The method of producing dimethylethylene
(57) Abstract:Usage: in the petrochemical industry, in particular as raw material in the synthesis naphthalenesulphonic acids. The inventive product-dimethylethylene (DMT). Reagent 1: 5-(o-, m - or p-tolyl)Penta-1 or 2-ene or 5-phenylhexa-1 or 2-ene, with a water content of not more than 0.5 wt.%. Reaction conditions: heating at 148-250°C, pressure, providing zhidkofaznoi process, in the presence of a catalyst-ultrastable (with respect crystalline zeolite type Y having a molar ratio of SiO2/Al2O3equal to (4-10):1, the pore size corresponding to 12-membered oxygen cycle and the size of the unit cell , when the content of 0.005 to 3.5% Na per metal by weight of zeolite. Mainly the catalyst used in the H form with the addition of 0.05-3% of one of the noble metals Pt, Pd, Ir or Rh, based on the metal to the weight of the catalyst. The latter may also contain from 0.01 to 5% of the transition metal: Cu, Sn, Au, Pb or Ag, based on the metal to the weight of the catalyst. The catalyst may be supported on a carrier is an inert porous refractory inorganic oxide and contain less than 15% of adsorbed water per mass of zeolite. In the process produces a liquid mixture containing at Mel of 5-(m-tolyl)Penta-1 or 2-ene; C) 1,7-, 1,8-, 2,7 - or 2,8-DMT or a mixture of 5-(p-tolyl)Penta-1 or 2-ene; d)1,3-, 1,4-, 2,3-, 5,7-, 5,8- or 6,7 - DMT or a mixture of 5-phenyl-Gex-1 - or 2-ene. 4 C.p. f-crystals, 1 Il, 2 tab. The invention relates to the field of reception of dimethylmethylene (DMT) of 5 - (o -, m - or p-tolyl)-Penta-1 - or-2-ene or 5-phenyl-Gex-1 - or-2-ene used as an intermediate for obtaining naphthalenesulphonic acids.Naphthalenesulphonate acids are used as monomers to obtain a variety of polymers. For example, poly(ethylene-2,6-naphtalate) derived from 2,6-naphthaleneboronic acid and ethylene glycol, has better thermal stability and mechanical properties than polyethylene terephthalate, and useful in the production of films and rubbers.Dimethylnaphthalene is a necessary starting compound to obtain the corresponding naphthaleneboronic acid by oxidation. Known convenient process of obtaining naphthalenesulphonic acids involves the oxidation of dimethylnaphthalene oxygen in the liquid phase in a solution of acetic acid at elevated temperature and pressure in the presence of a catalyst comprising the components of cobalt, manganese and bromine.Usually dimethylnaphthalene (DMN) is obtained by purification of the gas is very time consuming and expensive. Therefore, a method of obtaining individual isomers dimethylnaphthalene or a mixture of two or three isomers dimethylnaphthalene high frequency and quality is highly desirable. One such method is a multistage synthesis, including (1) formation of alkenylbenzene the reaction of o - or p-xylene with butadiene, (2) the cyclization of the obtained alkenylbenzene with the formation of one or more dimethylethylene related to one or two of the three groups of isomeric dimethylethylene, group a contains 1,5-, 1,6-, 2,5 - and 2,6-dimethylaniline; group B contains 1,7-, 1,8-, 2,7 - and 2,8-dimethylethylene and group C contains 1,3-, 1,4-, 2,3-, 5,7-, 5,8- and 6,7-dimethylethylene, (3) dehydrogenation of dimethylmethylene with the formation of the corresponding dimethylnaphthalenes and (4) the isomerization of the resulting dimethylnaphthalenes to the desired isomer dimethylnaphthalene.For example, in [1-4] describes the processes cyclization of isomers alkenylbenzene in one or more isomers of dimethylmethylene at 200-450aboutWith the presence of any suitable solid acidic cyclization catalyst such as an acid crystalline zeolite, such as silicon, aluminum, silicon and magnesium, and silicon-aluminum-zirconium and phosphoric acid, for the wedge in the atmosphere of hydrogen at 300 to 500aboutWith and in the presence of solid catalysts for dehydrogenation as noble metals on carriers and oxides homoalanine, and then isomerization of each of the above dimethylnaphthalene in the desired isomer in the triad of dimethylnaphthalenes to which this isomer belonged when 275-500aboutWith the presence of a solid oxygen isomerization catalyst, the same type as described for the cyclization. On the other hand, cyclization, and isomerization can be carried out in the liquid phase, in this case, the cyclization is carried out at 200-275aboutWith solid postinoculation catalyst, at 70-140aboutWith acidic ion exchange resin, acidic crystalline zeolite, hydrofluoric or sulfuric acid as a catalyst or porous silicon catalyst.In particular in  describes the cyclization of 5-(m-tolyl)Penta-2-ene to 1.6 - and 1.8-dimethylethylene, which then digitalout to 1.6 - and 1.8-dimethylnaphthalenes, which in turn will someresult 2.6 - and 2.7-dimethylnaphthalene respectively.In  describes the cyclization of 5-phenyl-hexene-2 to 1.4-dimethylethylene that digitalout to 1,4-dimethylnaphthalene, which, in turn, will someresult 2.3-dimethylnaphthalene.In  operatory in turn will someresult 2.6-dimethylnaphthalene.In  describes the cyclization of 5-(p-tolyl)-pentene-2 to 1.7-dimethylethylene that digitalout to 1.7-dimethylnaphthalene, which in turn isomerized 2.7-dimethylnaphthalene.The problem of the known methods is the presence of other isomers dimethylnaphthalene, unreacted dimethylethylene and alkenylbenzene as impurities and by-products in the final desired specific isomer dimethylnaphthalene. The presence of these impurities and by-products significantly reduces the usefulness and commercial value of the required isomer dimethylnaphthalene, especially as a source for obtaining naphthaleneboronic acid for use as a monomer in the production of polymers. Moreover, at high temperatures, used in gas-phase processes, the catalysts have a tendency relatively quickly deactivated. Thus, it is highly desirable to use a liquid-phase processes at a relatively low temperature and to improve the completeness and selectivity of each stage of the multistage process, in particular the cyclization stage.The purpose of this invention is to provide an improved method with high yield and selectivity poluchivshego of alkenylbenzene, which satisfies the above requirements for selectivity, completeness and catalytic activity.The purpose of the invention is achieved by using the proposed improved method of producing dimethylethylene of 5-(o-, m - or p-tolyl)Penta-1 - or-2-ene or 5-phenyl-Gex-1 - or-2-ene as a feedstock, comprising contacting in the liquid phase feedstock to the cyclization catalyst comprising a crystalline aluminosilicate zeolite of the Y type molecular sieve, which is substantially free of adsorbed water in the temperature range from 148aboutWith up to 250aboutWith and at high enough pressure to maintain the original substance in the liquid phase from 0.3 to 5 MPa, preferably of 1.3 MPa. The original raw material, if it contains water, the concentration of water in it does not exceed 0.5% by mass.When the quality of raw materials using 5-(o-tolyl)-Penta-1 - or-2-ene, then we obtain a liquid mixture of dimethylmethylene containing at least 80 wt. % 1,5-, 1,6-, 2,5- or 2,6-dimethylaniline or mixtures thereof, is used to obtain 2,6-dimethylnaphthalene in multistage synthesis.When the quality of raw materials using 5-(m-tolyl)-Penta-1 - or-2-ene, get zhina or mixtures thereof, used to obtain the 2,6 - and 2,7-dimethylnaphthalenes.When the quality of raw materials using 5-(p-tolyl)-Penta-1 - or-2-ene, then we obtain a liquid mixture of dimethylmethylene containing at least 80 wt. % 1,7-, 1,8-, 2,7- or 2.8-dimethylethylene or mixtures thereof, is used to obtain 2,7-dimethylnaphthalene.When the quality of raw materials using 5-phenyl-Gex-1 - or-2-ene, then we obtain a liquid mixture of dimethylmethylene containing at least 1,3-, 1,4-, 2,3-, 5,7-, 5,8- or 6,7-tetralin or their mixtures are used to obtain 2,3-dimethylnaphthalene.The cyclization reaction can be carried out with a solvent or without solvent for the corresponding source. It is preferable not to use a solvent. If a solvent is used, it must be inert in the process and may include such paraffin, as tetradecane, or such aromatic hydrocarbons as anthracene, or a mixture which boils preferably about 270aboutC. On the cyclization stage, if water is present, its concentration is less than 0.5%, preferably less than 0.1% by weight of alkenylbenzene. More preferably in a reaction medium in the cyclization stage water is missing.The process cyclists is mportant layer, moving bed, fluidized bed, with a layer of catalyst suspended in the liquid phase, or by mixing solid particles in the liquid in the vessel. In General, however, the use of devices with a porous layer preferably commercially for further operations.The increase in the conversion source and the selectivity of the formation of the desired product or range of products of the cyclization stage is the result of the selected conditions of temperature and pressure, as well as high activity and selectivity of the used catalyst, which in turn allows the use of less stringent conditions, i.e., lower temperature and pressure, and this can be achieved by increased selectivity and reduced disable catalyst.The catalyst used for the cyclization process in the method of the present invention contains an acidic ultrastable (with respect, i.e., thermally stable or delaminating, crystalline aluminosilicate zeolite of the Y type having a molar ratio of silicon dioxide to aluminum oxide of 4 : 1, preferably from 5 : 1 to 10 : 1, preferably 6 : 1, and having a pore size corresponding to dvenadtsatikolonnom oxygen cycle, and razmery elemental Union carbide under the name LZ-y72 or LZ-y20.Preferably the zeolite is free from adsorbed water. If water is present, it can be removed by heating the zeolite in an inert atmosphere at 250aboutC for 0.5-1 hours alternatively, and less preferably, the presence of water in concentrations up to 15% by weight of zeolite can be valid, if the reaction temperature of the above interval is at least 180aboutC.The above-mentioned zeolite is used as catalyst for the cyclization stage in the method of the present invention is in the protonated form and contains about 0.05 to 3.5% by weight sodium, considering the elemental sodium by weight of zeolite. If phase cyclization is carried out in a periodic variant, the catalyst preferably contains 1-3,5% sodium, considering the elemental sodium by weight of zeolite. If phase cyclization carried out continuously, the cyclization catalyst preferably contains 0.05-0.5% sodium, considering the elemental sodium by weight of zeolite. Preferably, the catalyst contains from 0.01, preferably from 0.05 to 3, preferably 1.5 wt. % component comprising a first metal selected from the group consisting of platinum, palladium, iridium and rhodium, considering the elemental sodium by weight of zeolite. Oh, if the cyclization reaction is carried out in a continuous embodiment, the cyclization catalyst also contains from 0.01, preferably 1-5, preferably 3 wt. % component comprising a second metal selected from the group consisting of copper, tin, gold, lead and silver, considering the elemental metal to the weight of the catalyst. More preferably, when the second metal component comprises copper, tin or gold.The above-mentioned zeolite can be used without carrier and deposited on a porous refractory inorganic oxide, which is inert in the conditions of use as, for example, oxides of silicon, aluminum, silicon, aluminum, magnesium bentonite, and the like. If the media is used, preferred are oxides of silicon, aluminum, and silicon-aluminum. If a carrier is used, the content of the zeolite is from about 10, preferably from about 20 to about 90, preferably up to 80% relative to the weight of the catalyst.If the cyclization is conducted periodically, the catalyst charge in the amount of from about 5, preferably up to 3%, based on the zeolite component of the catalyst, counting on a lot alkenylbenzenes source, and the reaction time is from about 0.5, Pres the speed is in the range from about 0.1, preferably from 1 to about 10, preferably up to 5 hours alkenylbenzenes original 1 hour zeolite component of the catalyst per hour.The invention will be more clear from the following specific examples.P R I m e R s 1 - 8. In each of examples 1-8 20-1000 g alkenylbenzene placed in a glass reactor with a stirrer in an atmosphere of dry nitrogen to prevent the reaction medium from moisture. Used alkenylbenzene is 5-(o-tolyl)-Penta-2-ene in examples 1-6, 5-(p-tolyl)-Penta-2-ene in example 7 and 4-phenyl-Gex-2-ene in example 8. Ultrastable (with respect crystalline aluminosilicate catalyst Y type without media, molecular sieve (Union Carbid LZ-y72), having dimensions of the unit cell and 24,15 containing 2.5 wt. percent sodium (counting on the oxide sodium), is slowly added to alkenylbenzene into the reactor at a temperature below the beginning of the cyclization of alkenylbenzene. The catalyst is a powder without media in examples 1-4, 7 and 8 and the pellets containing 80 wt. % same sieve printed at 20 wt. % aluminum media in examples 5 and 6. The catalyst is kept in a dry, free of moisture atmosphere before use in the examples 1-3 and 5-8, but was allowed to adsorb moisture from the saturated when it 30-60aboutWith air in the sample is then quickly raised to the desired reaction time. Samples of the products obtained is withdrawn from the reactor after various time intervals and analyzed to monitor the progress of the reaction. The desired cyclization product was 1,5-dimethylethylene in examples 1-6, 1,7-dimethylethylene in example 7 and 1,4-dimethylethylene in example 8. The conditions of the experiment, the composition of the original and derived products containing up to 13 carbon atoms, % conversion of the original alkenylbenzene and selectivity of the formation of the desired product from the total number of the reacted alkenylbenzene for each of examples 1-8 are shown in table. 1.When calculating the % selectivity to desired products was considered to be the amount of 1,5-dimethylethylene (1,5-DMT) and 1.5-dimethylnaphthalene in examples 1-6, the amount of 1.7 dimethylethylene and 1.7-dimethylnaphthalene in example 7 and the amount of 1,4-dimethylethylene and 1,4-dimethylnaphthalene in example 8.Comparing the results of examples 2 and 4 shows that even with a low ratio source:catalyst in example 4, a large amount of water in it significantly reduces the degree of conversion, even when the reaction time is about 12 hoursP R I m e R s 9 - 23. In each of examples 9-23 the cyclization catalyst is placed in a reactor made of stainless steel and immersed reactor in a sand bath with PS is tena-2 in the liquid phase and nitrogen. At least once in a single catalytic cycle resulting products are selected from the stream and analyzed. The conditions of the experiment, the composition of the source and destination of products containing up to 13 carbon atoms, % conversion of the original alkenylbenzene and selectivity of the formation of the target product of the total number of the reacted alkenylbenzene for each of the experiments 9-23 presented in table. 2.The catalytic cycle is the periodic submission of 5-o-talipanan-2 reactor and blowing it with nitrogen at the reaction temperature for the removal of hydrocarbons. Then the reactor is heated to 500aboutWith and blow air up until the CO2in the output stream is less than 0.1 wt. %. This procedure leads to the regeneration of the catalyst. Then the reactor is cooled to the desired reaction temperature and continuously miss a mixture of 5-o-tolyl-2-pentene in the liquid phase and nitrogen.In each of examples 9 to 12 and 19 to 23 of the reactor has an outside diameter of 0.25 inch, an inner diameter of 0.18 and a length of 5.5, it is loaded 1 g of the catalyst.In each of examples 13-18, the reactor has an outside diameter of 0.375 inch, internal 0.28 and a length of 5. Charged to the reactor 2.5 g of catalyst.In each of t by mixing 30 g of industrial ultrastable (with respect to Y sieves (Union Carbid LZ-y20), 15 ml of distilled water and 30 g of an aqueous solution containing 1 wt. % H2PtCl6.6H2O, counting on platinum, and 2 wt. % copper in the form of nitrate of copper, counting on elemental copper. The resulting mixture is stirred until homogeneous and then dried. The resulting product is calcined at 500aboutWith air-4 hours, pulverized and sieved, receiving particles 0,0164-0,0278 inch (24-40 μm).In each of examples 15-18 apply ultrastable (with respect to the Y-sieve containing platinum and copper components. This catalyst is obtained by grinding and sifting the industrial design, the particles of which contain 80 wt. % Union Carbid LZ-y20 printed at 20 wt. % aluminum oxide, receiving particles with sizes 24-40 mesh. 10 g of sieves on the media is added to 11 ml of 0.9% solution of N2tCl6counting on platinum, and 1.8 wt. % copper in the form of nitrate of copper, counting on elemental copper. The resulting mixture is stirred until homogeneous and then dried. The obtained solid product is calcined in air at 500about4 hours outcome of the process and conditions are given in table. 2.In each of examples 19 to 23 were used apparatus and methods of examples 9-12, the reaction temperature 154aboutWith and volumetric flow rate of the source alkenylbenzene gas to 5-o-carpenter-2 was 1.3 in example 19 and 2.1 in examples 20-23. The catalyst in each example was applied without a carrier, in example 19 - Y, ultrastable (with respect sieve (Union Carbid LZ-y20) and in each of examples 20 and 21 Y, ultrastable (with respect sieve containing 2 wt. % copper in the form of nitrate of copper, considering the elemental copper in example 22 - ultrastable (with respect to the Y-strainer processed SiCl4in example 23 - ultrastable (with respect to the Y-sieve containing 2 wt. % copper in the form of nitrate of copper, and 1 wt. % of platinum in the form of H2PtCl6. In each of examples 19 to 23 samples of the product stream was sampled and analyzed several times after the beginning of the catalytic cycle. From these measurements was calculated output of 1.5-dimethylethylene and put it on the schedule (see the drawing) against the number of hours, starting from when the catalyst was regenerated.The results show that the addition of copper to the sieve or the processing of the silicon tetrachloride increases the selectivity of the catalyst, but the catalytic Akti you want to make decreases with time. However, additive and platinum, and copper to the sieve leads to significantly increased selectivity while maintaining high catalyst activity. 1. The METHOD of producing DIMETHYLETHYLENE by contacting 5-(o-, m - or p-tolyl)-Penta-1 - or-2-ene or 5-phenyl-Gex-1-, ature and pressure, providing a liquid-phase state of the feedstock and its cyclization with the formation of a liquid dimethylethylene containing at least 80 wt.% 1,5-, 1,6-, 2,5- or 2,6-dimethylaniline or mixtures thereof in the case when the quality of raw materials using 5-(0-total)-Penta-1 or-2-ene, or the formation of a liquid dimethylethylene containing at least 80 wt.% 1,5-, 1,6-, 1,7-, 1,8-, 2,5-, 2,7- or 2.8-dimethylethylene or mixtures thereof in the case when the quality of raw materials using 5-(m-total)-Penta-1 - or 2-ene, or the formation of a liquid dimethylethylene containing at least 80 wt.% 1,7-, 1,8-, 2,7- or 2.8-dimethylethylene or mixtures thereof in the case when the quality of raw materials using 5-(p-tolyl)-Penta-1 or-2-ene, or the formation of a liquid dimethylethylene containing at least 80 wt.% 1,3-, 1,4-, 2,3-, 5,7-, 5,8- or 6,7-dimethylethylene or mixtures thereof in the case when the quality of raw materials using 5-phenyl-Gex-1 - or-2-ene, characterized in that the catalyst used ultrastable (with respect crystalline zeolite type Y, essentially free of adsorbed water and having a molar ratio of silicon dioxide and aluminum oxide from 4:1 to 10: 1 and the pore size corresponding to dvenadtsatikolonnom key is hydrated sodium by weight of zeolite, and the process is carried out at 148-250oWith, and use raw materials, the concentration of water in which, if present, less than 0.5% by weight of raw materials.2. The method according to p. 1, characterized in that the use of the zeolite catalyst in the hydrogen form containing 0.05-3% of a component of the noble metal selected from the group consisting of platinum, palladium, iridium and rhodium, considering the elemental metal, by weight of the catalyst.3. The method according to p. 2, characterized in that the use of the zeolite catalyst additionally contains from 0.01 to 5% component of a transitional metal selected from the group consisting of copper, tin, gold, lead and silver, considering the elemental metal, by weight of the catalyst.4. The method according to PP.1-3, characterized in that the use of the zeolite catalyst deposited on an inert porous refractory inorganic oxide as a carrier.5. The method according to PP.1-4, characterized in that the use of the zeolite catalyst containing less than 15% of adsorbed water, considering the weight of the zeolite.
FIELD: medicine, pharmaceutics.
SUBSTANCE: invention relates to pharmaceutical industry, namely to biologically active compound, which has analgesic action. Lignan, which has analgesic action, whose structure is described as (1R,2S)-1-[(1R,2S)-1-(3,4-dihydroxyphenyl)-6,7-dihydroxy-3 - [(1R,2S)-1,2,3-tricarboxypropoxy]carbonyl-1,2-dihydronaphthalene-2-carbonyl]oxypropane-1,2,3-tricarboxylic acid: .
EFFECT: lignan has directed action at proton-driven ion channel ASIC3, which initiates neuronal response under pain stimuli.
7 dwg, 8 ex
FIELD: basic organic synthesis, chemical technology.
SUBSTANCE: invention relates to the improved method for isomerization reaction of pentane-hexane fraction with aim for preparing high-octane additive for gasoline. Pentane-hexane fraction is subjected for isomerization reaction in reaction-rectifying process using a low-temperature platinum-alumina catalyst. The parent raw is subjected for preliminary separation for pentane and hexane fractions. These fractions are subjected for separate isomerization that is carried out in vapor phase in reaction zone in bottom of reaction-rectifying column. Catalyst is placed under plates of zone and pressure in reaction zone in maintained in the range from 0.6 to 3.6 MPa, temperature - from 110.0oC to 200.0oC in the mole ratio hydrogen : hydrocarbons at inlet into column from 0.03:1 to 4:1. Method provides enhancing conversion of n-pentane, n-hexane and methylpentanes to high-octane isomers, elevating octane number of isomerizate and constructive simplifying the process.
EFFECT: improved preparing method.
1 dwg, 1 ex
FIELD: petrochemical processes catalysts.
SUBSTANCE: catalyst based on crystalline element-alumino-phosphates and having structure A1PO-31 (SATO) is prepared by providing first reaction mixture containing aluminum source, phosphoric acid, and one or more sources of substituting element as well as organic structure-forming compound followed by crystallization of above mixture under hydrothermal conditions required to form crystals with structure A1PO-31 and isolation of solid crystallization product, to which further modifying group VIII metal is added. Structure-forming compound mentioned above is selected from di-n-pentylamine and mixture thereof with other di-n-alkylamines and substituting element is selected from magnesium, zinc, silicon, cobalt, manganese, nickel, and cadmium. Method of isomerization of n-paraffins at elevated temperature and hydrogen pressure in presence of above-described catalyst is also disclosed.
EFFECT: increased activity and selectivity of catalyst.
4 cl, 1 dwg, 3 tbl, 17 ex
FIELD: petrochemical processes.
SUBSTANCE: feedstock is brought into contact with preliminarily activated zeolite-containing catalyst, namely mordenite-supported Pt, at 250-300°C, pressure 1.5-3.5 MPa, hydrogen-containing gas-to-feedstock ratio 300-1000 nm3/m3, and feed flow rate 1.0-4.0 h-1. Preliminary activation of zeolite-containing isomerization catalyst is conducted in two successive steps: drying catalyst in inert gas flow; reducing catalyst in hydrogen-containing gas flow; and supplying feedstock and setting steady-state isomerization process. Drying of zeolite-containing catalyst in inert gas flow is effected under conditions of gradually raised temperature from 120°C at temperature raise rate 10-15°C/h and ageing for 2-5 h at 120°C to 350°C followed by ageing at this temperature, whereupon temperature is lowered to 130°C. Reduction of zeolite-containing catalyst in hydrogen-containing gas flow is effected at gradually raised temperature to 220-350°C at temperature rise rate 15-25°C/h and ageing for 2-6 h at 220-350°C, whereupon temperature is lowered to 180°C. Initial feedstock is supplied at 180°C in circulating hydrogen-containing gas flow, aged for 4 h at 180°C and then gradually heated to 250°C at heating rate 5°C/h, after which further heated at heating rate 5°C a day to achieve process characteristics meeting product quality requirements.
EFFECT: increased catalyst activity, selectivity, and working stability.
2 cl, 2 tbl, 17 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: organic synthesis.
SUBSTANCE: invention pertains to obtaining branched alkanes with general formula CnH2n+2, where n = 4-10. CCI4 is gradually added to a mixture of hexane, triethylaluminium - Et3Al and a catalyst - PdCl2, in an argon atmosphere at atmospheric pressure and temperature of 10-60°C for a period of 0.5-2 hours. The molar ratio of hexane: Et3Al : CCl4 : PdCl2 is 75:10:20:0.1.
EFFECT: obtaining of a mixture of branched alkanes with high output.
1 tbl, 1 ex
SUBSTANCE: invention pertains to a catalyst and a method for selective increase in quality of paraffin raw material, with the aim of obtaining concentrated isoparaffin product as a benzine component. Description is given of the catalyst, which consists of a carrier from a sulphated oxide or hydroxide of group IVB (IUPAC 4) metals. The first component is, at least, from one lanthanide element or an yttric component, which is mainly ytterbium, and at least, one metal of the platinum group, which is mainly platinum, and a fireproof oxide binding substance, on which is dispersed at least, one metal of the platinum group. Description is given of the method of making the above mentioned catalyst, including a sulphated oxide or hydroxide of a group 1VB metal, depositing of the first component, mixing the sulphated carrier with the fireproof inorganic oxide of the oxide carrier, burning, depositing of the second component and subsequent burning. Description is given of the method of converting hydrocarbons through contacting with raw materials with the catalyst described above.
EFFECT: selective increase in quality of paraffin raw materials.
12 cl, 2 tbl, 2 dwg, 7 ex
SUBSTANCE: catalyst includes carrier, which contains tungsten oxide or hydroxide of at least one element from grope IVB ("ИЮПАК 4"), first component from at least one element from lanthanide line, yttrium and their mixture, and second component, which contains at least one component of metal from platinum group or their mixture. Also described is method of hydrocarbons transformation by contacting of raw material with solid acid catalyst, described above, with transformed product formation. Described is method of paraffin raw material isomerisation by its contacting with said catalyst at temperature from 25 to 300°C, pressure from 100 kPa to 10 MPa and volumetrical speed of liquid feeding from 0.2 to 15 hour-1 , with further product release, enriched by isoparaffins.
EFFECT: stability in hydrocarbons transformation process, increase of isoparaffins content.
10 cl, 1 tbl, 2 ex, 8 dwg
SUBSTANCE: invention relates to method of polymerisation of raw material flow containing C5-C6 hydrocarbons, which includes: loading of hydrogen and raw material, containing at least, normal C5-C6 hydrocarbons into isomerisation zone and contacting of hydrogen and raw material with isomerisation catalyst in conditions that favour increase of degree of hydrocarbons branching in raw material flow and ensuring formation of outgoing flow from isomerisation zone, which contains, at least, butane, normal pentane, normal hexane, methylbutane, dimethylbutane, methylpentanes and hydrocarbons which have seven or more carbon atoms, isomerisation conditions including temperature from 40° to 235°C and pressure 70 kPa abs. to 7000 kPa abs; passing outgoing flow from isomerisation zone through deisohexanizer zone in order to divide it into four flows, flow outgoing from upper part of deisohexaniser zone, containing, at least, butane, first side flow from deisohexaniser zone, containing, at least, methylbutane and dimethylbutanes, second side flow from deisohexaniser zone, containing, at least, methylpentanes and normal hexane, and lower flow from deisohexaniser zone, containing, at least, hydrocarbons, consisting of seven and more carbon atoms; and supply of first side flow from deisohexaniser zone into zone of isomerizate stripping in order to separate upper flow from isomerisate desorber which contains, at least, butane, from product flow from zone of isomerisate stripping, containing methylbutane and dimethylbutanes.
EFFECT: application of claimed method allows to reduce capital outlays and reduce cost of energy supply due to excluding of column-stabiliser.
9 cl, 4 dwg
SUBSTANCE: invention relates to method of obtaining bicyclo-[3,3,0]-octane-2 by isomerisation of cyclooctadiene-1,5 on catalyst system based on nickel complexes, characterised by the following: as catalyst system bis[1,2:5,6-η-cyclooctadiene-1,5] nickel is used in combination with boron trifluoride etherate with mole ratio Ni: BF3·OEt2=1:2.
EFFECT: simplification of bicyclo-[3,3,0]-octane-2 obtaining and increase of its output.
1 cl, 4 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing a mixture of hexacyclo[8.4.0.02,7.03,14.04,8.09,13]tetradecene-5 and hexacyclo[6.6.0.02,6.05,14.07,12.09,13]tetradecene-3 through isomerisation of binor-S under the effect of phosphoric anhydride P2O5 (P4O10), characterised by that the reaction is carried out in a dichloromethane medium at temperature ranging from 25 to 35°C with addition of aluminium oxide Al2O3 to P2O5 in the following ratio of reagents : [Al2O3]: [P2O5]: [binor-S]=0.2-0.3:0.2-0.3:1. Use of this method allows for 80% olefin output without using tetrachloromethane.
EFFECT: reduced energy consumption, duration of reaction and reduced consumption of P2O5.
1 cl, 5 ex
FIELD: petroleum chemistry.
SUBSTANCE: olefin hydrocarbons are obtained by dehydration of paraffin hydrocarbons in presence of catalyst. Claimed method includes: preparation of mixture from direct and recycled paraffin hydrocarbon streams; vaporization; vapor heating; and overheating in oven before feeding into reactor; cooling of contact gas in disposal boiler and scrubber with water by using two circulating contours with different water temperature and air cooling of water; followed by tree-step contact gas compression with intermediate condensation; condensation; absorption of uncondensed hydrocarbons; and recovery of paraffin-olefin cut by fractionation of obtained hydrocarbon condensate. Temperature of contact gas fed into compression is stabilized on predetermined level by alteration of contact gas temperature on wet scrubber input and temperature of circulating water fed into top of wet scrubber, while said circulating water is cooled in one or two steps according to contact gas temperature on wet scrubber input; and circulating water temperature is changed either using or without air cooling.
EFFECT: decreased losses of raw material and catalyst, increased utilization coefficient of contact gas heat, and improved process stabilization.
2 cl, 1 dwg, 10 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: catalyst contains, wt %: potassium oxide and/or rubidium oxide, cesium oxide 10-40, magnesium oxide 2-10, cerium(IV) oxide 2-20, sulfur 0.2-5, and ferric oxide the rest.
EFFECT: increased selectivity and mechanical strength of catalyst.
1 tbl, 17 ex
FIELD: industrial organic synthesis.
SUBSTANCE: in two-stage isoprene production process via dehydration of isopentane, contact gas produced in each stage is condensed and non-condensed hydrocarbons are absorbed and then desorbed. Hydrocarbon condensate is separated by rectification to give low-boiling hydrocarbon distillate fraction and bottom product. The latter is separated with the aid of extractive rectification to give isopentane and isoamylene fractions after the first dehydration stage and isoprene and isoamylene fractions after the second dehydration stage. Non-condensed low-boiling hydrocarbon vapors recovered after rectification are combined with non-condensed hydrocarbons from the first dehydration stage, preliminarily compressed, separated, and subjected to absorption.
EFFECT: maximized utilization of C5-hydrocarbons leading to reduced consumption of isopentane.
2 dwg, 4 tbl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention relates to production of alkylaromatic hydrocarbon dehydrogenation catalysts and can be employed in chemical and petrochemical industries. Catalyst according to invention comprising molybdenum oxide MoO2, ferrous oxide F2O3, cerium dioxide CeO2, and iron, potassium, calcium , and magnesium compounds is characterized by containing solid solution of potassium ferrites and, additionally, cesium and/or rubidium ferrites MFeO2 and M2Fe10O16, where M=K+Contains and/or Rb, and also ferrite Ca2(MgZn)1Fe2O3 Catalyst may be granulated in the form of trefoil with holes in each foil, which are shifted toward the center of granule, or it may be in the form of circle with three, four, or five internal spokes. Catalyst preparation process and a process of dehydrogenation of alkylaromatic hydrocarbons in presence of indicated catalyst are also described.
EFFECT: enabled preparation of strong catalyst showing high activity and selectivity, and ensuring reduced pressure in reactor owing to lowered hydraulic resistance.
11 cl, 4 tbl, 10 ex
FIELD: hydrogenation and dehydrogenation catalysts.
SUBSTANCE: catalyst according to invention is composed of, wt %: potassium and/or lithium, and/or rubidium, and/or cesium compound 5-30, magnesium oxide 0.5-10, cerium(IV) oxide 5-20, calcium carbonate 1-10, molybdenum oxide 0.5-5, ferric oxide - the balance. Catalyst is characterized by loose density at least 1.0 g/cc but not higher than 2.00 g/cc and apparent density at least 2.0 g/cc but not higher than 3.5 g/cc. Starting ferric oxide has loose density 1.0-1.5 g/cc.
EFFECT: increased selectivity and strength of catalyst.
1 tbl, 13 ex
SUBSTANCE: catalyst for dehydration of alcylaromatic hydrocarbons containing oxides of iron, alkaline-earth metals, cerium (4), molybdenum, titanium and/or vanadium and potassium is described. The diffraction pattern of said catalyst contains reflexes of potassium polyferrite and hematite phase related to iron (3) oxide in α-form. The relative intensities of said reflexes are (1÷40) and 100% respectively. Catalyst component ratio may be as follows: potassium oxide 5-30 Wt%; oxides of alkaline-earth metals 1-10 Wt%; cerium (4) oxide 5÷20 Wt%; molybdenum oxide 0.2-5 Wt%; titanium and/or vanadium oxide 0.2-5 Wt%; iron (3) oxide - the rest. Additionally catalyst can contain up to 30 Wt% of rubidium oxide and/or cesium oxide. The catalyst is prepared by calcinating at temperatures 500-750°C during 1-3 hr and 800-900°C during 0.5-1.5 hr. Bulk density of catalyst is in the range 0.95-1.5g/sm2.
EFFECT: development of catalyst providing high conversion and selectivity in relation of end products in the process of alcylaromatic hydrocarbons dehydration; increasing of catalyst service cycle.
5 cl, 1 tbl, 15 ex
SUBSTANCE: invention pertains to modification of the Houdry method of dehydrogenation of aliphatic hydrocarbons. Description is given of the method of dehydrogenation of aliphatic hydrocarbons, defining the cycle, which includes the following stages: (a) loading the dehydrogenation catalyst into the reactor with obtaining of a catalyst layer, where the layer sets the boundary of the upper section, middle section and the lower section; (b) evacuation of the catalyst layer; (c) restoration of the catalyst layer through hydrogen and evacuation of the catalyst layer; (d) introduction of the aliphatic hydrocarbon into the zone of the catalyst layer in the form of gaseous product with a given speed of flow and in such a way that, the initial product comes into contact first in the upper section and come out after contact in the lower section, after the dehydrogenation of the hydrocarbon; (e) blowing out the vapour and regeneration of the catalyst layer; (f) repetition of stages (b)-(e); duration of stages (b)-(e) is controlled by a device for regulating the sequence of the cycles, differentiated by that, (1) the duration of the cycle increases due to delays, at least, in the form of one preliminarily defined time interval, of at least one stage of the cycle; and (2) hydrogen gas is introduced at percentage molar concentrations of up to 7% H2 in the reaction during stage (d). The method of dehydrogenation of aliphatic hydrocarbons (alternatives) is also given.
EFFECT: increased lifetime of the catalyst; increase in its activity and selectiveness; maintenance of the output of the desired olefins.
17 cl, 1 tbl, 3 ex
SUBSTANCE: present invention pertains to perfection of the method of obtaining at least, one product of partial oxidation and/or ammoxidising of propylene, chosen from a group, comprising propylene oxide, acrolein, acrylic acid and acrylonitrile. The starting material is raw propane. a) At the first stage, raw propane, in the presence and/or absence of oxygen, is subjected to homogenous and/or heterogeneous catalysed dehydrogenation and/or oxydehydrogenation. Gas mixture 1, containing propane and propylene is obtained. b) If necessary, a certain quantity of the other components in gas mixture 1, obtained in the first stage, besides propane and propylene, such as hydrogen and carbon monoxide is separated and/or converted to other compounds, such as water and carbon dioxide. From gas mixture 1, gas mixture 1' is obtained, containing propane and propylene, as well as other compounds, besides oxygen, propane and propylene. c) At the third stage, gas mixture 1 and/or gas mixture 1' as a component, containing molecular oxygen, of gas mixture 2, is subjected to heterogeneous catalysed partial gas-phase oxidation and/or propylene, contained in gas mixture 1 and/or gas mixture 1', undergoes partial gas-phase ammoxidising. Content of butane-1 in gas mixture 2 is ≤1 vol.%. The method increases output of desired products and efficiency of the process.
EFFECT: increased output of desired products and efficiency of the process.
72 cl, 10 ex
SUBSTANCE: invention relates to organic chemistry and petrochemistry, particularly to designing and using catalysts. Described is a catalyst for dehydrogenation of isopentane and isopentane-isoamylene fractions based on platinum and tin, deposited on a carrier - zincalume spinel. The catalyst is distinguished by that, the carrier is in form of nanocrystalline particles with average crystal size of 22-35 nm with components in the following ratio, wt %: platinum - 0.05-2.0, tin - 0.1-6.0, zincalume spinel - the rest. Also described is a method of preparing said catalyst, involving grinding and mixing oxygen-containing zinc and aluminium compounds, gradual addition of water until obtaining a homogeneous pasty mass, stirring and moulding, drying the granules at room temperature and calcination, subsequent saturation of the formed carrier with an aqueous solution of platinum and tin compounds, final drying of the catalyst mass in air; the method is distinguished by that, the carrier is calcined while gradually raising temperature to 800-900°C at a rate of 10-200°C/hour, and then for 5-40 hours at 850-1000°C, while constantly controlling size of the formed crystals until formation of nanocrystalline particles with average crystal size of 22-35 nm.
EFFECT: increased efficiency of dehydrogenation process due to increased output of isoprene, with high selectivity on dehydrogenation products, as well as due to longer inter-regeneration period of the catalyst.
3 cl, 1 tbl, 14 ex