The method of extraction of benzene hydrocarbons from coke oven gas
(57) Abstract:The inventive coke oven gas is treated in the absorber light coal oil. The absorbed benzene hydrocarbons are distilled. Obtention oil assign for treatment of polymer products in the amount of 1.5 to 5.0 wt.% from the time oil consumption and absorption, mixed with aliphatic hydrocarbons, wikipedii within 60 to 120°C. in a volume ratio of aliphatic hydrocarbons and oils, equal to (2 - 5): 1. The oil mixture with the aliphatic hydrocarbons are separated from the formed precipitate the polymer product by decantation. Aliphatic hydrocarbons are removed by distillation. Peeled from the polymer products of the oil return into the cycle. Preferably, in the exhaust purification from polymer products obtention oil add coal tar mass ratio of oil and coal tar (1,5 - 5,0):1. 1 C.p. f-crystals, 3 tables. The invention relates to the extraction of benzene hydrocarbons from coke oven gas by absorption of light coal oil, followed by separation from the circulating oil by distillation with water vapor and can be used in the process is The method for extracting the benzene hydrocarbons from coke oven gas by absorption of light coal oil with subsequent distillation of a busy working oil with water vapor at a temperature of 135-180aboutAnd return obessessing oil after cooling again to the absorption of benzene hydrocarbons, as described in the technical literature. The disadvantage of this method is the high consumption of fresh absorbing oil for full or partial replacement of working capital due to higher viscosity and density of the latter due to the polymerization of unsaturated compounds and copolymerization of other components of coke oven gas and absorbing oil during its periodic heating and cooling.The closest analogue of the present invention is a method of extraction of benzene hydrocarbons from coke oven gas by absorption of light coal oil with subsequent distillation of the oil at a temperature of 135-180aboutWith water vapor and the release of a portion of the circulating absorption oil polymers by distillation nepalitano faction and return it to the cycle of the circulating oil. The polymers are of the cycle of the circulating oil in liquid form is a private part of the oil, high loss of oil polymers limited number displayed for separating polymers circulating oil, which is limited by the flow of steam in the distillation column distillation of the benzene hydrocarbons from the circulating oil. For example, according to published data, when the number of circulating oil 136 m3/h in the regenerator is served only 0.4 t/h circulating oil from which Argonauts nepalitano faction only about 0,228 t/H. At the same time to maintain good quality recycling oil regeneration (highlighting polymers) must display at least 1.5% of the circulating oil.If the regenerator output 1% of the working oil and the distillation polimernoi his part to serve the whole of acute water vapor supplied to a distillation column for distillation of circulating oil benzene hydrocarbons, at a temperature of 170aboutWith regenerator otnosyatsa 79.5% of oil. If there are no plants to water vapor high oil regeneration (highlighting polymers) is practically impossible, and in practice, the plants have to apply the update working oil to the simple conclusion it from circulation and replaced by fresh, which leads to increased oil consumption th adsorption of coal oil, reducing the consumption of fresh replenishment cycle and the possibility of using low-grade heat transfer fluids.This objective is achieved in that the selection of polymers by mixing the output from the cycle of the circulating oil with an aliphatic hydrocarbon wikipedie within 60-120aboutWith in a volume ratio of aliphatic hydrocarbons oil within 2-5, followed by decantation of the layer of oil hydrocarbons and distillation of aliphatic hydrocarbons by distillation.To significantly improve the quality of the circulating absorption oil for separation of polymers from the series output of 1.5-5% of time flow rate of the circulating oil.To reduce the consumption of fresh oil on the replenishment cycle of working to be displayed on the selection of polymers circulating oil is added coal tar mass ratio of oil and resin in the range of 1.5-5.P R I m e R 1. The flow of coke oven gas 100 thousand m3/h with the content of benzene hydrocarbons 40 g/m3washed in the absorbers in a counter light coal oil density 1050 kg/m3and a viscosity of 1.5aboutE (6,74 cSt), supplied in a quantity of 180 m3/hours After absorption benzoe distillation of him benzene hydrocarbons. Obtention absorbing oil after distillation column is cooled to 25-30aboutS and 9 m3/h assign to selection of polymers, and 171 m3/h mixed with 0.20 m3/h fresh absorbing oil and 8.8 m3/h regenerated and again served on the absorption of the benzene hydrocarbons.To maintain constant density and viscosity 9 m3/h output from the cycle of the circulating oil is mixed with 27 m3/h aliphatic hydrocarbons (benzene boot). After settling of the mixture deposited polymers pumped in coal tar, and the upper layer of solution adsorption of oil in the gasoline is fed to the column for distillation of gasoline at a temperature of 140aboutC. warded off petrol vapours condense and return to the mixing with the output of cycle 9 m3/h circulating oil, and obezbecivanje regenerated absorbing oil in the amount of 8.8 m3/h after cooling to 25-30aboutWith mix with the main stream of the circulating absorption oil supplied to the absorption of the benzene hydrocarbons from coke oven gas. To compensate for the loss absorbing oil in the cycle continuously add fresh light coal oil gas amounted to 2.2 g/m3and production of crude benzene 3890 kg/hP R I m m e R 2. The flow of coke oven gas 100 thousand m3/h with the content of benzene hydrocarbons 40 g/m3washed in the absorbents in a counter light coal oil density 1064 kg/m3and a viscosity of 1.6aboutE, submitted in the amount of 180 m3/PMAfter washing the gas saturated benzene hydrocarbon oil served on a distillation column for distillation of him benzene hydrocarbons at a temperature of 145aboutWith the supply of acute water vapor 9.6 t/h Obtention oil after distillation column is cooled to 25-30aboutS and 9 m3/h assign to selection of polymers, and 171 m3/h mixed with 9 m3regenerated and again served on the absorption of benzene hydrocarbons from coke oven gas.To maintain constant density and viscosity of the working oil 9 m3/h output from the cycle oil mixed with 1.8 m3/h coal tar and 30 m3/h gasoline. After settling deposited polymers with a heavy part of the coal tar is directed to a Stripping cube and after the distillation of gasoline pumped into marketable coal tar or processed by WPI is the distillation of gasoline at a temperature of 140-150aboutC. In the same column and assign the pairs of Stripping cube for Stripping polymer. Distilled petrol vapours condense and return to the mixing with the new portion of the circulating absorption oil and coal tar, and uparennoe from gasoline absorbing oil in the amount of 9 m3/h mixed with 171 m3/h working capital and serves on the absorption of benzene hydrocarbons from coke oven gas. In this mode of regeneration circulating oil loss benzene hydrocarbons from the coke gas was 2.4 g/m3, production of crude benzene 3910 kg/h, and fresh oil for replenishment cycle, the reverse was not required.To confirm the possibility of use as selective solvents aliphatic hydrocarbons of different molecular structures, or mixtures thereof described experiments, the results of which are given in table. 1.In all experiments, the volumetric ratio of oil and solvent is maintained equal to 1 2. The source of circulating oil had a viscosity of 3aboutE and density 1096 kg/m3.To select the optimal volume ratio of oil and solvent is conducted experiments with circulating absorption oil with the initial viscosity of 3.2aboutE and density 1098 kg/m
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