The way to separate and/or joint receipt of methylacetylene and allen
(57) Abstract:The invention relates to the petrochemical industry and relates to a method of separate and/or joint receipt of methylacetylene and Allen from C3-hydrocarbon fraction by extractive distillation in the presence of acetonitrile as a selective solvent for the first stage of the process in the mode of extractive distillation in the presence of acetonitrile as a selective solvent for the first stage of the process in the mode of extractive distillation at elevated pressure to separate the propane-propylene fraction to a residual content of C3-fraction of propane and propylene with 0.1 - 35%, providing phlegmatization distillate fractions. Subsequent separation of the cubic product of the extractive distillation is carried out, preferably, in the presence of acetonitrile or without solvent with obtaining Allen or Allen together with methylacetylene and cubic product - extract methylacetylene or methylacetylene - allene faction in acetonitrile. From the extract is then separated by distillation methylacetylene or methylacetylene-allene faction. Clear selection of all distillate fractions regulate the flow ristorantino marketable products: allene and methylacetylene with a high degree of purity and recovery (90%), and the mixture Allen and methylacetylene with any concentration of these hydrocarbons. 2 C. p. F.-ly, 1 Il., table 2. The invention relates to the petrochemical industry and, more specifically, to method separate and/or joint allocation methylacetylene and Allen from C3-fractions of pyrolysis. Methylacetylene-allene fraction (IRF) is used as a substitute for acetylene in the gas-flame processing of metals and in chemical technology; individual hydrocarbons - methylacetylene and allene are used as raw materials for various valuable products and medicines.In accordance with ed.St. N 761447, class C 07 C 7/04, 1978  individual methylacetylene and Allen get a low-temperature rectification of the LFA. Due to the proximity of the boiling points of the components of the LFA, which serves as raw material for allocation methylacetylene and Allen, are the columns of a clear rectification (up to 140 plates) at a high reflux (> 25). To ensure the safe conditions of the process requires a deep cold. Raw material for production of target products is concentrated LFA; use3-fractions of pyrolysis in this process is disadvantageous because of the large material and energy costs. Some of the measures Department which requires additional process steps and leads to loss of target products. Furthermore, the method cannot be used to obtain the LFA.Joint or separate receiving methylacetylene and Allen from C3-hydrocarbon fraction according to the method described in application laid Germany N 3539553, class C 07 C 11/14, 1987 , is carried out by absorption Allen and methylacetylene selective solvent, for example dimethylformamide.From absorbate containing propane, propylene, methylacetylene, and allene, separating the bulk of propane and propylene. Then, at the next stage, when a lower pressure is conducted subsequent Stripping of propane and propylene. At the same time in the head of the Stripping column serves fresh dimethylformamide for absorption Allen, flowing exhaust from the top of the column flow. This separate additional amount of propane and propylene with the addition of Allen and methylacetylene. At the third stage separates the residual quantity of propane and propylene from dimethylformamide, enriched Allen. To reduce ash Allen flue gases absorb fresh dimethylformamide. The concentrates methylacetylene and Allen in dimethylformamide with the second and third stages is directed to the regeneration of the solvent with simultaneous separation of kontsentrirovaniya large energy and material consumption, cumbersome process scheme. Clean the MAF and individual methylacetylene and Allen is possible at the cost of significant loss of target products due to the fact that the basis of the method is absorption, do not allow for a clear separation of mixtures. Dimethylformamide is a relatively high-boiling and corrosive solvent that is used as the absorbent, causes polymerization Allen and methylacetylene, reducing the degree to which they retrieve from3-factions.There is a method of allocating methylacetylene-allene fraction (IRF) of the propane fraction of pyrolysis by extractive distillation using diluted with water and acetonitrile as solvent (ed.St. USSR N 439143, CL 7/08 C 07 C, 1972) . The method allows to allocate methylacetylene and allene in the form of a mixture. Next, the LFA by low temperature rectification divided into methylacetylene and allene. Use of diluted acetonitrile at the stage of selection of the LFA leads to increased energy consumption for regeneration of the solvent. However, due to the hydrolysis of acetonitrile creates a corrosive environment, and as a consequence, additional material costs. In addition, the water flowing with acetonitrile in viscotemp and violations. The separation of the LFA on the individual components associated with the use of columns clear rectification and a large reflux ratio, which requires large energy and material costs, accompanied by a loss of Allen and methylacetylene propane and propylene, with which these target products form an azeotrope. In addition, as in the method , to ensure the safety of the process requires a deep cold.The objective of the invention is a method to separate and/or joint receipt of methylacetylene and Allen increased productivity and process security with reduced cost of energy and materials while simplifying technology.It was found that the problem is solved, in accordance with the present invention, by way of separate and/or joint receipt of methylacetylene and Allen, comprising mixing WITH the3-hydrocarbon fraction with aprotic selective solvent is acetonitrile and the separation in the first stage of the process in the mode of extractive distillation at high pressure propane-propylene fraction to a residual content OF3-fraction of propane and propylene with 0.1-35 wt.%, providing phlegmatization distillate fracc is the existing topics that subsequent separation of the cubic product of the extractive distillation is carried out with obtaining Allen or Allen together with methylacetylene and cubic product - extract methylacetylene or methylacetylene-allene faction in acetonitrile, which is separated methylacetylene or methylacetylene-allene faction, and clarity of the selection of all of distillate fractions regulate the flow of solvent and/or phlegmy, and subsequent separation of the cubic product of the extractive distillation is carried out in the presence of acetonitrile; acetonitrile regenerate the drying and/or rectification.In the method corresponding to the invention achieves improved performance by increasing the degree of extraction while reducing entrainment of target products in their selection of raw materials, and also due to more marketable products - propane-propylene fraction. How is the material and energy saving, which is a consequence of the application of the simplified technology directly from the cubic product of extractive distillation to isolate individual components and methylacetylene-allene faction. This ensures the safety of propileno is a phlegmatizer. A significant decrease in temperature level of heat and refrigerants used in the process, leads to a significant reduction in both energy and material costs, for example, because of the possibility to refuse the use of powerful compressor.The application of the present invention anhydrous acetonitrile also leads to reduction of corrosion activity and consumption reduction due to management recycling the regenerated solvent.The method according to the invention, moreover, allows one process to get methylacetylene, allene, and mixtures thereof almost any desired concentration.The drawing shows a process diagram of a method of joint and/or separate receiving methylacetylene and Allen from hydrocarbon WITH3-faction. In accordance with the invention WITH3-faction to separate and/or joint receipt of methylacetylene and Allen sent in the middle part of the extractive distillation column K-1, in its upper part serves extractant - acetonitrile. As distillate from K-1 through the heat exchanger T-1, water-cooled, placing a major portion of the propane-propylene fraction, which is more marketable product. Small is Ronny K-1 CBM product extractive distillation, representing the extract methylacetylene and Allen in acetonitrile with a mixture of propane, propylene and hydrocarbons4after the heat exchanger T-3 is sent to the Stripping column K-2, the upper part of which operates in the mode of extractive distillation, or without solvent. As distillate K-2 after the heat exchanger T-4 are selected commodity products: Allen - tank E-1 or methylacetylene-allene fraction of the necessary ingredients - tank E-3 (i.e., the LFA can be obtained with high, compared with the average composition, the content of Allen or methylacetylene). Part of his return as phlegmy in column K-2, steam flow which creates boiler T-5. CBM product extract methylacetylene or LFA in acetonitrile, sent after the heat exchanger T-6 in the next distillation column K-3, working as a stripper. From the top of column K-3 after the heat exchanger T-7 as a commercial product divert methylacetylene in the capacity of E-2 or trademarks LFA - tank E-3. Steam flow in K-3 create a reboiler T-8. CBM product - acetonitrile, after cooling in heat exchangers T-9 and T-10 return in column K-1 and partially after the heat exchanger T-11 to K-2.Provides useint T-14 and drier s-1. Regeneration is conducted periodically as needed; select top pure acetonitrile, cleaned of hydrocarbons4. Regenerated acetonitrile optionally subjected to drying and return in recycling or in the storage capacity of acetonitrile E-4. As raw materials are used WITH a3the fraction of ethylene containing propane, propylene, allene, methylacetylene and mixture of hydrocarbons WITH4.The invention is illustrated by the following examples of specific performance, illustrating, but not limiting it.Example 1. (Separate receipt Allen and methylacetylene). Extractive distillation is carried out in column K-1 with a working pressure 8-10 ATA at reflux the number to 4 and a temperature of from 15 to 155oC.Raw propane fraction of pyrolysis, containing, wt.%: propane + propylene 59; Allen + methylacetylene 40;41, in the amount of 2527,0 kg/h to send in column K-1. In the top part of it in the amount of 25000 kg/h serves acetonitrile, which, passing from top to bottom, absorbs Allen, methylacetylene, hydrocarbons4and the amount of propane and propylene, which should be contained in commercial products as phlegmatizer. From the top of column K-1 OTB extractive distillation of column K-1 in the number 26100 kg/h, cooled in the heat exchanger T-3 and sent to the column K-2.In the upper part of the Stripping distillation column K-2 with a working pressure of 2.5-3.5 ATA, reflux ratio to 3 and temperature from -12 to +115oServed with 5000 kg/h of pure acetonitrile. From the top of column K-2 assign commodity Allen in tank E-1 in the amount of 500 kg/h, the part of Allen's return to the column in the form of phlegmy. CBM product of the column - extract methylacetylene in acetonitrile in the number 30600 kg/h after heat exchanger T-6 is sent to the Stripping column K-3.From the top of a Stripping distillation column K-3 has an operating pressure of 1.5 to 2.5 ATA, reflux number of 3.5 and a temperature of -10 to +110oC) assign the trademarks of methylacetylene in tank E-2 in the amount of 600 kg/h, the part of methylacetylene return in the form of phlegmy in the head of the column. CBM product columns - acetonitrile in the amount of 30,000 kg/h to send in columns K-1 and K-2.If necessary regeneration of circulating acetonitrile, part of it (3000 kg/h) is heated in the heat exchanger T-12 and sent to distillation column regeneration To-4, where the solvent is cleaned from impurities hydrocarbons WITH4. Working conditions on the K-4: reflux number 1, working pressure 1-2 ATA and a temperature(85-110)oC. From the top of column K-4 purified acetonitrile the TP is x products are presented in table.1.Example 2. (Getting methylacetylene and the LFA and Allen and LFA). The method is carried out as in example 1, except that the temperature of the column K-1 supports up to 140oC. as distillate column K-2 in tank E-3 divert approximately 1000 kg/h LFA containing 65-75% Allen + methylacetylene, including Allen 30%, the so-called methylacetylene-allene fraction enriched Allen. The average composition of the LFA, wt.%: Allen 30 + methylacetylene 45, propane + propylene - rest. CBM product extract methylacetylene in acetonitrile after heat exchanger T-6 is sent to the Stripping column K-3. From the top of column K-3 after the heat exchanger T-7 commodity methylacetylene in the amount of about 70 kg/h assign to the tank E-2, part of its return in the form of phlegmy in the column.Ash Allen and methylacetylene with distillaton K-1 less than 0.03 wt.%. The mixture of target products is presented in table.1.Examples 3-5. The method is carried out in accordance with examples 1 and 2 except that in column K-1 the temperature in the cube is brought to 150oC. In the column K-2 as distillate selected Allen, CBM product - LFA in acetonitrile. In K-3 as distillate allocate the LFA, enriched with methylacetylene. The composition polocaine be obtained separately allene and methylacetylene faction, and the mixture Allen and methylacetylene in almost any relationship and any concentration (depending on user requests), including concentrated Allen, concentrated methylacetylene, concentrated LFA and LFA, rich Allen or methylacetylene. In addition, this method allows to get the propane-propylene fraction with a purity of > 99,0%, i.e. more marketable product.In table. 2 shows the results obtained when using the invention. As seen from the above table.2 data, the degree of extraction of Allen and methylacetylene greater than 99%, while their losses with the propane-propylene fraction of 0.3%. In accordance with the method of the prototype, the degree of extraction of Allen and methylacetylene not greater than 96%, while the loss of them with a propane-propylene fraction reach 4.5%. This is due to the fact that separate receiving methylacetylene and Allen carried out using as raw material methylacetylene-allene faction, the components of which form azeotrope propane, containing 12% Allen and methylacetylene. The way to separate and/or joint receipt Allen and methylacetylene, in accordance with the present invention, may bgia get methylacetylene and Allen and their mixtures from C3-pyrolysis fractions more simple, convenient and economical than existing in the industry to date. In addition, it allows you to get a more marketable product - propane-propylene fraction. 1. The way to separate and/or joint receipt of methylacetylene and Allen, comprising a mixture of C3-hydrocarbon fraction with aprotic selective solvent is acetonitrile and the separation in the first stage of the process in the mode of extractive distillation at high pressure propane-propylene fraction to a residual content of C3-fraction of propane and propylene with 0.1-35%, providing phlegmatization distillate fractions, and subsequent separation of the cubic product extractive distillation at a lower pressure, characterized in that subsequent separation of the cubic product of the extractive distillation is carried out with obtaining Allen or Allen together with methylacetylene and cubic product - extract methylacetylene or methylacetylene-allene faction in acetonitrile, which is separated methylacetylene or methylacetylene-allene faction, and clarity of the selection of all of distillate fractions regulate the flow of solvent and/or phlegmy.3. The method according to p. 1 or 2, characterized in that the acetonitrile regenerate the drying and/or rectification.
SUBSTANCE: invention relates to a method for synthesis of 1-aminomethyl-α,ω-alkadiines of general formula (1): , where R2N = piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC≡C-(CH2)n-C≡CH, where n=4, 6, 8, react with gem-diamines R2NCH2NR2, where R2N is as defined above, in the presence of a copper (I) chloride catalyst (CuCl), taken in molar ratio α,ω-diacetylene: gem-diamine: CuCl=10:10: (0.3-0.7),preferably 10:10:0.5 mmol without a solvent at temperature of 80°C and atmospheric pressure for 4-5 hours. 1-aminomethyl-α,ω-alkadiines can be used in fine organic synthesis and particularly in synthesis of scarce polycyclic compounds, as well as in synthesis of biologically active substances.
EFFECT: method increases output of the desired products.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to a method for synthesis of asymmetric α,ω-di(aminomethyl)alkadiines of general formula (1): where R2N = piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC=C-(CH2)n-C=CH, where n=4, 6, 8, react with an equimolar amount of N,N,N1N1-tetramethyldiaminomethane (bisamine) in the presence of a catalyst 6-hydrate samaric nitrate (Sm(NO3)2*6H2O), taken in molar ratio of α,ω-diacetylene: bisamine: (Sm(NO3)2*6H2O) =10:10:(0.3-0.7), preferably 10:10:0.5 moles, without a solvent at temperature 80°C and atmospheric pressure for 3 hours, with subsequent addition to the reaction mass of gem-diamine R2NCH2NR2, where R2N is as defined above, in amount which is equimolar to bisamine and stirring the reaction mass for 3-5 hours. The asymmetric α,ω-di(aminomethyl)alkadiines can be used in fine organic synthesis, particularly for synthesis of scarce polycyclic compounds.
EFFECT: improved synthesis of said derivatives.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing α,ω-di(aminomethyl)alkadiines of general formula (1) , where R2N=piperidyl, morpholyl, N-methylpiperazyl, characterised by that α,ω-diacetylenes HC=C-(CH2)n-C≡CH, where n=4, 6, 8 react with gem-diamines R2NCH2NR2, where R2N is as described above, in the presence of a copper (I) chloride (CuCl) catalyst, taken in molar ratio α,ω-diacetylene: bisamine: CuCl=10:20:(0.3-0.7), preferably 10:20:0.5 mmol, at temperature 80°C and atmospheric pressure for 4-6 hours. α,ω-aminomethylated diacetylenes can be used in fine organic synthesis, particularly for producing hard-to-get polycyclic compounds.
EFFECT: method increases output of the desired products.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing 1,1,1,3-tetraphenylpropyne from a metal derivative of phenyl acetylene and triphenyl chloromethane in the medium of an organic solvent. The method is characterised by that the metal derivative of phenyl acetylene used is lithium tetraphenyl ethinyl alanate, and the organic solvent used is pure 1,4-dioxane. The reaction is carried out while heating at boiling point of the solvent for 1 hour.
EFFECT: invention provides a method of producing 1,1,1,3-tetraphenylpropyne, which provides reproducible results with good output of the end product.
1 cl, 1 ex
SUBSTANCE: invention relates to method of obtaining 1-alkynyl adamantanes from derivatives of adamantine and acetylene compounds with catalysis with Lewis acid, taken in equimolar amounts. Method is characterised by the following: as initial components used are 1-adamantanol and 1-alkene or 1-trimethylsilylalkene, which are heated at temperature of 1,2-dichloroethane boiling in presence of 5 molar percent of gallium triflate as Lewis acid until initial compounds are fully consumed.
EFFECT: application of claimed method makes it possible to obtain target compound from commercially available initial compounds with good output of target product.
1 cl, 1 tbl, 10 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: C5-hydrocarbons with different degrees of saturation are separated by extractive rectification in extractive rectification column using dimethylformamide as extractant followed by desorption of pentenes or pentadienes therefrom and passing desorbed extractant to extractive rectification column. Part of hot desorbed extractant is subjected to liquid-phase mixing with starting hydrocarbons at vigorous stirring, after which resulting mixture is introduced into column in liquid form.
EFFECT: reduced power consumption.
2 dwg, 1 tbl, 5 ex
FIELD: petrochemical processes.
SUBSTANCE: C4-hydrocarbon fractions obtained by cracking and/or pyrolysis of hydrocarbon feedstock in presence of amine-type extractant are subjected to rectification additionally involving butylene-isobutylene fraction resulting from butylene-to-isobutylene isomerization and containing 30-70% butylenes, 25-65% isobutylene, and 3-8% butanes. Weight ratio of C4-hydrocarbon fractions to added butylene-isobutylene fraction is 1:(3-7).
EFFECT: increased separation efficiency.
FIELD: petroleum industry.
SUBSTANCE: process in carried out in column having divider arranging in longitudinal direction to form the first section, the second one and the third bottom joint section, wherein extractive scrubber is includes before divider.
EFFECT: simplified technology.
16 cl, 3 dwg
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalysate of reforming of long gasoline fractions containing more than 2% benzene is separated by rectification into three fractions: light-boiling fraction containing mainly nonaromatic C4-C6-hydrocarbons and no more than 1%, preferably no more than 0.5%, benzene; high-boiling fraction containing mainly aromatic and nonaromatic hydrocarbons C7 or higher and no more than 1%, preferably no more than 0.5%, benzene; and benzene fraction boiling within a range of 70-95°C and containing no more than 0.1%, preferably no more than 0.02%, toluene and no more than 0.02% nonaromatic hydrocarbons with boiling temperature above 110°C. Benzene fraction is routed into benzene isolation process involving extractive rectification with polar aprotic solvent having ratio of dipole moment to square root of molar volume above 0.3 db/(cm3/g-mole)1/2, preferably above 0.4 db/(cm3/g-mole)1/2, and boiling temperature 150 to 250°C.
EFFECT: improved quality of benzene.
4 dwg, 2 tbl, 5 ex
FIELD: petrochemical processes.
SUBSTANCE: process involves extractive rectification in presence of extractant mainly containing aliphatic N-alkylamide, while toluene is introduced into rectification column point disposed between extractant inlet and the top of column.
EFFECT: reduced loss of extractant with distillate.
6 cl, 3 dwg, 6 tbl, 6 ex
FIELD: petrochemical processes.
SUBSTANCE: invention provides a process flow rate comprising at least (i) zone of extractive rectification in presence of polar extractant to produce distillate mainly containing butanes and butane(s); (ii) desorption zone wherein desorption of extractant gives stream containing mainly 1,3-butadiene and. as impurities, at least 2-butene(s) and acetylene hydrocarbons; and (iii) optionally rectification zone for mainly 1,3-butadiene-containing stream. In the latter, α-acetylene hydrocarbons are subjected to liquid-phase selective hydrogenation with hydrogen or hydrogen-containing mixture in presence of solid catalyst containing metal(s) exhibiting high activity in hydrogenation process, preferably non-precious metal(s) on solid support. Temperature is maintained within a range 5 to 75°C at contact time ensuring hydrogenation of no more then 6%, preferably no more than 2% of butadiene present. After hydrogenation, 1,3-butadiene is optionally additionally separated from impurities via rectification.
EFFECT: simplified process.
13 cl, 3 dwg, 2 tbl, 10 ex