide-platinum catalyst isomerization in the process hydrodesulphurization unit is not known. Pre-activation of the catalyst allows to achieve a desired degree of purification of hydrocarbons from sulfur compounds. It is the activation of known industrial catalyst allows the process of hydrodesulfurization at lower temperature is feasible in industry, as evidenced by the following examples.Example 1. Testing is carried out at a flow setting of continuous operation. Before carrying out the process of conducting the preliminary preparation of the catalyst, which are as follows: charged to the reactor known industrial aluminium oxide-platinum catalyst (TU 3810173-77. Catalyst FE-62 is a platinum uniformly distributed on the external and internal surfaces of the extrudates fluorinated activity of aluminum oxide. Mass fraction of platinum 0,550,03; mass fraction of fluorine 3,50,5; mass fraction of iron, not more than 0.02; mass fraction of sodium, not more than 0.01; the bulk density of the catalyst, calcined at 550oC 0,650,05 kg/l; the ratio of the strength of the catalyst is not less than 0.97 kg/mm; the diameter of the extrudates 2,80,2 mm). The reactor is heated to activate the catalyst with hydrogen at atmospheric pressure, after which install in the reactor specified temperature and pressure and do not stop the flow of hydrogen into the reactor served raw. The reaction product is purified from sulfur-containing impurities of the hydrocarbon fraction is removed from the reactor in the collection and analyzed for total sulfur content (GOST 19121-73). The process of cleaning hydrocarbons from sulfur compounds conduct is mperature in the reactor 80oC, hydrogen pressure of 10 ATM.. Purified hydrocarbon fraction is directed to a collection, then taken and analyzed for total sulfur content, which is 0.0001 wt.%. The degree of purification from sulfur compounds thus equals 98,33%. As hydrocarbon use fraction C5-C7 c tKip.60-100oC.Example 2. Experience in the conditions of example 1, but the temperature in the reactor support 150oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 3. The experience is conducted under the conditions of example 1, but the temperature in the reactor support 200oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 4. The experience is conducted under the conditions of example 1, but the temperature in the reactor support 250oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 5. The experience is conducted under the conditions of example 1, but the temperature in the reactor support 300oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 6. Experience conducting condition in which one faction is 0,00005 wt.%. The degree of desulfurization is 99.7%. As hydrocarbon use fraction C5-C7with tKip.30-90oC.Example 7 the Experience carried out in the conditions of example 6, but the temperature in the reactor support 150oC. the Content of total sulphur and unsaturated in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 8. The experience is conducted under the conditions of example 6, but the temperature in the reactor support 200oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 9. The experience is conducted under the conditions of example 6, but the temperature in the reactor support 250oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.Example 10. The experience is conducted under the conditions of example 6, but the temperature in the reactor support 300oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.These examples show that the optimal conditions for the desulfurization process are a temperature of 80-300oC and a pressure of 10-15 bar. The invention allows to reduce energy consumption and the related compounds. Method of purification of liquid hydrocarbons from sulfur compounds at elevated temperature in the presence of hydrogen, the catalyst containing platinum, wherein the cleaning is performed at 80 - 300oWith aluminium oxide-platinum catalyst, pre-activated with hydrogen.
FIELD: desulfurization and hydrogenation catalysts.
SUBSTANCE: invention relates to preparing hydrodesulfurization and dearomatization catalysts useful in processes of deep purification of motor fuels from sulfur-containing compounds and aromatics. A sulfur-resistant catalyst is provided including active component deposited on porous inorganic support including montmorillonite or alumina and characterized by that support is composed of zeolite H-ZSM-5 with Si/Al atomic ratio 17-45 (80-65%) and montmorillonite or alumina (20-35%), while active component is platinum or palladium, platinum and palladium in quantities, respectively, 0.2-2.0, 0.2-1,5. and 0.4-0.2% based on the total weight of catalyst. Described is also catalyst comprising platinum (0.2-2.0%) or palladium (0.2-1.5%), or platinum and palladium (0.4-2.0%) supported by Ca or Na form of montmorillonite, and also catalyst with the same active components supported by zeolite H-ZSM-5 with Si/Al atomic ratio 17-45.
EFFECT: increased sulfur-caused deactivation resistance of catalyst at moderate temperatures and under conditions efficiency in hydrodesulfurization and aromatics hydrogenation processes.
8 cl, 4 tbl, 30 ex
FIELD: oil refining industry and petrochemistry; hydrorefining of petroleum distillates.
SUBSTANCE: hydrorefining of petroleum distillates is carried out at elevated temperature and increased pressure in presence of catalyst containing carrier - highly porous cellular material on base of aluminum α-oxide modified by aluminum γ-oxide or sulfated zirconium dioxide; used as active component is palladium or palladium modified by palladium nano-particles or palladium in mixture with zinc oxide in the amount of 0.35-20.0 mass-%. The process is carried out at temperature of 150-200°C and pressure of 0.1-1.0 Mpa.
EFFECT: enhanced efficiency; facilitated procedure; possibility of hydrorefining of gasoline and diesel distillates.
2 cl, 1 tbl
FIELD: petroleum processing and catalysts.
SUBSTANCE: field of invention is production of catalysts for catalytic hydrotreatment (desulfurization) of gasoline fractions, e.g. straight-run gasoline. Herein disclosed is block-type high-porosity cellular catalyst for hydrotreatment of straight-run gasoline having porosity at least 90-93% and microporosity up to 30%, average pore size being ranging from 0.5 to 2.0 μm. Catalyst consists of α-alumina-based carrier and active catalyst portion containing sulfated zirconium dioxide and metallic palladium in concentration 0.5-0.9 wt %. Catalyst preparation method is also claimed and is as follows. Carrier is prepared from reticular polyurethane foam and impregnated with slurry containing more than 30 wt % α-alumina, after which calcined at 1300-1500°C, impregnated with water-soluble zirconium salts, dried at 100-200°C, calcined at 450-950°C, treated with 5-10% sulfuric acid, dried, calcined at 500-550°C, treated with palladium nitrate, dried, and calcined at 400-450°C, whereupon palladium oxide is reduced to metallic palladium.
EFFECT: lowered pressure and temperature of hydrotreatment process, considerably reduced process duration, lowered sulfur level in straight-run gasoline due to developed surface of catalyst, and prevented crumbling and loss of catalyst due to cellular structure and high strength.
FIELD: chemistry, organic, processing of hydrocarbons.
SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.
EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.
14 cl, 1 ex
SUBSTANCE: invention relates to a method of purifying lower alkanes from methanol through contact between the raw material and a catalyst which contains aluminium oxide at high temperature and pressure. The method is characterised by that the catalyst used is an aluminiuim-platinum catalyst and contact takes place at temperature of 180-400°C, pressure of 1.5-4.0 MPa, volume rate of supply of material of 0.4-4 h-1 and volume ratio of material : hydrogen equal to 1:(5-900).
EFFECT: invention increases degree of purity of lower alkanes from methanol.
3 cl, 9 ex
SUBSTANCE: invention relates to a method of hydrofining synthetic oil, realised by bringing synthetic oil, obtained via Fischer-Tropsch synthesis and having content of C-9-21 hydrocarbons greater than or equal to 90 wt %, into contact with a hydrofining catalyst which has a support which contains one or more solid acids selected from ultra-stable Y-(USY) zeolite, aluminosilicate, zirconia-silicate and aluminium-bromine oxide catalyst and at least one metal selected from a group comprising group VIII metals, deposited on the support, in the presence of hydrogen with regulation of the reaction temperature when the hydrofining catalyst is in contact with the synthetic oil, in order to hydrofine the synthetic oil such that content (wt %) of C8 or lower hydrocarbons in the synthetic oil after contact is 3-9 wt % higher than before contact. The invention also relates to a method of producing base fuel material.
EFFECT: obtaining base oil with excellent low-temperature rheological properties with good output of the middle fraction of the synthetic oil.
6 cl, 8 ex, 2 tbl, 1 dwg
FIELD: oil and gas industry.
SUBSTANCE: paraffin hydrotreating method involves the first stage at which paraffin with content C21 or higher of normal paraffins 70% wt or higher is used as basic material, and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking, catalyst consisting of metal of group VIII of the Periodic Table, which is put on carrier containing amorphous solid acid; the second stage at which raw material from paraffin is replaced for some time with light paraffin with content C9-20 of paraffins 60% wt or higher, and light paraffin contacts with catalyst at reaction temperature of 120-335 °C in presence of hydrogen for hydrocracking; and the third stage at which raw material of light paraffin is replaced with paraffin and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking. Also, invention refers to method for obtaining material of fuel system, which involves the above method.
EFFECT: use of this invention allows improving activity of hydrocracking catalyst, which deteriorates with time.
6 cl, 1 tbl, 4 ex, 1 dwg
SUBSTANCE: invention relates to a catalyst for realising a method of hydrogenating olefins and oxygen-containing compounds in synthetic liquid hydrocarbons obtained via a Fischer-Tropsch method, containing a porous support made from γ-aluminium oxide on which a catalytically active palladium component is deposited, characterised by that pores in the support have effective radius of 4.0-10.0 nm, wherein content of foreign-metal impurities in the support is not more than 1500 ppm, and content of palladium in the catalyst is equal to 0.2-2.5 wt %. The invention also relates to a hydrogenation method using said catalyst.
EFFECT: invention enables to obtain saturated hydrocarbons from liquid Fischer-Tropsch synthesis products, which are a complex mixture of paraffin hydrocarbons with 5-32 carbon atoms, with ratio of normal paraffin hydrocarbons to isoparaffin hydrocarbons ranging from 1:1 to 7:1, containing up to 50% olefins and up to 5% oxygen-containing compounds.
2 cl, 1 tbl, 7 ex
SUBSTANCE: invention discloses a method for producing diesel fuel from a hydrocarbon stream, comprising: hydrotreating the main hydrocarbon stream and a co-feed hydrocarbon feedstock containing diesel fuel in the presence of a hydrogen stream and a pre-purification catalyst to produce a pre-purified effluent stream; hydrocracking a pre-purified effluent stream in the presence of a hydrocracking catalyst and hydrogen to produce an effluent hydrocracking stream; fractionating, at least, a portion of the hydrocracking effluent to produce a diesel fuel stream; and hydrotreating the diesel fuel stream in the presence of the hydrogen stream for hydrotreating and a hydrotreating catalyst to produce an effluent stream.
EFFECT: producing diesel fuel with low sulfur and ammonia content.
10 cl, 2 dwg