Lower alkane purification method
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
The invention relates to a method of purification of lower alkanes from methanol and can be used in the refining and petrochemical industry, namely, upon receipt of the hydrocarbons used as solvents in the polymerization processes of olefins.
Know the use of adsorbents to remove impurities methanol and ethers of hydrocarbon streams, such as olefins, natural gas and light hydrocarbon streams. For these purposes a solid porous adsorbents with large surface, such as zeolites, alumina, silica gel, aluminosilicates (RF patent No. 2264855, IPC7B01J 20/18, publ. 27.03.2003; RF patent №2288026, IPC7B01D 53/72, publ. 27.11.2005). The disadvantages of the above adsorbents are low sorption capacity, high temperature regeneration and low selectivity towards methanol.
Known methods of purification of lower hydrocarbons from oxygen-containing impurities, which are used in catalytic purification with the use of catalysts based on silica-alumina zeolites, as well as copper-zincaluminum and zincaluminum catalysts for conversion of methanol (Catalytic purification of hydrocarbon mixtures from methanol. Gospelmusic, Lambiance, Adiastasia etc. /M: World oil, 2007, No. 5, p.30-32). The efficiency of these catalysts, basically, op is Adelaide methanol content in alkane and process conditions (temperature and pressure). However, the drawbacks of these methods is that these catalysts are characterized by low efficiency of methanol and are of limited use for heavy flows due to the conversion of hydrocarbons and rapid deactivation of the catalysts.
The closest in technical essence is a method of purification of hydrocarbon mixtures from methanol (RF Patent No. 2293056, IPC SW 3/22, SS 1/20, publ. 10.02.2007), including contact etanolsoderjasimi hydrocarbon with a zinc-chromium or copper-zinc-chromium catalyst or a catalyst based on zeolite group of pentelow. The contact is carried out at a volumetric feed rate of the raw material 3-15 h-1at a temperature of 220-400°C and pressure up to 1.8 MPa. When using the catalyst for conversion of methanol to hydrocarbons containing 70% of zeolite HZSM-5 and 30% Al2About3the reaction temperature is 400-450°C. the content of methanol in the feedstock is 1.5-5 wt.%, in the purified product from 0.01 to 0.05 wt.%.
The disadvantage of this method is the high residual impurity content of methanol in the hydrocarbon streams.
The objective of the invention is to increase the degree of purification of the lower alkanes from methanol.
To solve this problem is proposed a method of purification of lower alkanes from methanol by contact of the feedstock with a catalyst containing alumina when the appreciation is the R temperature and pressure, at the same time as the catalyst is used aluminium oxide-platinum catalyst and the contact is carried out at a temperature of 180-400°C., a pressure of 1.5 to 4.0 MPa, the space velocity of the raw material 0,4÷4 h-1, a volume ratio of raw materials: hydrogen=1:(5÷900).
Hydrogen can be directed to an adsorption purification from moisture and returned to recycling.
Part of the purified lower alkanes can be used as a diluent cleaned lower alkanes.
As aluminium oxide-platinum catalyst can be used is known, industrially produced catalysts AP-56, FE-62, AP-64, C-2, FE-82 and other catalysts containing platinum and aluminum oxide.
As the lower alkanes can be used fractions of ethane, propane, butane, isobutane, pentane, isopentane and hexane, and others.
For the method of cleaning the lower alkanes from methanol what is new is the use of contact of the hydrocarbons with aluminium oxide-platinum catalyst in the presence of excess hydrogen, which confirms compliance with the patentability criteria of "novelty" and "inventive step". The possibility of applying this method on an industrial cleaning process hydrocarbon fractions confirms the criterion of "industrial applicability".
The method of purification of lower alkanes from methanol is carried out by contacting the purified hydrocarbon fra the Nations of the lower alkanes at a temperature of 180-400°C, a pressure of 1.5 to 4.0 MPa, obymnu feed rate of the raw material 0.4 to 4 h-1a volume ratio of raw materials: hydrogen =1:(5÷900). You can use the pure product (recycle) to dilute the feedstock mass ratio of raw materials: recycling =1:(0,5÷4) and the hydrogen-containing recycle gas to fresh hydrogen in a volume ratio (10÷350):1 respectively.
When the claimed conditions is achieved by clearing fractions of lower alkanes to the content of methanol not more than about 5 ppm., that meets the requirements of polymerization processes.
The implementation of the method is illustrated by the following examples.
Example 1. Cleaning is performed in a reactor with a fixed catalyst bed. As raw materials use propane fraction, containing 3000 ppm. methanol supplied with a bulk velocity of 0.4 h-1the pressure of 1.8 MPa. Raw material is fed into the mixer where it is mixed with dry hydrogen in a volume ratio of 1:100, respectively, and direct contact with the catalyst in the reactor. The process is carried out at a temperature of 280°C on aluminium oxide-platinum catalyst brand FE-62M (TU 38.10173-88). The reaction products from the bottom of the reactor is directed to the selection purified from methanol propane. The reaction products analyzed by hydrocarbon composition by gas chromatography. Analysis of the purified propane shows no admixture of methanol.<> Example 2. Cleaning is performed in the conditions of example 1, but with the content in the propane fraction 16600 about ppm. of methanol. Raw material is fed into the mixer where it is mixed with dry hydrogen in a volume ratio of 1:200, respectively, and direct contact with the catalyst in the reactor. In purified propane impurity content of methanol is 1.2 ppm.
Example 3. Cleaning is performed in the conditions of example 2. As hydrogen is a mixture of fresh and dried hydrogen and recycle hydrogen, drained and cleaned sorbent NaA from oxygen-containing impurities taken in a volumetric ratio of 1:220, respectively. As catalyst, use of FE-82 (TU 21-149-04610600-99). In purified propane impurity content of methanol is 1.0 ppm.
Example 4. Cleaning is performed in the conditions of example 3, but in the propane fraction containing 33300 about ppm. methanol, add recycle propane mass ratio of 1:2,2, respectively. In purified propane impurity content of methanol is 1.6 ppm.
Example 5. Cleaning is performed in the conditions of example 4, but the process is conducted at a temperature of 340°C, a pressure of 3.0 MPa, with a bulk velocity of 1.0 h-1. As hydrogen is a mixture of fresh and dried hydrogen and recycle hydrogen, drained and cleaned sorbent NaA from oxygen-containing impurities taken in volumetric zootoxin and 1:300. The volumetric ratio of raw materials: hydrogen of 1:400. In purified propane impurity content of methanol is about 1 ppm.
Example 6. Cleaning is performed in the conditions of example 5, but is used as raw material butane-butylene fraction, containing to 25.0 wt.% butylene content of methanol in 53.6 ppm about. In a purified product of the methanol content of about 1 ppm. The content of butylene in purified butane 5% wt.
Example 7. Cleaning is performed in the conditions of example 5, but is used as raw material hexane fraction containing methanol 890 ppm. Cleaning is performed on the catalyst P-64 (TU 2177-011-04749189-95). In a purified product of the methanol content of about 1 ppm.
Example 8. Cleaning is performed in the conditions of example 5, but is used as raw material pentane fraction containing methanol 12000 ppm. Cleaning is performed on the catalyst AP-56 (TU 2177-011-04749189-95). In the purified product of the methanol content of 1.2 ppm.
Example 9. Cleaning is performed in the conditions of example 5, but is used as raw material isopentane fraction with methanol content of 2000 ppm. Cleaning is performed on the catalyst C-2 (TU 2177-009-04706192-00). In a purified product of the methanol content of about 2 ppm.
As seen from the examples, the inventive method allows you to clean hydrocarbons from methanol to curing purity (not more than 5 ppm by vol.). In addition, the proposed method allows you to clean alkanes is not only the co from methanol, but from unsaturated hydrocarbons contained in the treated hydrocarbons.
1. The method of purification of lower alkanes from methanol by contact of the feedstock with a catalyst containing alumina at elevated temperature and pressure, characterized in that the catalyst used aluminium oxide-platinum catalyst and the contact is carried out at a temperature of 180-400°C., a pressure of 1.5 to 4.0 MPa, the space velocity of the raw material 0,4÷4 h-1, a volume ratio of raw materials:hydrogen, 1:(5÷900).
2. The method according to claim 1, characterized in that the hydrogen is directed to an adsorption purification from moisture and return in recycling.
3. The method according to claims 1 and 2, characterized in that the lower part of treated alkanes used as diluent cleaned lower alkanes.
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
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: 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: 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
SUBSTANCE: invention relates to methods of preparing catalysts for purifying ethane-ethylene fractions of pyrolysis gas from acetylene impurities through selective hydrogenation. The invention describes a method of preparing a palladium catalyst on an alumina support for selective hydrogenation of acetylene in an ethane-ethylene fraction, which involves preparation of a support, heating the support and a solution of a palladium organometallic complex, saturation of the support with the solution, removal of solvent from the support and reduction of the metal. The method is distinguished by that, heating and saturation are carried out at 1.0≤T/Tcr≤1.2 and 1.3≤P/Pcr≤5.6 with benzonitrile dissolved in carbon dioxide or with styrene or with a cyclohexane complex of palladium chloride. The solvent is removed from the support through simple release of pressure to P<Pcr and reduction is carried out in a hydrogen current at temperature of about 470 K, where T is temperature, K; P is pressure, MPa; Tcr is critical temperature of the solvent; Pcr is critical pressure of the solvent.
EFFECT: obtaining a highly active, highly selective, finely divided catalyst with long continuous operation periods between regeneration periods, and the method of preparing the said catalyst is characterised by low power consumption owing to a considerably short period for removing the solvent.
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SUBSTANCE: invention relates to a method of purifying styrene from phenylacetylene impurities through hydrogenation with molecular hydrogen at high temperature in the presence of a gold-containing catalyst which contains gamma aluminium oxide. The method is characterised by that the catalyst is in form of gold metal particles with average size of 2-3 nm, and total content of gold in the catalyst is 0.01-0.03 wt %; the process is carried out in gaseous phase at temperature 140-160°C.
EFFECT: use of the method enables sharp reduction in consumption of precious metal in the catalyst while ensuring complete purification of styrene from phenylacetylene, prevention of loss of styrene and stable operation of the catalyst.
1 cl, 2 dwg, 2 ex, 1 tbl
FIELD: petrochemical processes.
SUBSTANCE: invention provides a process flow rate comprising at least (i) zone of extractive rectification in presence of polar extractant to produce distillate mainly containing butanes and butane(s); (ii) desorption zone wherein desorption of extractant gives stream containing mainly 1,3-butadiene and. as impurities, at least 2-butene(s) and acetylene hydrocarbons; and (iii) optionally rectification zone for mainly 1,3-butadiene-containing stream. In the latter, α-acetylene hydrocarbons are subjected to liquid-phase selective hydrogenation with hydrogen or hydrogen-containing mixture in presence of solid catalyst containing metal(s) exhibiting high activity in hydrogenation process, preferably non-precious metal(s) on solid support. Temperature is maintained within a range 5 to 75°C at contact time ensuring hydrogenation of no more then 6%, preferably no more than 2% of butadiene present. After hydrogenation, 1,3-butadiene is optionally additionally separated from impurities via rectification.
EFFECT: simplified process.
13 cl, 3 dwg, 2 tbl, 10 ex
FIELD: petrochemical processes.
SUBSTANCE: hydrocarbon fractions are brought into contact, in presence of hydrogen-containing gas, with catalyst containing palladium on porous carrier, which contains mesopores with diameters no less than 4 nm and no large than 20 nm constituting 80 to 98% of the total volume of pore within a range of 4 to 20 nm.
EFFECT: deepened hydrogenation process due to increased catalyst activity regarding diolefins and selectivity regarding aromatic hydrocarbons.
2 cl, 1 tbl, 10 ex
SUBSTANCE: invention relates to catalytic chemistry, specifically to catalysts for oxidation of hydrocarbons in an oxygen-containing gas and methods of preparing said catalysts. The invention describes a catalyst for oxidising hydrocarbons, which contains an active component - manganese oxide and a support in form of granular zirconium oxide with the following content of components, wt %: manganese oxide (MnO2) 5.0-20.0; zirconium oxide (ZrO2) 80.0-95.0. Described also is a catalyst which contains manganese oxide and a granular support made from powdered aluminium oxide in a mixture with crystalline mesoporous aluminium silicate with molar ratio Si/Al equal to 10-60:1, with the following ratio of components, wt %: manganese oxide (MnO2) 5.0-20.0; aluminium oxide (Al2O3) 40.0-85.0; crystalline mesoporous aluminium silicate (AlxSiyOz, where x=0.017-0.1, y=1, z=2.026-2.15) 10.0-40.0. The invention describes a method of preparing catalysts (versions) described above, involving preparation of a support - zirconium oxide or granular mixture of powdered aluminium oxide and crystalline mesoporous aluminium silicate and depositing onto the support manganese oxide, obtained through calcination at 500-600°C of the support saturated with aqueous manganese hydroxide solution after drying in an a temperature interval from 60 to 110°C.
EFFECT: higher catalytic activity and life of the catalyst.
6 cl, 1 tbl, 6 ex