The method of purification from carbon monoxide-olefins and saturated hydrocarbons
(57) Abstract:The inventive a-olefins and saturated hydrocarbons clear of carbon monoxide by contacting at 0-150°C with a catalytic system containing a mixture and/or product of the reaction of copper oxide with one or more oxides of metals of the II group of the Periodic table at a molar ratio of copper oxide and a metal oxide IV In groups of from 1:10 to 10:1. 7 C. p. F.-ly, 1 table. The invention relates to a method of removing carbon monoxide from a-olefins and saturated hydrocarbons, in order to make the above-olefins and saturated hydrocarbons suitable for use in the processes of polymerization Ziegler-Natta. In particular, the method of the invention can be successfully used for cleaning2-C4-olefins, obtained by a process of thermal cracking, which constitute the main source of production of the above-olefins.It is known that olefins, obtained by thermal cracking of petroleum products, even after the complex treatment of the separation and purification contain small amounts of impurities, many of which, including carbon monoxide, have a deleterious effect on the catalyst CIG is giving a halide of titanium, put on magnesium chloride, and the connection alkyl aluminum as socializaton.Carbon monoxide is usually present in the above-olefins in an amount ranging from 0.5 to 10 million shares (hereinafter, assume that million shares are moles), and at such levels, it significantly lowers the efficiency of the catalysts of the Ziegler-Natta. On the other hand, not so easy to further reduce said concentration of carbon monoxide in C2-C4-olefins by means of simple distillation, given the low boiling point above-olefins. In particular, when the concentration of carbon monoxide is lower than or equal to 2 million shares distillation becomes even disadvantageous from an economic point of view.Economic damage due to the presence of carbon monoxide in the polymerization process, is enhanced when, as often happens, the carbon monoxide concentration varies within the above limit, because it causes oscillation of the polymer yield at the stage, where the latter emerges from the polymerization reactors, and is forced to take continuous and expensive operation to regulate the supply systems of the catalyst and not always with positive results. This dokatyvayutsya catalysts of the Ziegler-Natta becomes insignificant.The methods used to date to reduce the specified content of carbon monoxide in-olefins, obtained by processing petroleum products (including thermal cracking), based essentially on the use of the ability of some compounds of transition metals, in particular copper compounds, in the form of an aqueous solution, or dispersed on an inert solid support such as alumina or dvuoksid silicon), to form complexes with carbon monoxide.For example, in accordance with U.S. Pat. USA 3014973-olefins, which must be cleaned, in particular ethylene and propylene, treated with an aqueous copper-ammonia solution and then selectively emit thus to separate them from carbon monoxide, which remains bound in the complex compound of copper.To further reduce the content of carbon monoxide assumed the additional processing-olefins by contacting them with alkali metal hydroxide at temperatures higher than 170aboutC.From the data presented in U.S. patent 3014973, it is not necessary is made possible by use of the above-mentioned method of reducing the concentration of the horns and requires an additional stage liquefaction purified olefin, whenever, as often happens in the case of propylene and 1-butene, want to carry out the polymerization in liquid monomer.According to the invention offers a method of removing carbon monoxide from a-olefins and saturated hydrocarbons, whereby carry out the contacting of the olefin or saturated hydrocarbon containing carbon monoxide, at temperatures in the range from 0 to 150aboutWith, preferably, from 20 to 95aboutWith, with a catalytic system comprising the mixture and/or reaction product:
A) one or more metal oxides selected from the group consisting of cu, Fe, Ni, Co, Pt and Pd; and
FIELD: petroleum processing.
SUBSTANCE: catalyst contains 15-30% hydrogenation components including groups VU and VIII metals, 20-40% acid component, and 1-4% promoter, the rest being binder: alumina, aluminosilicate, clay, or their mixture. Catalyst is distinguished by having three-component system composed by nickel, molybdenum, and tungsten in the form of their oxides at weight ratio Ni/Mo/W equal to 25:35:40. Above-mentioned acid component contains aluminum fluoride and promoter contains boron oxide and/or zirconium oxide. Preparation technology is simple and completely suppresses production of waste water. Invention describes hydrocracking process in presence of the claimed catalyst, which is carried out at 380-430оС, pressure 3 to 10 MPa, and volume flow rate 1 -3 h-1 at H2/feedstock ratio 250 to 1000. Process is especially appropriate for diesel fuel production.
EFFECT: enabled preparation of high-activity and high-selectivity catalyst at any catalyst production plant without additional equipment.
2 cl, 3 tbl, 7 ex
FIELD: petrochemical processes.
SUBSTANCE: 1,3-butadiene is obtained via catalytic dehydrogenation of n-butylenes at 580-640°C and essentially atmospheric pressure while diluting butylenes with water steam at molar ratio 1:(10-12) and supplying butylenes at space velocity 500-750 h-1. Catalyst is composed of, wt %: K2O 10-20, rare-earth elements (on conversion to CeO2) 2-6, CaO and/or MgO 5-10. MoO3 0.5-5, Co2O3 0.01-0.1, V2O5 0.01-0.1, and F2O3 the balance. Once steady condition is attained, dehydrogenation is carried out continuously during all service period of catalyst.
EFFECT: increased yield of 1,3-butadiene and process efficiency.
FIELD: industrial inorganic synthesis and catalysts.
SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.
EFFECT: increased ammonia synthesis productivity.
8 cl, 2 tbl, 19 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic system is prepared by consecutively charging into reactor alumino-cobalt and alumino-nickel-molybdenum catalysts containing 12.0-25.0% molybdenum oxide, 3,0-6.0% nickel oxide, and 3.0-6.9% cobalt oxide provided that alumino-cobalt and alumino-nickel-molybdenum catalysts are charged at ratio between 1.0:0.1 and 0.1:1.0, preparation of catalysts employs mixture of aluminum hydroxide and/or oxide powders, to which acids are added to pH 1-5. More specifically, aluminum hydroxide powder mixture utilized is a product of thermochemical activation of gibbsite and pseudoboehmite AlOOH and content of pseudoboehmite in mixture is at least 70%, and aluminum oxide powder mixture utilized comprises powders of γ-Al2O3 with particle size up to 50 μm and up to 50-200 μm taken at ratio from 5:1 to 2:5, or γ-Al2O3 powders with particle size up to 50 μm, 50-200 μm, and up to 200-400 μm taken at ratio between 1:8:1 and 3:6:1.
EFFECT: method of preparing catalytic systems for large-scale high-sulfur hydrocarbon feedstock hydrofining processes is provided allowing production of products with desired levels of residual sulfur and polycyclic aromatic hydrocarbons.
4 tbl, 3 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: catalyst composition intended for hydrogen processing contains component of non-precious metal of group VIII, two components of group VIB metals, and 1 to 30% of combustible binder including at least 50 wt % carbon.
EFFECT: achieved preparation of high-strength catalyst easily controllable during a process.
FIELD: production of catalytic compositions.
SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.
EFFECT: enhanced efficiency.
29 cl, 8 ex
FIELD: petroleum processing.
SUBSTANCE: invention provides oil stock hydrotreatment catalyst containing alumina-supported hydrogenation components: cobalt, molybdenum, and tungsten in the form of oxides at weight ratio Co/Mo/W = 20:45:35 (15-25% in total), aluminum fluoride (10-30%), and promoter (2.5-16.5%): silicon oxide and/or rare-earth element oxides, in particular lanthanum oxide or lanthanum/cerium oxide mixture. Promoter may further contain up to 3% zirconium oxide. Alumina functions as binding material. Invention also covers oil stock hydrotreatment process, which is conducted in presence of claimed catalyst at 340-430°C, pressure 3-10 MPa, oil stock flow rate 0.5 to 3 h-1, and hydrogen-to-oil stock ratio 250 to 1000 nm3/m3. Catalyst is characterized by elevated hydrocracking and hydro-desulfurization activity and selectivity in oil stock hydrotreatment processes resulting in production of diesel distillates meeting European requirements (EN-590). Catalyst can be prepared on any existing catalyst preparation equipment.
EFFECT: simplified catalyst preparation technology and avoided formation of effluents.
5 cl, 3 tbl, 6 ex
SUBSTANCE: invention describes method of obtaining aggregated catalyst for hydrogen treatment of oil fractions. The catalyst is a composition of components in the form of compounds of one VIII group metal and two VIB group metals. Method involves mixing and chemical interaction of components, producing active complex by mechanic and chemical activation of components, which remain in solid state during the whole process performed in aggregates of mechanic and/or hydrodynamic effect, preferably in planetary centrifugal mill, at room temperature for 5-30 minutes, with free pass distance of milling bodies equal to 4.0-5.0 cm, relative collision speed of milling bodies equal to 17-34 m/s, reaction layer thickness for component mix on the surface of milling bodies equal to (0.4-2.6)·10-2 cm, with further drying, tempering and sulfidation. Active complex is dried for 10-15 minutes.
EFFECT: high-grade purification of oil products from sulfur.
1 cl, 1 tbl, 2 dwg, 5 ex
SUBSTANCE: invention relates to catalyst production, particularly to production of catalysts for dehydrogenating olefin hydrocarbons. Described is a catalyst based on iron oxide, containing potassium compounds, chrome oxide, molybdenum oxide, ceric oxide and portland cement with the following ratios of components, wt %: potassium compounds (in terms of potassium oxide) 10.0-25.0; chrome oxide 0.5-7.0; molybdenum oxide 0.7-7.0; ceric oxide 1.0-15.0; portland cement 0.5-13.0; the rest is iron oxide.
EFFECT: increased selectivity of catalyst.
3 cl, 1 tbl, 2 dwg, 16 ex
SUBSTANCE: present invention relates to a method and catalyst composition, used in hydroconversion of heavy hydrocarbon starting material. A catalyst composition is described, which is suitable for use in hydroconversion of heavy hydrocarbon starting material. The said catalyst composition contains: a component based on a group VIB metal; a component based on a group VIII metal; a component based on phosphorus; and carrier material, which contains aluminium oxide, where the said carrier material is characterised by average pore diametre ranging from 100 Å to 140 Å, pore size distribution width less than 33 Å, and pore volume at least equal to 0.7 cm3/g, where less than 5% of the said pore volume in the said carrier material is made up of pores in the said carrier material, exceeding 210 Å, and the carrier material contains less than 3 wt % silicon dioxide. A method of hydroconversion of heavy hydrocarbon starting material is also described, where the said method involves the following stage: bringing the said heavy hydrocarbon starting material into contact with the above mentioned catalyst in suitable conditions, where the said catalyst is effective in hydroconversion of at least part of the said heavy hydrocarbon starting material, obtaining lighter hydrocarbons. A composition is also described, which is suitable for use as a component of the carrier material based on aluminium oxide or a catalyst composition, meant for use during hydroconversion of heavy hydrocarbon starting material, where the said composition contains: aluminium oxide, which enables obtaining the said carrier material based on aluminium oxide which has pores which are characterised by average diametre in the range from 100 Å to 140 Å, pore size distribution width less than approximately 33 Å, pore volume at least equal to 0.75 cm3/g where less than 5% of the said pore volume is made up of the said pores with diametre exceeding 210 Å, and where the carrier material contains less than 3 wt % silicon dioxide.
EFFECT: catalyst compositions with improved catalyst activity and stability with respect to hydroconversion of heavy hydrocarbon starting material.
8 cl, 5 tbl, 3 dwg, 6 ex
FIELD: petroleum chemistry, chemical technology.
SUBSTANCE: crude alpha-olefin is heated, raw vinylidene olefins are isomerized in the presence of catalyst and alpha-olefin is separated from isomerized vinylidene olefin by rectification. Separation of alpha-olefin is carried out for at least two successive steps at similar temperatures on top of vat and reducing pressure of rectifying column at each following step. Condensed phase removing from top of the rectifying column at previous step is fed to feeding zone of the following step and the rectifying column at top and vat section is sprayed. For spraying the top section of column the condensed phase removing from the top of rectifying column at the same step is used and for spraying the vat section of column the vat liquid of rectifying column at the same step is used. Separated alpha-olefin is purified additionally from oxygen-containing impurities by adsorption up to polymerization degree of purity. Raw heating, isomerization, separation and adsorption are carried out in atmosphere in inert gas. The unit used for treatment of alpha-olefin includes reactor for isomerization of vinylidene olefins in raw, rectifying column wherein feeding zone is joined with reactor outlet and wherein alpha-olefin of high purity degree is removed from the column top. The unit includes also at least one rectifying column for additional treatment of alpha-olefin of high purity from isomerized vinylidene olefins and adsorption column for separation of oxygen-containing impurities in alpha-olefin of high purity wherein the column inlet is joined with the top outlet of the last rectifying column used for additional treatment of alpha-olefin of high purity and outlet is used for removing alpha-olefin of the polymerization purity degree. Invention provides enhancing quality of the end product.
EFFECT: improved method for treatment.
8 cl, 1 dwg, 1 ex
FIELD: petrochemical processes.
SUBSTANCE: invention relates to treatment of C5-hydrocarbons in order to remove cyclopentadiene impurities, which process may be, in particular, used in rubber production industry when producing hydrocarbon monomers applicable in stereospecific polymerization processes. Treatment of hydrocarbons is accomplished with cyclohexane in presence of organic solvent and alkali catalyst, after which C5-hydrocarbons are separated from reaction products via rectification. Organic solvent is selected from alkylene glycol monoalkyl ethers including their mixtures taken in amounts 0.5 to 5.0 wt % based on C5-hydrocarbons.
EFFECT: increased degree of cyclopentadiene extraction at lower reagent consumption.
8 cl, 1 tbl, 23 ex
FIELD: organic chemistry.
SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.
EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.
8 cl, 2 tbl, 1 dwg, 1 ex
SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.
EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.
46 cl, 1 dwg