Method of obtaining high-octane number component of motor fuel
SUBSTANCE: method involves hydrocarbon transformation in a reactor in the presence of modified catalyst containing, mass %: 53.0-60.0 of ZSM-5 high-silica zeolite with the ratio of SiO2/Al2O3=39, 34.0-38.0 of Al2O3, 2.0-5.0 of B2O3, 1.0-5.0 of Zn, 0.0-5.0 of W, 0.0-3.0 of La, 0.0-3.0 of Ti at 300÷700°C, including separation of liquid and solid transformation products, followed by burning oxidation of gaseous products and addition of the obtained mix of carbon dioxide and water vapour to the source hydrocarbons at the rate of 2.0÷20.0 mass %. Before the raw material intake the reaction system is flushed by an inert gas (nitrogen), starting from 300°C and to the transformation temperature. Hydrocarbons used are alkanes, olefins or alkane olefin mixes C2-C15 without preliminary separation into fractions. Gaseous transformation products undergo burning and complete oxidation in the presence of an oxidation catalyst of vanadium/molybdenum contact piece, V2O5/MoO3. To sustain continuous process two identical reactors are used, where the catalyst is transformed and recovered in turns.
EFFECT: longer working transformation cycle due to the continuous process scheme; higher yearly output of aromatic hydrocarbons; reduced energy capacity and improved ecology of the process.
The technical field
The invention relates to the catalytic conversion of paraffinic, olefinic hydrocarbons and mixtures thereof and can be used to obtain as high-octane motor fuel, and individual aromatic compounds - benzene, toluene, ethylbenzene, ortho-, meta-, para-xylene, cumene, durene.
The level of technology
There is a method of processing a mixture of hydrocarbons, C1-C10such as light naphtha, at 300-700°in the presence of high zeolite with additions of Cu, Cr or Zn (JP No. 59-152337, CL SS 15/00, 1984). The disadvantage of this method is significant formation of coke deposits on the catalyst, which significantly reduces its activity.
Also known is a method of obtaining aromatic hydrocarbons by contacting the paraffin hydrocarbons With3-C11with a catalyst based on zeolite ZSM-5 at 380-580°involving separation of the products of the contacting liquid and gaseous (DD No. 251710, CL B01J 29/28, 1986). The disadvantage of this method is the low yield of the target product, a high degree of sakartveloshi catalyst and a small length of the working cycle of the process.
The closest to the invention is a method for aromatic hydrocarbons by conversion of paraffin hydrocarbons With3-C11at present the AI-based catalyst high ZSM-5 at 380-580° With involving separation of the products of transformation of liquid and gaseous, subsequent combustion of the gaseous oxidation products in the presence of known oxidation catalyst (e.g., vanadium-molybdenum - V2O5/M0About3) and adding the resulting mixture of carbon dioxide and water vapor to source raw materials in the amount of 2.0 to 20.0 wt.% (RU # 2030376, CL SS 15/02, 10.03.1995). The used catalyst of transformation in this way (RU # 2024305, CL B01J 29/28, 15.12.1994) contains, wt.% 57,0 high zeolite ZSM-5 with the ratio of SiO2/Al2O3=39, 36,5-Al2About3, 3,5 - In2O3, 3,0 - Zn.
The yield of aromatic hydrocarbons With6-C9is 57%, the period of stable operation of the catalyst is equal to 400 hours, which is quite a good result, but the possibility of improvement is maintained.
Disclosure of inventions
The purpose of the claimed invention is the increase in time stable operation of the catalyst, the duration of the working cycle of the process, increasing the yield of aromatic hydrocarbons and ultimately increase their annual production. To achieve the goal in a method of producing aromatic hydrocarbons according to the prototype by contacting in a reactor paraffin hydrocarbons with a catalyst based on high ZSM-5 at 380-580°With, is with the division of food contact liquid-target and gaseous-side, subsequent combustion of the gaseous oxidation products in the presence of a known catalyst for the oxidation of light hydrocarbons and carbon monoxide and adding the resulting mixture of carbon dioxide and water vapor in the amount of 2.0 to 20.0 wt.% to the original hydrocarbons, first:
before the intake of raw materials, the reaction system is purged with inert gas-nitrogen, starting with 300°and to the temperature of the probe;
- as a source of raw materials, in addition to the paraffin hydrocarbons, are olefinic hydrocarbons and any paraffin-olefin mixture C2-C15;
- combustion and complete oxidation of gaseous products carried out sequentially: first, the combustion in the annular space of the reactor conversion and then oxidation in a special apparatus with vanadium-molybdenum catalyst V2O5/M0About3;
the process of transformation carried out alternately in two identical reactors periodic actions;
- as a catalyst for transformation using the modified catalyst containing, wt.%: 53,0-60,0 high zeolite ZSM-5 with the ratio of SiO2/Al2O3=39, Al2About3is 34.0-38,0, In2About3- 2,0-5,0, Zn - 1,0-5,0, W - 0,0-5,0, La - 0,0-3,0 and Ti - 0,0-3,0.
In addition, thanks to the rational technological scheme implemented is I process achieved additional 2 effect: energy, providing the operating temperature of all devices - reactor conversion and oxidation, rectification columns and stabilization, separators and condensers by burning gaseous side products of transformation of CH4With2H6With3H8With4H10and not by supplying energy from outside, for example, the main gas or electric power, environmental, ensuring the emission of only carbon dioxide and water vapor is chemically harmless substances.
The essence of the method is that, once loaded into the reactor of the developed catalyst of transformation, having the composition, wt.%: 55,5 high zeolite ZSM-5 with the ratio of SiO2/Al2About3=39, 36,5 - Al2About3, 3,5 - In2O3, 3,0 - Zn, 1.0 to W, 0.3 to La, 0.2 to Ti, it is heated up to 300°With air flow, then instead of the air supplied to the nitrogen and continue to heat the catalyst in a stream of nitrogen to a temperature of transformation 450-550°C for 4 hours. This process removes oxygen from the reaction system and adsorbed on the catalyst surface oxygen-containing compounds that prevent resinification of the original hydrocarbons in their subsequent intake, thus reducing kokoulina on the surface of the catalyst and the hydrocarbon is leciva time stable operation of the catalyst by 12-15%. In addition, the presence of oxygen in the zone of transformation can lead to the destruction of the catalyst due to a sharp temperature increase in the combustion of hydrocarbons.
This unique catalyst allows it to be used as a raw material without separation into fractions of a wide range of paraffin-olefin hydrocarbons:
associated gas production, gas terminal stages of separation, propane-propylene-butane-butylene fraction, NGL - wide fraction of light hydrocarbons, gaseous and liquid waste processing (including gases, torches), gas condensate, stable natural gasoline, naphtha, compressed and any liquid mixture of paraffin-olefin hydrocarbons.
The process of converting paraffin hydrocarbons into aromatic on the catalyst flows through a stage of dehydrogenation - with the formation of olefins as an intermediate product. Therefore, the use of olefins as feedstock, multistage process of aromatization is reduced by one stage, and thereby increases the time stable operation of the catalyst in the range of 9-11% and decrease respectively the inputs.
Side gaseous products of conversion are first subjected to combustion in the annular space of the reactor in order to utilize the heat of combustion to maintain the working is that the temperature of the process of transformation, without the supply of heat from outside, for example without burning the main gas that causes additional thermal effect, saving process. Then the exhaust gases of combustion are subjected to complete oxidation to carbon dioxide and water vapor in the oxidation reactor in the presence of a known catalyst for the oxidation of V2About5/M0About3in the form of granules, which eliminates the leakage of carbon monoxide and light hydrocarbons and helps to ensure a truly binary mixture of carbon dioxide and water vapor, thereby, on the one hand, environmentally friendly emissions of wastes and, on the other hand, adding its binary mixture) in an amount of 10 wt.% for starting materials (if applying in the reactor) reduces to 16-18% kokoulina on the catalyst due to the partial regeneration:+CO2→2SD and C+H2O→CO+H2during the transformation.
Accommodation in the technological scheme of production of the second identical reactor conversion is a good solution, because it allows you to switch from batch to continuous. So, when one reactor is turning in the other the regeneration of the catalyst, and Vice versa. However, annual production target production increases by 20-50%, depending on the actual number of regenera the second catalyst during the year, taking into account operation of one reactor of periodic action.
Modification of the catalyst of transformation by introducing additional promoters W, La, Ti allows to reduce the activity of the acidic centers of coking, increase dimerize, cyclessa and dehydrating properties of the catalyst, which leads to an increase in its time stable operation and in accordance with the time mezhregionalnogo mileage and to increase the yield of aromatic hydrocarbons.
Below are examples of the method of synthesis catalyst based on zeolite ZSM-5 and for implementing a method of obtaining a high-octane component of motor fuel in the presence of the prepared catalyst.
The preparation of the catalyst is carried out in a vessel with stirrer. 11 l of a solution of ammonium sulfate with a concentration of 30 g/l (in an amount to provide 5 EQ. NH4 +1 EQ. Na+in the zeolite) download with stirring 1245 g high zeolite ZSM-5 in the sodium form, the resulting suspension is heated to 60°C and maintained at this temperature for 2 hours, the Suspension of the zeolite is drained on a suction filter and after wringing the mother liquor was washed with 12.5 liters of demineralized water. The resulting pellet is discharged from the suction filter and subjected to repeat similar processing is cation exchanged with a solution of ammonium sulfate and subsequent washing to a residual content of Na+in C the Olite not more than 0.04%. The obtained ammonium form of the zeolite is treated at a temperature of 60°C for 2 h in 6,8 l 0.5 n solution of zinc acetate.
After a suspension of the zeolite was filtered and successively treated with subsequent filtering, respectively solutions of parabolicamara ammonium acetate lanthanum and of titanium in amounts corresponding content in the catalyst of 1.0% W, 0.3% of La and 0.2% of Ti. Then the resulting mass of the zeolite is filtered and sent to the granulation with a binder Al2About3and with the addition of In2O3to reduce the acidity of the binder. The procedure for preparation of the masses for molding: in the mixer load the estimated amount of the zeolite mass - 1305 g, Al2About3- 793,9 g2About3is 76.1 g and are peptization mixture adding HNO3to pH 3. The mass is stirred until homogeneous and evaporated to the desired granulating humidity - 40-48%.
Ready to moldable mass plastificator on rollers and is then formed on the screw granulator. Granules provalivajut on the air for 20 h and then dried in a chamber dryer for 10 hours Obtained granules are calcined in an electric furnace at a temperature of 550°C for 6 hours At this temperature rise carried out with a speed of 100°With in the hour. The prepared catalyst has the following composition, wt.%: vysokokremnistykh the y zeolite ZSM-5 (with the ratio of SiO 2/Al2O3=39) - 55,5, Al2About3- 36,5, In2O3- 3,5, Zn - 3,0, W - 1,0, La - 0.3, And Ti Is 0.2. Similarly prepared catalyst samples with different content of each of the additional promoters - W, La, Ti, and the sample not containing these promoters.
Then spend the activation of the catalyst with a gas mixture containing, vol.%: carbon monoxide - 6; carbon dioxide - 7; water vapor - 12; hydrogen - 10; oxygen - 5; nitrogen - else if 500°C for 6 hours After completion of the gas treatment catalyst pellet rinsed with air and cooled in air to room temperature. Then the granules are discharged into the hopper, then scatter from dust and fall asleep in a plastic bag, inserted in the barrel. The catalyst thus prepared, maintains stable activity for a long time. Assessment of the stability of the catalyst in the reaction multistage transformation of initial hydrocarbons (this reaction is dehydrogenation, cracking, isomerization, disproportionation, dimerization, cyclization, hydrogenation, pyrolysis, oligomerization) is carried out on the yield of liquid hydrocarbons. The operational lifetime of the catalyst is calculated by the decrease of the yield of the target products by 30% compared with the initial activity.
Below is a specific example of the method according to izopet the of - high octane component of motor fuel.
For laboratory studies, the addition of catalyst is 100 g, the pilot tests using the catalyst in the amount of 4 kg, containing, wt.%: 55,5 high zeolite ZSM-5 with a ratio of SiO2/Al2O3=39, 36,5 - Al2About3, 3,5 - In2About3, 3,0 - Zn, 1.0 to W, 0.3 to La and 0.2 - Ti. A portion of the catalyst placed in the reactor and in air flow with a flow rate of 10 h-1heated to a temperature of 550°With a speed of no more than 100°/H. Then the temperature of the reactor in a stream of air is reduced to 300°and instead of the air supplied to the nitrogen with a bulk velocity 4 h-1. Then the temperature of the catalyst in a stream of nitrogen to increase the temperature of transformation 480°speed ≈ 100°C/H. Then the reactor is fed feedstock is a mixture of paraffin-olefin hydrocarbons. It is either NGL composition With2-C6or propane-butane-butylene fraction composition With3-C4or oil fraction C2-C15or, for example, a mixture of the following composition,%: isobutane - 32,4; n-butane - 36,8; isopentane and 17.6 and n-pentane is 13.2. Coming out of the reactor products are becoming gradually cooled and separated into liquid and gaseous products. The latter are by-products and are directed into the annular space of the reactor for sigani and maintain the temperature of transformation instead of using the main gas. Then the exhaust after the combustion gases consisting of CO2N2O, and not entered in the combustion of hydrocarbons (slippage), proceed in the apparatus with a catalyst for complete oxidation of V2O5/M0About3where advanced as oxygen for combustion serves the air. In the guaranteed form only carbon dioxide and water vapor, which is directed to the discharge into the atmosphere. Part of the mixture of CO2+H2O in an amount of 10 wt.% from the source of hydrocarbon fed into the reactor conversion.
In the reaction of dehydrocyclization the yield of liquid hydrocarbons in the end of 40 h of transformation is 69.7% (including aromatic hydrocarbons6-C10of 62.3%) with an octane number according to research method 104,3÷106,1, gas - 29,4% (including H2is 2.2%, SN4of 3.6%, With2is 6.7%, With3+C4at 16.9), coke - 0.9%. The operational lifetime of the catalyst (to reduce activity by 30%) amounts to 530 hours. Similar similar results - within ±3% were obtained when using different mixtures of hydrocarbons as a source of raw materials and when using catalysts with different contents additional promoters. In the case of using the catalyst without additional promoters having the composition 57,0% ZSM-5 (SiO2/Al2O3=39), 36.5% of Al 2About3, 3.5% In2About3and 3.0% Zn, the yield of aromatic hydrocarbons is 57.1%, and the duty cycle of the catalyst - 410 hours.
The process of regeneration of the catalyst in an industrial environment carried out within 5 days; which consists of the following steps: lowering the reactor temperature to 300°With, the supply of raw materials, purging the reaction system with nitrogen for a long time, adding to the nitrogen in the reactor of air from the minimum amount to 100% of the content, the gradual raising of the temperature of the reactor up to 600°With, the carrying out of the process of regeneration of the catalyst prior to the termination of content in air flow monoxide and carbon dioxide, lowering the reactor temperature to a temperature holding transformations 480°, purging the reaction zone with nitrogen. If you take the duration mezhregionalnogo mileage catalyst 530 hours (22 days), although in real industrial conditions this value with the increase in the number of regenerations will be reduced, then the year will need ≈ 330/22=15 regenerations, ie 5×15=75 days or ≈ 23% of the time in the year the products are not produced. Therefore, the annual production of the end product using a single periodic reactor will be in the best case, 77%, which ultimately will be determined by the actual number of regenerations of the catalyst during the year works the reactor batch and, undoubtedly, this value will be less. The inclusion in the technological tying the second reactor periodic action allows more than 23% increase annual output of high-octane component of motor fuel. However, when one reactor is turning in the other the regeneration of the catalyst and, on the contrary, when the first regeneration, the other transformation.
Thus, the method according to the invention improves not only the period of stable activity of the catalyst and the output, respectively, of aromatic hydrocarbons, but also significantly increase their annual production.
A method of obtaining a high-octane component of motor fuel by conversion in the reactor hydrocarbon in the presence of a catalyst based on high ZSM-5 at 300÷700°involving separation of the products of transformation of liquid and gaseous, subsequent combustion of the gaseous oxidation products and adding the resulting mixture of carbon dioxide and water vapor to the original hydrocarbons in the amount of 2.0 to 20.0 wt.%, wherein the first, before the intake of raw materials, the reaction system purge with an inert gas (nitrogen), starting with 300°and to the temperature of transformation; as hydrocarbons used paraffins, olefins or paraffin-olefin mixture C2 -C15without prior separation into fractions; gaseous products of conversion are sequentially subjected to first burning and then complete oxidation in the presence of known oxidation catalyst; to ensure continuity of the process uses two identical reactor, which in turn processes of transformation or regeneration of the catalyst; the process of transformation is carried out in the presence of the modified catalyst containing, wt.%: 53,0-60,0 zeolite ZSM-5 with the ratio of SiO2/Al2O3=39, 34,0-38,0 Al2About3, 2,0-5,02About3, 1,0-5,0 Zn, 0,0-5,0 W, 0,0-3,0 La, 0,0-3,0 Ti.
FIELD: gas treatment.
SUBSTANCE: invention relates to catalytic treatment of natural gas to remove higher hydrocarbons and sulfur compounds contained therein while simultaneously converting hydrocarbons into aromatics and methane. Catalyst comprises crystalline aluminosilicate expressed by molar ratio in following way: xQ : (0.01-0.1)M2O : (0-0.08)Z2O3 : SiO2 : (0.0001-0.5)Me, wherein Q denotes tetrapropylammonium bromide; Z aluminum, gallium, or mixture thereof; x = 0-0.5; M represents at least proton or metal cation selected from sodium and potassium cations; and Me is at least one metal selected from zinc and copper. Preferably, zeolite H-ZSM-5 is employed and gas is treated at temperature above 600°C and pressure, which is prevalent in gas transportation pipelines.
EFFECT: improved gas treatment process.
5 cl, 5 tbl, 14 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention provides high-silica zeolite catalyst comprising molybdenum and a second modifying element, namely nickel, content of the former in catalyst being no higher than 4.0 wt % and that of the latter from 0.1 to 0.5 wt %. Preparation of the catalyst involves modifying zeolite with molybdenum and second promoting element, the two being introduced into zeolite in the form of nano-size metal powders in above-indicated amounts.
EFFECT: enhanced efficiency of non-oxidative methane conversion process due to increased activity and stability of catalyst.
3 cl, 1 tbl, 7 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T2O3(10-1000)SiO2, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula CnH2n+1(CH3)3NAn (where n=12-18, An is Cl, Br, HSO4 -) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.
EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.
16 cl, 2 dwg, 2 tbl
FIELD: petroleum chemistry and petroleum processing.
SUBSTANCE: method involves contacting the raw containing 6-60 vol.% of propane and/or butane, and methane and/or ethane as a diluting agent also with catalyst comprising zeolite of the pentasil group. Contacting is carried out at temperature 480-600°C, the volume rate raw feeding 300-1000 h-1, under pressure 0.1-3 MPa and partial pressure of propane and/or butane 0.8 MPa, not above. Invention provides enhancing stability of the catalyst performance and retaining the high degree of raw conversion.
EFFECT: improved method for stability enhancement.
2 cl, 1 tbl, 7 ex
FIELD: petrochemical processes.
SUBSTANCE: feedstock olefins are submitted to oligomerization in contact with zeolite oligomerization catalyst and C4-hydrocarbons isolated from resulting products are then aromatized on zeolite aromatization catalyst. Hydrogen-containing dry gas recovered from aromatization products is used for oligomerization-preceding selective hydrogenation of butadiene in feedstock to give butylene-enriched starting material.
EFFECT: prolonged catalyst lifetime.
3 cl, 3 tbl
SUBSTANCE: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.
EFFECT: increase in catalyst activity and gasoline octane number, accompanied by increase in yield.
4 cl, 3 tbl, 4 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to catalyst for aromatization of alkanes, to a method of preparation thereof, and to aromatization of alkanes having from two to six carbon atoms in the molecule. Hydrocarbon aromatization method consists in that (a) C2-C6-alkane is brought into contact with at least one catalyst containing platinum supported by aluminum/silicon/germanium zeolite; and (b) aromatization product is isolated. Synthesis of above catalyst comprises following steps: (a) providing aluminum/silicon/germanium zeolite; (b) depositing platinum onto zeolite; (c) calcining zeolite. Hydrocarbon aromatization catalyst contains microporous aluminum/silicon/germanium zeolite and platinum deposited thereon. Invention further describes a method for preliminary treatment of hydrocarbon aromatization catalyst comprising following steps: (a) providing aluminum/silicon/germanium zeolite whereon platinum is deposited; (b) treating zeolite with hydrogen; (c) treating zeolite with sulfur compound; and (d) retreating zeolite with hydrogen.
EFFECT: increased and stabilized catalyst activity.
26 cl, 1 dwg, 5 tbl, 4 cl
FIELD: petrochemical processes.
SUBSTANCE: simultaneous dehydrogenation of mixture containing alkyl and alkylaromatic hydrocarbons is followed by separating thus obtained dehydrogenated alkyl hydrocarbon and recycling it to alkylation unit. Dehydrogenation reactor-regenerator employs C2-C5-alkyl hydrocarbon as catalyst-transportation carrying medium.
EFFECT: increased process flexibility and extended choice of catalysts.
FIELD: industrial organic synthesis and catalysts.
SUBSTANCE: liquid hydrocarbons that can be used not only as motor fuel components and additives in production of high-octane gasolines with content of aromatic hydrocarbons no more than 20 wt % but also as target products of organic synthesis are obtained catalytically in the form of mixture from dimethyl ether. Catalyst for this process based on zeolites and including zinc and/or cobalt oxides and alumina as binder is characterized by that zeolite utilized is CVM zeolite and/or clinoptilolite and further contains chromium and boron oxides, whereas proportions of catalyst constituents are the following, wt %: chromium oxide Cr2O3 2.0-4.0, cobalt and/or zinc oxide (CoO and/or ZnO) 2.0-4.0, boron oxide B2O3 3.0-5.0, CVM zeolite and/or clinoptilolite 10-30, and alumina - the rest.
EFFECT: increased yield of motor fuel components at content of aromatic hydrocarbons not exceeding 20%, and increased stability of catalyst.
2 cl, 2 tbl, 15 ex