Method of producing propylene and butene-1
SUBSTANCE: invention relates to a method of producing propylene and butene-1 from ethylene at high temperature in a continuous or periodic mode in the presence of a catalyst deposited on a support. The method is characterised by that the process is carried out at temperature 75-110°C in the presence of a catalyst containing the following in wt %: Re - 5-15, B2O3 - 3-10, γ-Al2O3 - the balance.
EFFECT: use of the present method simplifies the process and increases selectivity thereof during formation of propylene, and also enables to obtain a mixture of propylene and butene-1 as the end product.
2 cl, 6 ex, 2 tbl
The present invention relates to the field of organic chemistry, in particular to the process of conversion of ethylene, namely a previously unknown method for producing propylene and butene-1 directly from ethylene registersystem heterogeneous catalyst.
Propylene is an important petrochemical product, in particular, to obtain polypropylene, Acrylonitrile and propylene oxide. In the chemical industry propylene, together with ethylene, get, mainly in oil cracking. In the future propylene will be more popular than ethylene, because of its use for the preparation of polypropylene and propylene oxide. Propylene usually get or cracking of crude oil (69%) or catalytic cracking gasoline. Only 2-3% of the total amount of propylene falls on the reaction of dehydrogenation of propane. This method of production of propylene is associated with certain difficulties. The first source of propane must be located near the region's consumption of propylene. The second reason is economic. Propane is often more expensive than propylene. In addition, the process itself is costly, in particular, energy. Currently propylene is also produced by metathesis reaction, for which required, in addition to ethylene, butene-2, the latter has preliminarily who must be obtained by the reaction of ethylene with subsequent isomerization of butene-1 to butene-2 [M.Taoufic, E.Le Roux, J.Thivolle-Cazat, J.-M.Basset. Angewandte Chemie. 2007, 119, 7340 tel. Direct transformation of ethylene into propylene catalyzed by a tungsten hydride supported on alumina: trifunctional single-site catalysis].
Butene-1 is the raw material for the production of polybutene-1, ethylene-butenova plastics (including low density polyethylene), methyl ethyl ketone, acetic acid and other products. To obtain a propylene-butenova plastics (plastics) as a valuable product with good strength characteristics is used a mixture of propylene and butene-1. Usually butene-1 is produced by catalytic dimerization of ethylene. The process is carried out at elevated pressures (15-20 ATM) and a temperature of 50-60°C using a homogeneous Ti-containing catalyst, requiring special conditions for preparing and using in the process of producing butene-1. In addition to butene-1 as side products are formed which are difficult to separate oligomers, resulting in the obliteration of the polyethylene walls of the reactor and feed ethylene [Institute of problems of chemical physics RAS, Chernogolovka. Exhibition: the Forum and the presentation of new scientific and industrial technologies "Archimedes", "High technologies of XXI century". the 15th international exhibition "Chemistry 2009". The exhibition "Innovation Sciences 2010"].
From literature is known just a few examples of the conversion of ethylene to propylene. Thus, the described prevremeni the ethylene to propylene using a catalyst Mo(CO) 6deposited on Al2O3without details of a process [P.P.O''neill, J.J.Rooney. J. Am. Chem. Soc., 1972, 94, 4383. Direct transformation of ethylene to propylene on an propylene metathesis catalyst].
The conversion of ethylene to propylene was described in the presence of a catalyst containing 2.8 wt.% Mo/SiO2[T.Katsumi, T.Kenichi. J. Chem. Soc., Faraday Trans.1 1987, 83(6), 1859. Reactive intermediate for the ethylene homologation reaction on molybdena-silica catalysts]. However, the basic process indicators (conversion, selectivity) were low.
The closest solution of the problem is the method of obtaining propylene from ethylene in a continuous or periodic modes in the presence of a tungsten catalyst supported on alumina [US Pat no. 7638672, 2009]. The process is conducted at a temperature of 150°C. the Main byproducts are butenes (butene-1, butene-2, isobutene) and hexene.
The disadvantages of this process is not sufficiently high selectivity in the formation of propylene (maximum selectivity for propylene is 93 wt.% when the conversion 6-10 wt.%) and a higher reaction temperature (150°C). However, the main disadvantage of the proposed process is the use of freshly prepared catalyst in situ in a special unit (the box) with the use of harmful ORGANOMETALLIC compounds in the environment of hydrogen without traces of air. Inadmissibility of getting air in the cooking process, and the use of the catalyst. In the presence of even traces of air, the conversion of ethylene to propylene is not happening. All this complicates the process.
The present invention is to simplify the process and increase its selectivity in the formation of propylene, as well as the possibility of obtaining a mixture of propylene and butene-1 as the target product.
This object is achieved by the proposed method of obtaining propylene and butene-1 ethylene in a continuous or batch mode at a temperature of 75-110°C in the presence of a catalyst containing, wt.%: Re - 5-15, In2About3- 3-10, γ-Al2O3- the rest.
The process according to the invention is carried out at a relatively low temperature 75-110°C.
For preferential receipt of propylene, the process is conducted in a continuous mode at a flow rate of the feed 75-100 h-1. The selectivity for propylene reaches 96,7 wt.%, and conversion of 47.9 wt.%.
The carrier of γ-Al2O3has a specific surface area of 196 m2/g, granule size of 0.1 to 1.5 mm, preferably 0.3 to 0.6 mm
The catalyst is prepared by impregnation of γ-Al2O3a solution of N3IN3in distilled water, followed by drying for 1 h in air, then 1.5 h at 150°C. Next, the resulting solid mass is impregnated with the aqueous solution of NH4ReO4, allowed to stand for 1 hour in air, and then 1.5 hours at 150°C, place the t in the reactor and calcined in a stream of dry air at a temperature of 450-600°C for 1 hour.
In contrast to the catalyst of the prototype of the proposed catalyst calcined in a stream of dry air at a temperature of 450-600°C., preferably 480-550°C. the Catalyst can be repeatedly regenerated in the above conditions. The process of conversion of ethylene is carried out in an air environment.
The process according to the invention can be performed periodically in a static reactor. This method is preferred for preferential receipt of butene-1. In this way, the butene-1 obtained for the first time, as the product formed from propylene. However, for selective receipt of propylene, the process is preferably carried out in flowing conditions, when ethylene is introduced continuously. Compared with the prototype process is carried out at lower temperatures and with higher selectivity. In contrast to the prototype of propylene according to the invention is produced directly from ethylene without intermediate stages.
The technical result of the proposed method is a simplification of the process by holding it in an atmosphere of air, increasing the selectivity of obtaining propylene to 96.7 wt.%, obtaining butene-1 with access to 83,8 wt.%, as well as the mixture of propylene and butene-1 which can later be used without separation to obtain a propylene-butenova plastics.
The invention soo which corresponds to the criterion "novelty", as known in the scientific-technical and patent literature does not include a full set of features characterizing the present invention. The invention also meets the criterion of "inventive step"as the process in the presence of a catalyst to Re-In2About3/Al2O3to obtain propylene and butene-1 was not obvious, since according to literature data [K.I.Ivin, J.C.Mol. Olefins metathesis and metathesis polymerization, Academic Press, 1997, 93] Re/Al2O3the catalyst is not active in the conversion of ethylene and at Re/In2O3this process was not conducted.
The following examples illustrate the present invention but do not limit its scope.
Example No. 1. The method of preparation of the catalyst.
For the preparation of the catalyst charge of 1.46 g of N3IN3, dissolved in 21 ml of distilled water and impregnated with the obtained solution of 16.4 g of γ-Al2O3(S beats. 196 m2/g granules of 0.3-0.6 mm). Dried 1 h in air, then 1.5 h at 150°C. Next of 8.25 g of the obtained solid mass is impregnated with the aqueous solution of NH4ReO4(10 ml of N2Oh and 0.71 g NH4ReO4). Allowed to stand for 1 hour in air, and then 1.5 hours at 150°C, are placed in a reactor and calcined in a stream of dry air (6 l/h) at 530°C for 1 hour. The resulting catalyst has a composition, wt.%: 6 Re, 5 V2O3, 89 γ-Al2O3./p>
Similarly receive catalysts with different content components, the compositions of which are given in tables 1 and 2.
Example No. 2. Catalytic conversion of ethylene in a static reactor.
0.71 g of the catalyst prepared according to example No. 1 of the composition, wt.%: 6 Re, 5 V2O3, 89 γ-Al2O3placed in a glass flask of 50 ml volume filled with air, and then poured into the flask and 1.4 ml of n-octane and miss ethylene to establish a pressure of ethylene 80-90 kPa and heated the mixture at 8-10°C/min to a temperature of 91°C at a rotation speed of the stirrer approximately 100 rpm Over 1.7 hours the yield of propylene 33.2 wt.%, as butene-1 - 58,7 wt.% the total conversion of ethylene 91,9 wt.%.
Table 1 shows the results for various combinations of catalyst and process conditions in periodic mode.
|# example||the composition of the catalyst, wt. %||temperature op.,0||time slave., h||yield, wt.%||conversion, wt.%|
|2,0||of 37.9||of 60.5||98,4|
As can be seen from table No. 1, the proposed method allows to obtain butene-1 with a sufficiently high yield, reaching 83,8 wt.%, at high conversion of ethylene.
Example No. 6. Catalytic conversion of ethylene to propylene and butene-1 in a flow reactor.
of 1.75 g of the catalyst prepared as in example No. 1, composition, wt.%: 12 Re, 5 V2O3, 83 γ-Al2O3loaded into a quartz glass reactor, preheated in air to a temperature of 100°C, then let ethylene with a bulk velocity 80 h-1. Through 0,62 hours, the conversion of ethylene is 23.9 wt.% when the selectivity to propylene and butene-1 94 and 6 wt.% respectively.
Table 2 shows the results for various combinations of catalyst and process conditions in a continuous mode.
|the catalyst composition, wt.%||Top.,0||Vabout.,h-1||time slave., h||conversion, wt. %||selectivity, wt. %|
As can be seen from table No. 2, the proposed method is superior in selectivity in the formation of propylene prototype, and at higher conversions. In addition, according to example No. 11 in certain conditions it is possible to obtain almost the equilibrium mixture of propylene and butene-1.
1. The method of obtaining propylene and butene-1 ethylene at elevated temperature in a continuous or periodic mode in the presence of a catalyst supported on a carrier, distinguishing the I,
the process is conducted at a temperature of 75-110°C in the presence of a catalyst containing, wt.%:
2. The method according to claim 1, characterized in that the preferential receipt of propylene, the process is conducted in a continuous mode at a flow rate of the feed 75-100 h-1.
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to production of cyclic α-methylstyrene dimmer, in particular 1,1,3-trimethyl-3-phenylindane, which is used as base for lubricating materials, propellants, and heat carriers. Process is accomplished via dimmerization of α-methylstyrene using, as catalyst, complex AlCl4*CCl3 formed in situ during interaction of activated powdered metallic Al with CCl3 at 50°C and atmospheric pressure, Al/CCl3/α-methylstyrene molar ratio being 10:25:3.9. Reaction time is 2 min. Selectivity of formation of desired product is 94% and α-methylstyrene conversion is 100%.
EFFECT: increased yield of desired product.
< / BR>These compounds may find application in thin organic synthesis and in the synthesis of biologically active preparations containing substituents exclusively threo-configuration, special polymers
SUBSTANCE: invention relates to a method of producing butene-1 via dimerisation of ethylene at pressure 0.5-4 MPa and temperature 50-95°C in the medium of a hydrocarbon solvent in the presence of a catalyst system consisting of trialkyl aluminium - AlR3, in which R is a hydrocarbon radical containing 1-6 carbon atoms, titanium etherate - Ti(OR)4, in which R is a hydrocarbon radical containing 2-6 carbon atoms, in the presence or absence of a modifier - ether. At the end of the dimerisation reaction, a catalyst deactivator is fed into the reactor or into the reaction mass when the reaction mass comes out of the reactor, where the catalyst deactivator used is monoalkyl ethers of ethylene glycol.
EFFECT: use of the method increases selectivity of the process and purity of butene-1, lowers the probability of secondary reactions such as isomerisation of butene-1 into cis- or trans-butene-2, reduces the degree of polymerisation, improves working conditions and improves economic performance of the process.
3 cl, 11 ex, 2 tbl
SUBSTANCE: invention is related to method for dehydration of alkyl aromatic hydrocarbons, which are selected from at least one of ethyl benzene, propyl benzene, isopropyl benzene and methyl ethyl benzene, including contact of gas flow, which comprises at least one of hydrocarbons, with catalyst of dehydration at the temperature of reaction in direct flow in dehydration reactor with ascending flow, where average time of hydrocarbon contact to catalyst in zone of dehydration reactor makes from 0.5 to 10 seconds, and where average time of catalyst location in dehydration reactor with ascending flow makes from 0.5 to 40 seconds; and transfer of hydrocarbon and catalyst from dehydration reactor with ascending flow into separation device, where average time of hydrocarbon contact with catalyst at the temperature of reaction in separation device makes less than 10 seconds.
EFFECT: increased speed of target products making without reduction of selectivity.
11 cl, 5 dwg
SUBSTANCE: invention relates to two versions of a method of hydromerisation of C4 olefin double bond, one of which involves feeding hydrogen, carbon monoxide and a stream of material containing isobutane, isobutylene, 1-butene and 2-butene into a reaction zone, which is a catalytic distillation column, in which there is a hydroisomerisation catalyst for hydroisomerisation of double bonds; conversion of part of the said 1-butene to 2-butene; formation of a bottom product which contains 2-butene, and a distillate which contains isobutene and isobutylene, and feeding carbon monoxide into the said reaction zone in amount ranging from 0.001 to 0.03 mole of carbon monoxide per mole of hydrogen, where the said reaction zone has a defined length in the axial direction, and the said carbon monoxide is fed into the said reaction zone in several feed points, lying along the said length in the axial direction.
EFFECT: more efficient hydroisomerisation of 1-butene double bond with formation of 2-butene.
14 cl, 5 ex, 7 tbl, 14 dwg
SUBSTANCE: invention relates to a method of converting a C4 stream, containing 1-butene and 2-butene, preferably into 2-butene, involving: mixture of the said C4 stream with the first hydrogen stream to form the input stream, hydroisomerisation of the said input stream in the presence of first hydroisomerisation catalyst, so as to convert at least part of the said 1-butene to 2-butene and obtain an output hydroisomerisation product, separation of the output hydroisomerisation product in a catalytic distillation column, with a top end and a bottom end, to obtain a mixture of 1-butene at the said top end, a top output stream which contains isobutene and isobutylene, and a bottom stream which contains 2-butene, and hydroisomerisation of the said mixture of 1-butene at the said top end of the catalytic distillation column using a second hydroisomerisation catalyst to obtain additional 2-butene in the said bottom stream; where location of the said second hydroisomerisation catalyst in the top section of the column as a separate reaction zone is chosen to achieve maximum concentration of 1-butene, under the condition that, the hydroisomerisation stage with participation of the second isomerisation catalyst does not take place. The invention also relates to an apparatus for realsing this method and a method of producing propylene from a C4 stream.
EFFECT: selective hydrogenation of 1-butene to 2-butene which is more efficient than existing technologies.
30 cl, 7 dwg, 4 tbl, 2 ex
SUBSTANCE: invention relates to the method of producing low-molecular olefin hydrocarbons through pyrolysis of hydrocarbon material in the presence of an activating additive and water vapour. The method is characterised by that, the activating additive used are non-ionic surfactants.
EFFECT: increased output of low-molecular olefins during pyrolysis of vacuum gas oil.
3 cl, 6 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of olefins, namely, 1-butene of polymerization purity by a method of catalytic dimerization of ethylene. Invention describes the catalytic system for dimerization of ethylene to 1-butene based on titanium alcoholate of the general formula: Ti(OR)4 wherein R means (C2-C6), aluminum trialkyl of the general formula: AlR3 wherein R means (C2-C6) and ester chosen from group comprising tetrahydrofuran, dioxane or their mixture and wherein the mole ratio of ester to titanium alcoholate = (0.1-0.49):1 and that of aluminum trialkyl to tetraalkoxy-titanium = (2.6-6):1. Also, invention describes a method for dimerization of ethylene to 1-butene in hydrocarbon solvent medium at temperature 50-95°C and under ethylene pressure 0.3-0.4.0 MPa in the presence of the catalytic system. Invention provides enhancing selectivity of process, increasing yield of 1-butene as measured per unit of catalyst, reducing possibility for carrying out by-side reactions, such as polymer synthesis, isomerization of 1-butene to 2-butene and formation of butanes.
EFFECT: improved method of dimerization, valuable properties of catalytic system.
6 cl, 3 tbl, 12 ex
FIELD: organic chemistry, petroleum chemistry, chemical technology.
SUBSTANCE: the parent mixture consisting of preferably from C4-hydrocarbons comprising n-butenes, impurities of isobutene and/or butadienes and, possibly, butanes is subjected for a single or two-fold rectification with preliminary and/or simultaneous, and/or intermediate isomerization of 1-butene to 2-butenes preferably. From the distillate composition hydrocarbons with normal boiling points below -4°C and, possibly, n-butane in a remained flow containing 2-butenes preferably and, possibly, other part of n-butane are removed, and isomerization of 2-butanes to 1-butene is carried out, and 1-butene is isolated as a distillate, possibly, with impurity of n-butane. Invention provides simplifying technology of the process.
EFFECT: improved preparing method.
13 cl, 3 dwg, 2 tbl, 9 ex
SUBSTANCE: invention relates to a method of regenerating a catalyst layer and a method of producing acrolein and/or acrylic acid via heterogeneously catalysed partial gas-phase oxidation of propylene. The method of regenerating a catalyst layer which is deactivated during heterogeneously catalysed partial dehydrogenation of a hydrocarbon involves passing a regenerating gas through a layer of deactivated catalyst for a period of time t, said gas being at high temperature and containing molecular oxygen and an inert gas but not containing a hydrocarbon, under the condition that during the regeneration process total content GA of carbon oxides in the regenerating gas passed through the catalyst layer at the outlet of the catalyst layer within a period of time t at least periodically exceeds total content GE of carbon oxides in the regenerating gas passed through the catalyst layer at the inlet of the catalyst layer, wherein the corresponding content values are expressed as a percentage of the volume (vol. %) of the regenerating gas and wherein the difference ΔG=GA-GE before the end of the regeneration process passes through a maximum ΔGmax, where: a) 0.2 vol. % ≤ ΔGmax≤ to 5 vol. %, and b) content of molecular oxygen in the regenerating gas to be passed through the catalyst layer expressed in vol. % of the regenerating gas, for a period of time t before the end of the regeneration process, is increased at least thrice, wherein the increase in content of molecular oxygen each time is at least 2 vol. %. In the method of producing acrolein and/or acrylic acid, the catalyst layer is regenerated using the disclosed regeneration method from time to time.
EFFECT: susceptibility of the regenerated catalyst layer to deactivation is not different from susceptibility of a freshly loaded catalyst to deactivation.
22 cl, 3 tbl, 4 dwg, 3 ex
SUBSTANCE: method involves oxidative chlorination of methane, pyrolysis of the methyl obtained from methane oxychlorination, and is characterised by that after extracting chloromethanes from the methane oxychlorination step, the remaining still liquor, which primarily contains methylene chloride and chloroform, undergoes hydrodechlorination at temperature 150°-300°C on a palladium or nickel-molybdenum catalyst on a support, and the obtained stream of reaction gas is split into two fractions. One of said fractions with high-boiling point hydrodechlorination products, which contain unreacted methylene chloride and chloroform, is fed into a chloromethane separation unit for the methane oxychlorination step, and the other fraction with low-boiling point gases from the chloromethane hydrodechlorination process, which contain hydrogen, methane, hydrogen chloride and partially methyl chloride, is merged with the gas stream coming from the methyl chloride pyrolysis step, followed by combined separation thereof into hydrogen, methane, lower olefins and unreacted methyl chloride, which is returned to the catalytic pyrolysis step.
EFFECT: use of present method enables to increase output of methyl chloride and, consequently, light olefins obtained during conversion thereof.
1 cl, 1 tbl, 2 ex, 2 dwg
SUBSTANCE: method for heterogeneous catalytic partial dehydrogenation, where an input stream of a gaseous reaction mixture containing the hydrocarbon to be dehydrogenated passes through a solid catalyst layer in a column, and the input stream of the gaseous reaction mixture in the column is formed by adding a gas I to the input stream being fed to the solid catalyst layer in the column, where gas I contains molecular hydrogen and the hydrocarbon to be dehydrogenated. An input gas II containing molecular oxygen is added before the solid catalyst layer.
EFFECT: method provides completely satisfactory homogenisation of CO2 concentration after passing through an inert layer.
39 cl, 18 dwg
SUBSTANCE: invention relates to versions of the method of separating olefin from paraffin in the product stream from a dehydrogenation system. One of the versions involves a step (a) for feeding a stream of material essentially consisting of a mixture of at least one olefin and at least one paraffin; (b) dividing the stream of material into a first portion and a second portion; (c) feeding the first portion of the stream of material into a first separation column for products and feeding the second portion the stream of material into a second separation column for products, where the first separation column for products works at a higher pressure than the second column for products; (d) feeding at least a portion of the stream of overhead product from the second separation column for products into a heat pump with compression of the stream of the overhead product of the second product separator; and (e) feeding steam from at least one steam turbine, which activates the heat pump, into the reboiler of the first separation column for products.
EFFECT: extraction of a high-purity propylene product with lower power consumption.
17 cl, 3 dwg
SUBSTANCE: invention relates to a method for continuous, heterogeneously catalysed partial dehydrogenation of at least one dehydrogenated (C2-C4)-hydrocarbon in gas phase, comprising a procedure where at least one initial gas stream is continuously fed into a reaction space surrounded by jacket which touches the reaction space and has at least one opening for inlet of at least one initial gas stream in the reaction space and at least a second opening for outlet of at least one stream of the formed gas from the reaction space, said initial gas stream containing at least one dehydrogenated hydrocarbon; in the reaction space at least one dehydrogenated hydrocarbon passes through at least one layer of catalyst lying in the reaction space to obtain a gaseous product which contains at least one dehydrogenated hydrocarbon which does not react with the dehydrogenated hydrocarbon; and using an oxidative or a non-oxidative method, molecular hydrogen and/or water vapour are partially dehydrogenated to form at least one dehydrogenated hydrocarbon; at least one stream of the formed gas is continuously removed from the reaction space; the method is characterised by that the surface of the jacket on the side in touch with the reaction space is made from steel S, partially in a layer of thickness d equal to at least 1 mm, said steel having the following composition: from 18 to 30 wt % Cr (chromium), from 9 to 36 wt % Ni (nickel), from 1 to 3 wt % Si (silicon), from 0.1 to 0.3 wt % N (nitrogen), from ≥ 0 to 0.15 wt % C (carbon), from ≥ 0 to 4 wt % Mn (manganese), from ≥ 0 to 4 wt % Al (aluminium), from ≥ 0 to 0.05 wt % P (phosphorus), from ≥ 0 to 0.05 S (sulphur) and from ≥ 0 to 0.1 wt % one or more rare-earth metals, and in the rest Fe and impurities due to the synthesis process, where the percentages are associated with total weight, respectively. The invention also relates to a jacket in which the disclosed method is realised.
EFFECT: use of the present invention enables to reduce catalysed thermal decomposition of dehydrogenated hydrocarbon and/or a hydrocarbon capable of being dehydrogenated.
30 cl, 1 ex