A method of obtaining a lower mono - and dialkylphenols
(57) Abstract:Use: production of lower mono - and dialkylphenols. The inventive method of obtaining lower mono - and dialkylphenols (DUB) involves feeding benzene and lower olefin in the alkylation plant, equipped with a reactor unit for the interaction of benzene with a lower olefin in the presence of a catalyst complex on the basis of anhydrous aluminium chloride, a node separation of the catalyst complex from the alkylate, a node of a multi-stage rectification with the last stages of selection return benzene, lower alkyl benzene, the lower the DUB, partially refundable in the alkylation reactor, and partly allocated to the installation, and polyalkylbenzenes (PUB), while the lowest DUB before drainage installation is subjected to a clear rectification in three distillation columns, in the first of which emit light fraction stream which is returned to the node in the multi-stage distillation and reactor block, in the second column provide a complete separation of the light fraction, the flow of which return to the node in the multi-stage distillation and reactor unit, in the third column of the cubic product of the second column separates the lowest DUB from the PUB, which returns tdelay by rectification from the pitched product and return in the reactor block alkylation. 1 table, 1 Il. The invention relates to the production technology of lower mono - and dialkylphenols and can be used in petrochemical plants.A method of obtaining lower alkyl benzenes (AB) by the alkylation of benzene lower olefins in the presence of a catalyst complex on the basis of anhydrous aluminium chloride, in accordance with which the alkylate washed with water, neutralized and subjected to multi-stage distillation with the release of the reversionary benzene, lower alkyl benzenes and polyalkylbenzenes. The latter is mixed with fresh original benzene (mass ratio of benzene and polyalkylbenzenes 1:(0,41-0,72) and subjected to azeotropic dehydration. Drained the original benzene and polyalkylbenzene served on alkylation. This method makes it possible to obtain the lowest monoalkylbenzenes (selectivity 93,3-93,5 ), but lower dialkylphenol (DUB) it does not produce (1).For the production of DUB (diethylbenzene) ethylbenzene subjected to disproportionation at elevated temperature in the presence of a catalyst complex on the basis of anhydrous aluminium chloride. The process is carried in the ideal mode of displacement when the concentration of the catalyst komata rectification allocate commodity diethylbenzene, meet quality brand AND (TU-6-030387-75), and side pitched a product used as a component of fuel oil (2).Thus, for the production of AB and DUB, you must have two separate installations. At the same time, capital operating and other costs are significantly lower when combining on a single installation of production AB and DUB.Also known industrial method of obtaining lower AB and DAB on a single installation, which consists in the following. Benzene and lower olefin is fed to the alkylation plant, equipped with a reactor unit for the interaction of benzene with a lower olefin in the presence of a catalyst complex on the basis of anhydrous aluminium chloride, a node separation of the catalyst complex from the alkylate, a node of a multi-stage rectification with the last stages of selection return benzene, lower alkyl benzene, lower dialkylphenol partially returned to the alkylation reactor, and partly allocated to the installation, and polyalkylbenzenes. Exhaust with installation flow DUB (mix diethylbenzene) are used as high-octane additives to motor fuels (gasoline) (3).The disadvantages of this method is nevitta monomer, used in the synthesis ionoobmennyh resins). On the other hand, the drainage installation raw DUB and the PUB does not allow you to use contained polyalkylbenzene as the return of the commodity component, which leads to unnecessarily high unit costs source of ethylene and benzene (flow source, referred to the unit of product).Thus, a review of the prior art shows the need for developing a method of obtaining a lower mono - and dialkylphenols, allowing installation with one reactor alkylation-parallelomania to get lower mono - and dialkylphenols, suitable for the production of monomers with lowest specific costs source of ethylene and benzene.In accordance with the invention features a method of obtaining a lower mono - and dialkylphenols, including the filing of benzene and lower olefin in the alkylation plant, equipped with a reactor unit for the interaction of benzene with a lower olefin in the presence of a catalyst complex on the basis of anhydrous aluminium chloride, a node separation of the catalyst complex from the alkylate, a node of a multi-stage rectification with the last stages of selection return benzene, lower alkyl is, and polyalkylbenzenes; lower dialkylphenol before drainage installation is subjected to a clear rectification in three distillation columns, the first of which emit light fraction stream which returns the node multistage distillation and reactor block, in the second column provide a complete separation of the light fraction, the flow of which is returned to the reactor unit, in the third column of the cubic product of the second column separates the lower dialkylphenol from polyalkylbenzenes faction, which in return node multistage rectification on stage allocation polyalkylbenzene fraction in the reactor block.The expression "reaction block" in this description means the ability to use a single reactor or in multiple reactors that perform the same function, but this expression expansion cannot be interpreted: installation containing multifunctional reactors, such as reactor alkylation and disproportionation reactor of this invention do not have a relationship.The invention is illustrated in the figure "schematic diagram of obtaining mono - and dulcibella".On tropopause composition, wt. Al C1327; C6H633; monoalkylphenol 18; polyalkylbenzene 22. The catalyst complex is prepared in a separate apparatus (not shown in the figure, because the catalyst complex and a method of its preparation are not the object of the present invention). The catalyst complex can be fed continuously or intermittently, as known from the prior art) is preferable. The catalyst complex is prepared by any well-known from the prior art method.Line 2 on the installation serves the original benzene, line 3 of the lower olefin (ethylene or propylene). In practice it is possible to use pure olefins or hydrocarbon fraction containing, for example ethane-ethylene or propane-propylene fraction. On line 4 by alkylation return serves raw DUB, and on line 5 return benzene. All of these flows in the alkylation reactor 6. (The installation may contain one or more alkylation reactors, as noted above). The alkylation reactor may be any of those known in the prior art. In particular, it is possible to use the reactor column type, known from (3) or any other reactor for liquid-phase alkylation of benzene nlnoy capacity of about 30 tons From the top of the column 19 assign boiling impurities that on line 20 back to the alkylation reactor, and the other part (from 1 to 99.) in the distillation column 13. When receiving mono - and diethylbenzene in the upper part of the column 19 maintain a temperature of about 153oAnd at the bottom about 190oC. Extending from the lower part of the distillation column product line 2 serves in a distillation column 22, the separation capacity of about 50 tons In the upper part of the column 22 maintain a temperature of about 180oWith, and in the lower 200o(When receiving mono - and diethylbenzene). In the column 22 is a comprehensive removal of low-boiling products. Suitable rectification of the conditions under which loss of distillate DUB together with low-boiling products is minimal, for which the distillation should be carried out at reflux of the order of 10-20. The distillation column 22 through line 23 is mixed with the distillate of the column 19 and returned to the alkylation reactor and distillation column 13, line 31. CBM product of the column 22 through line 24 serves in a distillation column 25, the separation capacity of about 30 tons, operated at reflux numbers from 1.5 to 5. As distillate from the top of the column through line 20 assign DUB, the quality of the receiving mono - and diethylbenzene keep the temperature at the top and at the bottom of the column 183 and 193oS, respectively. As the cubic product from the bottom of the column through line 27 to divert the flow of high-boiling impurities (PUB and resin). Part of this flow on the return line 28 to column 16, and the other part on line 29 back to the alkylation reactor 6. The relationship between these flows is in the range from 2:1 to 1:95. The specific value of this ratio is determined depending on how much catalyst poisons contained in the product stream 27. With the increasing content of catalytic poisons in the product stream 27 should be an increase in flow directed to the column 13. On the contrary, when the decrease of catalytic poisons in the product stream 27 should be an increase in flow directed into the reactor 6. Column 19, 22, 25, it is advisable to operate at a pressure close to atmospheric. In the case of using propylene as the starting olefin is advisable to maintain the temperature of the top and bottom of the columns 19, 22, 25: 165/195oWITH, 180/205oWITH, 193/205oS, respectively. The catalyst complex is selected in the node 8 may be fully or partially returned to the reactor 6 through line 30, indicated in the figure by the dotted line.Expert it is clear that the figure shows the principal is as columns, pumps, intermediate capacity, automation and control, etc., not shown.Examples 1 and 2. Industrial plant collected under the scheme in accordance with the figure, conduct pilot runs with the aim of obtaining the ethyl - and diethylbenzene (example 1), and isopropyl - and diisopropylbenzene (example 2).The process conditions described above in the description of process flow diagram, consumption of basic raw material and product flows in the table.In accordance with example 1 are as ethylbenzene, meets the requirements of the production of styrene, diethylbenzene, which fully complies with the receipt of ion-exchange resins, and stream PUB+resin (POS. 17), which can be used as raw material for the production of surface-active substances (surfactants) or component fuel stove.In accordance with example 2, get isopropylbenzene, meets the requirements of the synthesis of phenol, acetone and/or alpha-methylstyrene, diisopropylbenzene that meets the requirements of obtaining ion-exchange resins, and stream PUB+resin (POS. 17), which can be used as Sinie new technical result, specified in the preamble of the description of the present invention. These examples illustrate some possible embodiments of the invention, but not limit its scope defined by the patent claims. A method of obtaining a lower mono - and dialkylphenols, including the filing of benzene and lower olefin in the alkylation plant, equipped with a reactor unit for the interaction of benzene with a lower olefin in the presence of a catalyst complex on the basis of anhydrous aluminium chloride, a node separation of the catalyst complex from the alkylate, a node of a multi-stage rectification with the last stages of selection return benzene, lower alibendol, lower dialkylphenol partially returned in the reactor block, and partially withdrawn from the installation, and polyalkylbenzenes, characterized in that the lower dialkyl before drainage installation is subjected to a clear rectification in three distillation columns, in the first of which emit light fraction stream which is returned to the node in the multi-stage distillation and reactor block, in the second column provide a complete separation of the light fraction, the flow of which return to the node in the multi-stage distillation and reactor bknai faction, you return to the site multistage rectification on stage allocation polyalkylbenzene fraction in the reactor block.
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: process comprises continuous-mode alkylation of benzene (20-25%) with α-olefins, in particular C8-C14 fraction (70-80%), in presence of catalyst complex (1.5-2%) at elevated temperature. Alkylate is neutralized and washed to remove catalyst complex, after which rectified to isolate desired product. Before alkylation, benzene and α-olefins are combined and azeotropically dried. Rectification is carried out at least in two steps and bottom temperature in any step is the same as boiling temperature of α-olefins and pressure in each subsequent step is below pressure of preceding step. Plant for alkylation of benzene with α-olefins is also disclosed.
EFFECT: increased conversion of benzene and increased yield of desired product.
6 cl, 1 dwg
FIELD: catalyst preparation methods.
SUBSTANCE: immobilized ionic liquid is prepared by anion-assisted immobilization of ionic liquid, for which purpose a carrier is treated with anion source, for instance with inorganic halide to produce ionic liquid or applying it onto carrier. Alternatively, ionic liquid may be immobilized because of cation covalently linked to carrier, e.g. through silyl groups, or incorporated into carrier via synthesis of carrier in presence of acceptable base. Immobilized ionic liquid are meant for use as catalysts, e.g. in Friedel-Krafts reaction.
EFFECT: optimized preparation procedures.
18 cl, 10 ex