The method of obtaining aromatic hydrocarbons
(57) Abstract:Use for producing high octane motor fuel. The inventive product - aromatic hydrocarbon, C6-C9Original raw material: paraffin hydrocarbon, C3-C11Conditions: 380 - 580°C, the catalyst based on zeolite ZSM - 5. Formed in the gaseous products are incinerated in the presence of a catalyst complete combustion oxidation of light hydrocarbons and add to the original paraffin hydrocarbons in the amount of 2 to 20 wt. %. table 1. The invention relates to the catalytic conversion of hydrocarbons and can be used to produce high octane motor fuel.There is a method of processing a light hydrocarbon feedstock in the presence of high zeolites (1). The method consists of passing a mixture of hydrocarbons containing FROM1-C10such as light naphtha, through the catalyst on the basis of high zeolite with additions of Cu, Zn or Cr at 300-700aboutC.The disadvantage of this method is the formation of compounds of carbon (coke deposits) on the catalyst, which significantly reduces its activity.
3-C11with the catalyst on the basis of high zeolite ZSM-5 at 380-580aboutWith, including the separation of the products of the contacting liquid and gaseous products (2).The process takes place on the catalyst containing the zeolite ZSM-5 (SiO2/Al2O320-100) and metals group 11b (Zn) alone or in combination with metals of group VIB (Cr) and/or group IB (Cu) in an amount of 0.01-5% metal.The disadvantage of this method is the low yield of the target product, as well as a high degree of sakartveloshi catalyst and a small length of the working cycle of the process.The purpose of this method is the increase of the yield of the target product.In addition, the proposed method allows to reduce energy costs in the process of catalysis of hydrocarbons.To achieve the goal in the known method, comprising contacting the paraffin hydrocarbons WITH3-C11with the catalyst on the basis of high zeolite ZSM-5 at 380-580aboutWith the separation of the products of the contacting liquid and gaseous products, gaseous products are subjected to complete combustion in the presence of the catalyst for complete oxidation of light hydrocarbons and is Alceste 2,0-20,0%.An additional effect is achieved due to the fact that the working temperature of the catalyst support due to combustion of gaseous side products, but not at the expense of energy supply.The essence of the method lies in the fact that when the catalytic conversion of paraffin hydrocarbons WITH3-C11in the process of aromatization reaction along with aromatic hydrocarbons are formed gaseous side products of the reactions of CH4WITH2H6N2WITH3H6that can be used to heat the catalyst instead of the main gas. In this case the presence of the oxidation catalyst, which can be used, for example copper in the form of plates or grid, leads to the formation of flue gases (carbon dioxide + water vapor), which by passing them through a zeolite catalyst together with the original paraffin hydrocarbons lead to a reduction of coke deposition on the catalyst.Adding a gas mixture of carbon dioxide with water vapor in the amount of 2.0 to 20.0% is the most effective, as when adding a smaller amount on the catalyst surface remains strong acid centers, which proceed actively processia the acidity of the catalyst surface due to lack of oxide and carbon dioxide.The increase in the content of the gas mixture more than 20,0% leads to a qualitative measurement of surface acid sites of the catalyst due to their damping water vapor, nitric oxide and carbon dioxide. The result is dramatically reduced catalytic activity of the catalyst. In both cases, the yield of the target products (aromatic hydrocarbons) lower than in the known method (2), which is confirmed by experimental studies of the dependence of the yield of the target product from the amount of additives of the mixture of flue gas to paraffin hydrocarbons according to below table.An example implementation of the method.In the process of obtaining aromatic hydrocarbons were used catalyst in the amount of 4 kg, containing 57,0% high zeolite ZSM-5 with a ratio of SiO2/Al2O3= 39, 36.5% of Al2O3AT 3.5% B2O and 3% Zn. The catalyst was placed in a steel reactor of the pilot plant, it heats up to 450aboutWith electric oven reactor by passing through the catalyst of air, preheated in an electric heater 200aboutWith a flow rate of 20 l/hAfter purging air for 4 h instead of air filed heated to 200aboutWith nitrogen the rod, %: isobutane 33; n-butane 26; isopentane 28 and n-pentane 13, at a temperature of 450aboutC, a pressure of 0.6 MPa. Gaseous products of the reaction were burnt to complete oxidation in the presence of complete oxidation catalyst (a catalyst for complete oxidation was used vanadium catalysts V2O5/MoO3in the form of granules). Side of gaseous products at 550aboutC, flow rate 250 h-1subjected to full oxidation (weight of catalyst for complete oxidation was 400 g) prior to the formation of carbon dioxide and water vapor.The mixture of carbon dioxide and water vapor mixed with the raw material in the preheater raw materials at 200aboutWith the amount of 15% to a mixture of paraffin hydrocarbons. The resulting mixture was fed to the reactor flavoring.As a result of aromatization reaction the yield of aromatic hydrocarbons (C6-C9after passing for 40 hours (40 hour) was 57% (in the prototype, in similar conditions, the yield of aromatic hydrocarbons amounted to 49%).The duration of the working period (to reduce the yield of the target products by 30% in comparison with the initial activity) amounted to 400 hours (in the prototype, the duration was 250 hours) 9) - 57%, of aliphatic hydrocarbons - 8.4%, and gases 33,0% (including hydrogen - 2,5%, methane - 4,0%, WITH2OF 7.5%, WITH3+ C4- 19%), Cox - 1,6%.Similar results were obtained when using as the catalyst for complete oxidation of granules of copper oxide. The METHOD of OBTAINING AROMATIC HYDROCARBONS by contacting a paraffin hydrocarbon, C3-C11with the catalyst on the basis of high zeolite ZSM-5 at 380-580oWith, including the separation of the products of the contacting liquid and gaseous products, characterized in that the gaseous products are subjected to complete combustion in the presence of the catalyst for complete oxidation of light hydrocarbons and the resulting mixture of carbon dioxide and water vapor is added to the original paraffin hydrocarbons in the amount of 2.0 to 20.0 wt.%
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: 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
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
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.
SUBSTANCE: invention describes zeolite-containing catalyst for transformation of aliphatic hydrocarbons C2-C12 to a mix of aromatic hydrocarbons or high-octane gasoline component containing zeolite ZSM-5 with silicate module SiO2/Al2O3=60-80 mol/mol and 0.02-0.05 wt % of residual sodium oxide content, zeolite structural element, promoter and binding component, with zirconium or zirconium and nickel oxides as zeolite structural component, and zinc oxide as promoter, at the following component ratio (wt %): zeolite 65.00-80.00; ZrO2 1.59-4.00; NiO 0-1.00; ZnO 0-5.00; Na2O 0.02-0.05, the rest being binding component. Also, a method for obtaining zeolite-containing catalyst is described, which involves mixing reagents, hydrothermal synthesis, flushing, drying and calcinations of sediment. The reaction mix of water solutions of aluminum, zirconium and nickel salts, sodium hydroxide, silicagel and/or aqueous silicate acid, inoculating zeolite crystals with ZSM-5 structure in Na or H-form, and structure-former, such as n-butanol, is placed in an autoclave, where hydrothermal synthesis is performed at 160-190°C for 10-20 hours with continuous stirring; the hydrothermal synthesis over, Na-form pulp of the zeolite is filtered; the obtained sediment is flushed with domestic water and transferred to salt ion exchange by processing by water ammonium chloride solution with heating and stirring of the pulp; the pulp obtained from salt ion exchange is filtered and flushed with demineralised water with residual sodium oxide content of 0.02-0.05 wt % on the basis of dried and calcinated product; flushed sediment of ammonium zeolite form proceeds to zinc promoter introduction and preparation of catalyst mass by mixing of ammonium zeolite form modified by zinc and active aluminum hydroxide; obtained catalyst mass is extruded and granulated; the granules are dried at 100-110°C and calcinated at 550-650°C; calcinated granules of zeolite-containing catalyst are sorted, ready fraction of zeolite-containing catalyst is separated, while the granule fraction under 2.5 mm is milled into homogenous powder and returned to the stage of catalyst mass preparation. The invention also describes method of transformation of aliphatic hydrocarbons to high-octane gasoline component or a mix of aromatic hydrocarbons (variants), involving heating and passing raw material (gasoline oil fraction direct sublimation vapours or gas mix of saturated C2-C4 hydrocarbons) through stationary layer of the aforesaid catalyst.
EFFECT: reduced number of components and synthesis stages of zeolite-containing catalyst; increased transformation degree of raw material; improved quality and yield of target products with the said catalyst.
4 cl, 8 tbl, 12 ex
SUBSTANCE: alkylbenzol with structure R1R2CH(Ph) is obtained from alkylphenyl alcohol with structure R1R2C(Ph)OH. Method includes following stages: (a) supply of initial flow, containing alkylphenyl alcohol with structure R1R2C(Ph)OH, into reactor with catalytic distillation zone; (b) simultaneously in reactor: (i) contacting of initial flow, containing R1R2C(Ph)OH, with hydrogen in catalytic distillation zone in order to convert R1R2C(Ph)OH into R1R2CH(Ph) and to form reaction mixture and (ii) separation of R1R2CH(Ph) from reaction mixture by fraction distillation in order to obtain higher than catalytic distillation zone, flow, which contains R1R2CH(Ph) with lower concentration of R1R2C(Ph)OH in comparison to initial reactor flow in position higher than catalytic reaction zone; R1 and R2 each represent hydrogen or hydrocarbon group with 1-10 carbon atoms and one of R1 and R2 is not hydrogen.
EFFECT: more pure alkylbenzol with smaller amount of undesirable by-products and using smaller number of stages.
6 cl, 5 tbl, 1 dwg
SUBSTANCE: invention refers to the method for preparation of aromatic hydrocarbons accompanied with simultaneous obtaining of hydrogen, methanol, motor oils and fresh water from the unstable hydrocarbon gas condensate obtained from gas condensate and oil fields including if necessary its desulphurisation, following obtaining of synthesis gas by one-stage oxidising with air oxygen, its conversion to methanol, following catalytic conversion of methanol to motor oils, separation of the water formed on all process stages, evaporation of the hydrocarbons residues including methanol and fatty hydrocarbons from the water (united and formed on all process stages), water bioremediation and mineralisation. The initial hydrocarbon gas is unstable hydrocarbon gas condensate without preliminary separation of methane and ethane from propane and butane, the said initial gas before its conversion to synthesis gas undergoes the catalytic aromatisation during heating. Then the obtained aromatic hydrocarbon and hydrogen are separated, hydrogen is at least partially used for synthesis gas obtaining in order to change the ratio H2:CO 1.8-2.3:1), and if necessary it is partially used on the stage of desulphurisation with synthesis gas obtaining from hydrocarbon gases (unreacted and formed on the aromatisation stage). The invention refers also to the device for implementation of the method described above.
EFFECT: increasing of the processing of the efficiency of unstable hydrocarbon gas condensate with enhanced obtaining of target products, to make the process more environmentally safe, to increase the quantity and quality of the obtained fresh water.
2 cl, 5 ex, 1 dwg
SUBSTANCE: method of hydrocarbon aromatisation includes: a) contacting of alkane containing from 2 to 6 carbon atom in molecule with at least one catalyst consisting virtually of platinum applied to zeolite MFI which lattice consists virtually from gallium, silicon and oxygen and b) separation of aromatic products. The preparation method for platinum-gallium zeolite catalyst used for hydrocarbon aromatisation is described, it includes: preparation of gallium zeolite containing silicon and gallium; precipitation of the platinum to said zeolite; and c) zeolite calcination. In the said method the said gallium zeolite catalyst consists virtually of platinum applied to zeolite MFI which lattice consists virtually from gallium, silicon and oxygen. The platinum- gallium zeolite catalyst for hydrocarbon aromatisation containing: a) gallium-silicon zeolite and b) platinum precipitated to gallium-silicon zeolite is also described. In the said method the said platinum-gallium zeolite catalyst consists virtually of platinum applied to zeolite MFI which lattice consists virtually from gallium, silicon and oxygen.
EFFECT: enhancing of the catalyst selectivity in transforming of lower alkanes to aromatic hydrocarbons.
30 cl, 3 dwg, 4 tbl, 2 ex
SUBSTANCE: invention relates to a method of producing aromatic hyhrocarbons and lower olefins, involving catalytic dehydrocyclisation of hydrocarbon material in the presence of a zinc-containing zeolite catalyst, at high temperature and pressure, separation of dehydrocyclisation products into product A - aromatic hydrocarbons C6+, and product B - mixture of non-aromatic hydrocarbons with hydrogen, subsequent hydrodealkylation of product A, obtaining commercial-grade benzol, and pyrolysis of product B, obtaining lower olefins, and characterised by that, the dehydrocyclisation material used is C2-C6 paraffins, the process is carried out at 0.9-1.3 MPa pressure, after separating the C10+ fraction, product A is subjected to hydrodealkylation, commercial-grade benzol, methane and ethane fractions, ethane fraction and product B are separated from hydrodealkylation products, or after separating over 50 vol % methane-hydrogen fraction from product B, product B is taken for pyrolysis, commercial-grade ethylene and propylene are separated from gaseous products of pyrolysis, liquid products of pyrolysis - pyrolysis condensate, containing aromatic hydrocarbons, is subjected to catalytic hydrogenation and hydrodesulphurisation, and subsequent hydrodealkylation, obtaining commercial-grade benzol, methane and ethane fractions, the latter is returned for pyrolysis.
EFFECT: increased output of lower olefins, significant improvement of economic parametres of the process due to increase of inter-regeneration period of dehydrocyclisation catalyst.
1 cl, 5 ex, 5 tbl
SUBSTANCE: invention relates to a method of aromatising alkanes and involves bringing alkanes, which contain from one to four carbon atoms, into contact with a Pt/ZSM-5 catalyst which is deposited on MFI zeolite, the lattice of which consists of aluminium, silicon and oxygen. Use of the given catalyst during aromatisation of alkanes prevents formation of methane and increases BTX selectivity.
EFFECT: higher content of ethane than methane in the light gas fraction enables use of exhaust gas as raw material for cracking apparatus.
15 cl, 2 tbl, 5 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
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 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: 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: 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