The method of producing monoalkylbenzenes
(57) Abstract:The invention relates to the field of petrochemicals, in particular the production of monoalkylbenzenes interaction of benzene with olefins in the presence of aluminum chloride recycle of polyalkylbenzenes. The technical result - the reduction of output polyalkylbenzenes resin. To do this, hold separate parallel alkylation reaction and parallelomania in two special devices. Parallelomania subjected fraction polyalkylbenzenes (Pubs) with content of heavy Pubs no more than 3 wt. % if 80oC and above. 2 C.p. f-crystals, 1 Il. The invention relates to a method of producing monoalkylbenzenes interaction of benzene with olefins in the presence of a catalyst system based on aluminum chloride recycle of polyalkylbenzenes.A known method of producing ethylbenzene by parallelomania polyalkylbenzenes resin in the presence of benzene and catalyst complex on the basis of aluminum chloride (ed. St. USSR N 988801, publ. 15.01.83,)
The disadvantage of this method is that in terms of parallelomania heavy polyalkylbenzene (Penta, exaustively) and deep-condensing (resin) contribute to the SS="ptx2">Closest to the proposed method is two-stage process for the production of cumene, which are consistently implemented alkylation reaction of benzene with propylene and parallelomania of polyalkylbenzenes involving alkylate the first stage in two special devices (see R. 3.Akhmedov, B. C. Lobkin, M. A. Dalin // refining and petrochemicals, N 6 - 1976 S. 34). The disadvantage of this method is the flow in the reactor parallelomania alkylate with a high content of cumene. Raw materials entering the reactor has a composition close to equilibrium with the presence of higher polyalkylbenzenes. When this catalyst system based on aluminum chloride, prone to active adsorption polyalkylbenzenes, quickly deactivated and, in the case of keeping this system in the reactor for a long time, leads to the formation of heavy hydrocarbons and resins. This not only reduces the yield of cumene, but increases the consumption of catalyst and other material and energy costs.The invention solves the problem of reducing the formation of products of deep alkylation of benzene with olefins and the condensation products (resin).To achieve the outlined technical R is a diversified holding alkylation reaction and parallelomania in two reactors. In the first reactor, flows through the reaction of alkylation of benzene with olefins in the second reaction parallelomania fraction polyalkylbenzenes containing not more than 3 wt.% heavy polyalkylbenzenes involving benzene.Distinctive features of the proposed method are simultaneous parallel conducting the alkylation reaction and parallelomania in two separately installed reactors involvement in the process of parallelomania at 80oC and higher fraction of light (di-, tri-) polyalkylbenzenes, this prevents flow in peralkylated significant amounts of monoalkylbenzenes (alkylate) and heavy polyalkylbenzenes (resin) that prevents overrun of the catalyst complex and reduces the yield of tar.The proposed method is illustrated by a drawing, which shows a diagram of the two-stage gain monoalkylbenzenes.The diagram shows peralkylated 1, alkylator 2.The method is as follows.In peralkylated 1 arrive fresh (I) or a mixture of fresh and return (I+IV) catalyst complex, benzene (II) 50 to 70 wt.% and the fraction of polyalkylbenzenes (III) 25 to 32 wt.%.In alkylator 2 arrive fresh EAGA system sludge and separation from the catalyst complex, come to the distillation Assembly. Using the proposed method allows to take into account peculiarities of the alkylation reaction and parallelomania separately and hold them in optimal conditions. This prevents the circulation of heavy polyalkylbenzenes in peralkylated, decrease the condensation reaction and the output polyalkylbenzenes resin.The method is illustrated by the following examples were conducted at the same time and pressure.Example 1. In peralkylated 1 arrive fresh catalyst complex, benzene, and the fraction of polyalkylbenzenes. The composition of the initial reaction mixture, wt. %: benzene 59,9; ethylbenzene 1,8; sum (di-, tri-) ethylbenzol 26,5 and the amount of polyalkylbenzenes above trialkylborane (heavy polyalkylbenzenes) of 1.4. The reaction mass after dealkylation system sludge from the catalyst complex contains the Mac. %: benzene 50,5; ethylbenzene 40,0; (di-, tri-) ethylbenzol 7,2; heavy 1,8; aluminium chloride 0,13 - temperature dealkylation 150oC.Example 2. In peralkylated arrive fresh catalyst complex, benzene, and the fraction of polyalkylbenzenes. The composition of the initial reaction mixture, wt. %: benzene 57,4; ethylbenzene 4,8; polyalkylbenzene 31,6; heavy 6,9. Recently 14,9; heavy 6,0; aluminium chloride is 0.25. The temperature in dealkylation 80oC.Example 3. In peralkylated 1 arrive fresh catalyst complex, benzene, and the fraction of polyalkylbenzenes. The composition of the initial reaction mixture, wt. %: benzene 59,2; ethylbenzene 8,1; polyalkylbenzene 29,4, heavy 2,9. Reaction mass dealkylation contains, wt%: benzene 44,9; ethylbenzene 42,2; (di-, tri-) ethylbenzol 9,6; heavy 3,0; aluminium chloride 0,19. The temperature in dealkylation 110oC.Example 4. In peralkylated 1 receives a mixture of fresh and return of the catalyst complex in the ratio 1:1, benzene and the fraction of polyalkylbenzenes.The composition of the initial reaction mixture, wt.%: benzene 71,4; diisopropylphenol 26,8; heavy polyalkylbenzene of 1.6. The reaction mass after dealkylation system sludge contains, wt%: benzene 59,4; isopropanol 31,9; diisopropylphenol 5,8; heavy polyalkylbenzene 0,4; aluminium chloride 0,12. The temperature in dealkylation 80oC.Example 5. In alkylator 1 arrive fresh catalyst complex, benzene, and the fraction of polyalkylbenzenes. The composition of the initial reaction mixture, wt.%: benzene 69,9; ethylbenzene 1,7; (di-, tri-) ethylbenzol 26,5, heavy 1,4. Reaction mass dealkylation posy of 0.4. The temperature in dealkylation 75oC.As seen from the above examples, the process of parallelomania fraction polyalkylbenzenes precluding admission peralkylated heavy polyalkylbenzenes and monoalkylphenol provides effective dealkylation (di-, tri-) ethylbenzol and yield heavy (resins). 1. The method of producing monoalkylbenzenes by two-stage implementation process of alkylation and parallelomania in two special apparatus in the presence of a catalyst system based on aluminum chloride, characterized in that parallelomania subjected fraction polyalkylbenzenes with content of heavy polyalkylbenzenes not more than 3 wt.%.2. The method according to p. 1, characterized in that the process parallelomania conduct parallel to the alkylation process.3. The method according to p. 1 or 2, characterized in that the process parallelomania carried out at 80oC and above.
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