The method of obtaining gasoline fraction
(57) Abstract:Usage: oil refining and petrochemical industry. The inventive product gasoline fraction, the yield of 47.6% of the octane number of 87 (motor method). Raw material: registergui gas. Catalyst: zeolite ZSM-5-CBM with a molar ratio of SiO2:Al2O3Zirconia, 20% zinc oxide 2% aluminum oxide to 100% of process Conditions: the main reactor: 350 370°C, 0.3 To 0.4 MPa, the feed rate of 300-C-1additional reactor: 550 to 600°C, 0.3 To 0.4 MPa, the feed rate of 300-C-1In both reactors turbulent fluidized bed of catalyst. In an additional reactor serves gases stabilization separated from the liquid phase of the reaction products, and sizerequirements catalyst. The catalyst and partially spent in the secondary reactor, moving from an additional reactor to the reaction products in the main reactor. Part of the catalyst from the primary reactor and led to the regeneration, and then serves it to the secondary reactor. 3 C. p. fly, 1 Il. 5 table. The invention relates to a method for producing a gasoline fraction from registertimer raw materials and can be used for efficient refining gas catalyse and petrochemical industries.Known methods for producing oligomers WITH5+incontacts low olefins, preferably propylene, butylene and mixtures thereof, and the exhaust gas catalytic cracking fluid (CCF) and gas dewaxing fluidized bed of catalyst containing 17% of zeolite N-ZS-5 with a molar ratio of SiO2:Al2O380, or a catalyst containing 35% zeolite Zn-ZSM-5 with a molar ratio of SiO2: Al2O3230 at a temperature of 150-350aboutC, flow rate of feed gas 1000-3000 h-1and a pressure of from 0 to 0.6 MPa [1 and 2] the Contacting is carried out in one reactor, in the lower part of which is under a distribution grid serving the feedstock, and in the upper part of the fluidized bed Stripping gas, so that the olefins oligomerization in the bottom, and oligomers uparivaetsya with the catalyst in the upper part.The disadvantage of these methods is the low yield of the target products5+in; so, when the transformations FCC off-gas outlet5+inis 66,1% while the conversion of propane-propylene mixture conversion in C5+inis 61%
Closest to the proposed method to the technical essence and the achieved result is a way of getting points on the research method) by catalytic conversion atlantabased light gas or fuel gas process CCF, containing up to 40 wt. ethylene and propylene, in a turbulent fluidized bed high zeolite catalyst ZSM-5 with an average temperature in the reactor 315-510aboutWith, preferably 315-430aboutWith, the weight flow rate of 0.1-5 h-1calculated on the total olefins in the feedstock, the pressure of 0.41-2.5 MPa recycle a significant part C4and below the product in the reactor  Exit5+inhydrocarbon is 67.3 wt. missed ethylene and propylene.The disadvantage of this method is the low output5+inproduct.The aim of the invention is to increase the yield of gasoline fraction from registertimer raw materials.According to the invention this goal is achieved by the proposed method of obtaining gasoline fraction by contacting registertimer gas with a catalyst containing 35 wt. high zeolite-type computers with a molar ratio of SiO2: Al2O331,5, 20 wt. zirconium oxide, 2 wt. zinc oxide and 43 wt. the aluminum oxide at a pressure of 0.3-0.4 MPa in the reactor with turbulent fluidized bed of partially spent catalyst at a temperature of 350-370aboutC, space velocity of the raw material 300-700 h-1the population gasoline fraction and a gas stabilization the contacting gases stabilization in the secondary reactor with turbulent layer of the same siegerehrung catalyst at a temperature of 550-600aboutC, flow rate of feed gases stabilization 300-500 h-1with further movement of the partially spent catalyst to the reaction products from the secondary reactor into the main reactor, and then in the regenerator.The drawing shows a schematic diagram of the process.Source registergui gas (I) passes through the heat exchanger 1, where it is heated to the reaction products from the primary reactor 2, the heating furnace 3 and is supplied under a distribution grid of the main reactor 2, where the layer of turbulent fluidized bed of partially spent catalyst at a pressure of 0.3-0.4 MPa, a temperature of 350-370aboutC, space velocity registertimer gas 300-700 h-1is the oligomerization of olefins. Excess heat is removed submersible refrigerators 4. The reaction products rise from the bottom up, are separated from the carried catalyst particles in cyclones 5, then in the filter 6 and fed to the separator 7, which are separated in the liquid phase volatile liquids, and gaseous phase (II). G what toroi selected gas stabilization, below is a stable condensate. Stable condensate is delivered to the column 9 where it is divided into target gasoline fraction NC-180aboutWith (III) and VAT residue 180aboutWITH QC (IV). Gas stabilization of the column 8 is heated in the furnace 10 and serves under a distribution grid additional reactor 11 at a temperature of 550-600aboutC, a pressure of 0.3-0.4 MPa and a space velocity of gas stabilization 300-500 h-1is contacting turbulent fluidized bed siegerehrung catalyst. The process is absorption of heat. The products of reaction in the secondary reactor 11 rise up and move partially spent catalyst from the secondary reactor 11 in the main reactor 2 through the Central transport riser 12; reaction products of primary and secondary reactors are mixed in the upper zone of the primary reactor 2, and the catalyst from the riser 12 is poured in a fluidized bed of the primary reactor 2. To maintain a constant activity of the catalyst in the primary reactor 2 part catalyst through line 13 to display in the regenerator 14, where sizerequirements the catalyst pipe 15 serves in an additional reactor 11. Regeneration is performed by the air (V).Distinctive features of the proposed method is the process in two reactors with transferring the partially spent catalyst to the reaction products from the secondary reactor into the main reactor.As a source of raw materials, the proposed method can be used purified hydrogen sulfide and carbon dioxide rich gas catalytic cracking, gas, coking, thermal cracking.The proposed method is tested on the pilot plant and is illustrated by the following example.P R I m e p is used as raw material registergui gas similar in composition to the greasy gas catalytic cracking (PL.1).The used catalyst has a composition, by weight. on dry weight: zeolite CUMS with a molar ratio of SiO2:Al2O331,5-35, Zirconia, ZrO220, zinc oxide ZnO 2,0, aluminum oxide (Al2O343. The bulk density of the calcined catalyst 0,607 g/cm3the content of particles with a size of 0-40 MK 5 wt. 0-100 MK 63 wt. 0-150 MK 87 wt. 0-200 MK 98 wt.The method of preparation of the catalyst is as follows.In steel apparatus with stirrer and heating pour 20 litres of water condensate and add aout the solution of nitrates of zirconium Zr(NO3)22H2O (434 g of salt in 2 liters of water condensate) and a solution of zinc nitrate Zn(NO3)26H2O (74,2 g of salt in 1 liter of water condensate). The resulting suspension is stirred for 1 h, after which the device is added a suspension of 450 g of zeolite NH4CUMS in 5 l of water condensate. The zeolite has the following characteristics: the degree of crystallinity of 100% silicate module SiO2:Al2O331,5, static capacity, cm3/g pairs with the water of 0.08, pairs of heptane to 0.24. After 30 min stirring measure the pH of the resulting system and bring it up to a 3.0 by the gradual addition of nitric acid. Then increase the temperature in the apparatus to 50-60aboutC, maintain the suspension at this temperature and stirring for 3 h, after which the slurry is directed to dispersion in a laboratory dryer radar-10 when the speed of rotation of the spray disk 7500-8500 rpm at 190-220aboutC. the resulting pellets are calcined in a muffle furnace at 550aboutC for 6 h and get 1000 g microspherical catalyst of the above composition.1.0 liter of catalyst loaded into the main reactor (0.8 l) and in an additional reactor (0.2 l). Source registergui gas after the pre is entom fluidized bed of catalyst at a temperature of 350-370aboutC, a pressure of 0.3-0.4 MPa and flow rate 300-700 h-1is the conversion of olefins. Gas stabilization after pre-heating to 580aboutComes with under a distribution grid additional reactor 11, where in a turbulent fluidized bed of catalyst at a temperature of 550-600aboutC, a pressure of 0.3-0.4 MPa and a flow rate of 300-500 h-1there are transformations of olefins and paraffins. Both streams are mixed and sent to the separation, after which the liquid portion is subjected to stabilization, gas stabilization sent as raw material in the secondary reactor, and stable condensate is separated in a distillation column on the target gasoline fraction NC-180aboutWith and cubic fraction 180aboutWITH-CC.For comparison with the known method conducted by contacting dorectory scheme without circulation in the reactor and dorectory circuit with circulation in the reactor gas stabilization.The compositions stabilization gas and fuel gas are presented in table.1, the choice of intervals of process conditions in both reactors the temperature, pressure and flow rate are shown in table. 2 and 3.From table. 2 and 3 shows that the proposed method the highest output is the temperature value in the main reactor 350-370aboutWith additional reactor 550-600aboutC, a pressure of 0.3-0.4 MPa, the space velocity of the feedstock in a primary reactor 300-700 h-1and volume rate of gas flow stabilization in the advanced reactor 300-500 h-1.In table. 4 shows a comparison of how the process dorectory scheme without circulation, dorectory circuit with circulation in the reactor and the proposed method.Comparison of main indicators under optimal conditions (table.4) shows that the proposed method yield of gasoline fraction NC-180aboutWith, as the yield of liquid products5+inthe olefins in the original leinstermen gas (47,6 and 80.4 wt. respectively), higher than dorectory scheme (42,3 and 68.7 wt. respectively) and dorectory scheme with gas circulation stabilization in the reactor (43,5 and 71.3 wt. respectively.The octane number of the gasoline fraction NC-180aboutWith the motor method comprises: 87 on the proposed method, 86 dorectory scheme with gas circulation stabilization in the reactor and 85 on dorectory scheme without circulation. Characteristics of the target of gasoline on the proposed method is as follows:
Physico-chemical characteristics of the target petrol FR is egostate at temperaturesabout43 30% of the same 76 50% of the same 105 70% the same 125 90% the same 147 the End of the boil, aboutWith 181 Iodine number, mg iodine/100 g 45 Resin actual, mg/100 g 6,5
Group hydrocarbon composition, wt. paraffin-naphthene hydrocarbons 40 olefinic 20 40 aromatic Octane number by the motor method 87 Total sulfur, wt. UTS.From the data table. 4 and material balances (table.5), it follows that the application of the proposed method allows to increase compared with the prototype of the yield of liquid products5+inin the calculation of the olefins in missed raw on 13 Rel. and the yield of the desired gasoline fraction NC-180aboutWith 9.5 Rel.The increased yield of the desired gasoline and increase its octane number allows you to improve technical and economic performance of the process of obtaining gasoline fraction from registertimer raw materials. 1. The METHOD of OBTAINING GASOLINE FRACTION by contacting registertimer gas in the main reactor with turbulent pseudouridine layer of high zeolite catalyst ZSM-5 at a temperature of 350 370oC and elevated pressures with subsequent regeneration of the catalyst, separation of the reaction products in liquid and gaseous phase, the stabilization of the liquid phase with the allocation of the gases stabilization send in an additional reactor, in which carry out the contacting at 550 600oWith a turbulent fluidized bed of catalyst supplied after regeneration, with transferring the partially spent catalyst to the reaction products from the secondary reactor into the main.2. The method according to p. 1, characterized in that the process in both reactors is carried out at a pressure of 0.3 to 0.4 MPa.3. The method according to PP. 1 and 2, characterized in that the process in the main reactor is carried out at space velocity registertimer gas 300 700 h-1.4. The method according to PP. 1 and 2, characterized in that the process in the main reactor is carried out at flow rate of the gas supply stabilization 300 500 h-1.
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.