Catalyst for conversion of methane into higher hydrocarbons.
(57) Abstract:Usage: petrochemistry. The inventive catalyst corresponds to the empirical f-Le: A1B1-2C1-3Ox, where A is titanium, zirconium or silicon; B-lanthanum or yttrium; C-sodium, lithium, potassium, cesium, magnesium, calcium, strontium or barium; X is the number of oxygen atoms determined by the valence state of items in the Inbox. Characterization of the catalyst: the selectivity for C2H4up to 33%, C2H6up to 42%. 5 table. The invention relates to a heterogeneous catalytic system capable of converting methane into higher hydrocarbons, mainly in C2the hydrocarbons.The largest source of methane is natural gas, the provision of energy is of paramount importance, whose role seems to be to increase in the future, it is also becoming a source of chemicals.In fact, currently, approximately 90% of natural gas used as fuel, with the remaining 10% are used for the indirect production of methanol, ammonia and its derivatives, chlorinated compounds and other minor compounds. The composition of natural gas varies depending on IP in order to stigate to 99% by volume, moreover, the residual quantity is light hydrocarbons, inert gases and chemical compounds with acidic character (CO2N2S).Therefore, the full use of this source of carbon atoms is of great importance.Weak reactivity to functionali shown light hydrocarbons, especially methane, always defines the limit for its use, for this reason, methane is mainly used as fuel. In the list of issues you can include the transportation of methane, because methane sources are usually located in regions that are removed from regions of the use of methane. Transportation techniques, known from the description above, associated with certain financial expenses. They may arise from the transportation by pipeline and gas liquefaction/re-transfer in the gaseous state.Hence the conversion of methane in an easily manipulated compound is of the utmost importance.The conversion of methane can be performed according to several methods, including the use of coreagent and/or catalysts, or without them.Simple Chino short contact times due to thermodynamic limitations. Patent literature reports some examples of catalytic systems with the ability to direct response. These methods do not have high selectivity and are rarely used in practice.Using coreagent can be carried out in the presence of a catalyst or without it.Regarding the first version of the response, was asked the following: oxygen obtaining methanol and formaldehyde [Chem. Ruv. 85(4), 235 (1985)], or chlorine (Benson method, U.S. patent 4 199 533), with higher hydrocarbons. The last publication of the Japan patent J 88/222126 discloses the synthesis of hydrocarbons, mainly WITH2hydrocarbons, the direct reaction of methane and oxygen under pressure.The conversion of methane is mostly carried out through catalytic methods, and coreagent take part in the reaction.The first attempts to relate to the forties: in industrial scale oxygen-containing products were obtained when using as oxidant (Fial Report N 1085, 31.03.1947).The reaction of production of methanol and formaldehyde mainly catalyzed by variously modified compounds based on molybdenum (see UK patent 1 398 385, 1971) Mega acid solution.The formation of hydrocarbon mixtures with a predominant content2compounds called "oxidative combination" and is usually conducted in the presence of oxygen or air, and the catalysts are predominantly oxidic character.The catalyst reagents can do or alternately or in parallel. In the first case, the active oxides are the oxides of low-melting metals such as cadmium, indium, tin, antimony, thallium, pigs, bismuth, magnesium, or as such or modified [J. Catal. 73 - 9-19 (1982) Union Carbide; U.S. patent No. 4 443 644 to 7, 4,444,984, 4,495,374, 4, 499:322 and 4,560,821 Atlantic Richfield Co].In the second case are mainly used oxides of alkaline-earth metals, modified alkali metals [U.S. patent 4 057 620 and 4 654 460 Phillips Petroleum; U.S. patent 4 801 7632 Atlantic Richfield Co.].Specific catalysts are catalysts made as a solid super-acid (G. A. Olan U.S. patent 4 513 164), in which in the presence of oxidants always come out WITH2the hydrocarbons.From the existing technical literature, there are other systems that have the ability to turn the methane into higher hydrocarbons: referred to the metals belonging to the first transition group is the NID, and rare-earth elements.There are a variety of patented materials with different compositions:
France 2 607 804 Inst. Fr. Petrole (Lir/KBr); U.S. 4751336 Amoco Corp (1% by weight CVG/calstat D), Japan 88/77826.The above-mentioned catalysts mostly do not allow obtaining high conversion of methane, which does not allow to obtain high productivity and selectivity.Many of these catalysts is subject to rapid aging, respectively, rapidly lose their activity and selectivity.Currently found a specific catalyst composition, which has high activity and selectivity in the oxidation combination of methane. Such a catalyst composition can reduce the disadvantages arising from the use of catalysts known from the prototype.The catalytic system in accordance with the invention differs in that it is subject to the following empiricheskoi formula:
Aa Bb Cc Ox, where A is an element selected from the group consisting of germanium, silicon, tin, titanium, zirconium;
B is an element selected from the group consisting of lanthanum, scandium,yttrium;
With alkaline or alkaline-earth metal;
a but of 0.05-2.5;
with the number included in the range of 0.1 to 10 and preferably of 0.05-2.5;
x is a number which determines the valence state in which some elements are present in the catalytic system.The preferred elements for A component are titanium and zirconium, for the B component is yttrium and lanthanum, for a component With alkali metals, particularly sodium.The catalytic system in accordance with the invention can be obtained in accordance with one of the methods known from the literature for similar compounds.Such methods can be: drying of sediment drying and mixing; drying raspadenie; gelatinization; deposition; coprecipitation, impregnation.Methods preferably are selected depending on different raw materials.Sometimes also conducting drying may be necessary or can achieve advantages.The resulting material, called catalytic precursor, fired at high temperature (but not above than 1000about(C) in several ways.thermal cycle used to produce the catalysts defined in the examples is as follows:
150 65,0 2,0
150 - 2,0
150->300 75,0 2,0
300 - 4,0
300->800 140,0 3,6
800 - 4,0
800->room tempera - 40,0 19,5
P R I m e R 1. According to the following methodology has been the catalyst titanium, lanthanum: sodium = 1: 1:1. When heated in ethanol was dissolved 28,90 g LaNO36H2O and of 5.40 g NaNO3. Then added 15,73 g (equivalent to approximately 15,04 ml) of Ti (OEt)4mixed with 30 ml of ethanol. Pseudorelativistic solution caused by adding a small amount of N2O. Entire mixture was dried in an oven at 80aboutC for 22 h and the catalyst precursor has consistently probalily in accordance with the above scheme.P R I m m e R 2. The catalyst is titanium, lanthanum:sodium = 1:2:1 was obtained by concentration by evaporation of an aqueous solution (250 ml) 2.86 g of TiO2, 25,81 g LaNO36H2O and 2,84 g NaNO3evaporation occurred before receiving thickened liquids. Thickened liquid is dried in an oven at about 100aboutC for 24 h, and the obtained solid substance was hot in accordance with the scheme presented above.P R I m e R s 3-4. Acting the same way as in example 1 and had the following catalyst: titanium, lanthanum: Li = 1:1:1 catalyst (example 2) of 28,92 g LaNO36H2O and 4,60 g LiNO3150 Ali = 1:1:1 catalyst (example 4) of 28,95 g LaNO36H2O and 6.75 g KNO3in 150 ml ethanol + 30 ml of N2Oh, to which was added 15,57 g (equivalent 13,91 ml) of Ti(OEt)4mixed with 30 ml of ethanol.P R I m e R s 5-6. Acting the same way as in example 2, using the reagents described in table.1, received the catalysts of titanium, lanthanum magnesium = 1:1:1 (example 5) and titanium, lanthanum, calcium = 1:1:1.P R I m e R 7. In a similar manner as in example 1, a catalyst, titanium, yttrium:sodium = 1:1:1 received from 23,57 g Y(NO3)36H2O and 4,90 g NaNO3, which was dissolved in 160 ml of ethanol, to which was added 13,44 g (12,01 ml of Ti(OEt)4mixed with 20 ml of ethanol.After adding an ethanol solution of Ti (OEt)4almost immediately there was pseudorelativistic, so did not add a small amount of water, as in example 1. P R I m e R s 8-9. In accordance with example 2, using the materials and amounts shown in the table.2, received Zirconia catalysts: lanthanum:sodium = 1:1:1 (example 8) and zirconium:yttrium:sodium = =1:1:1.P R I m e R 10. In 16 ml of ethanol + 7.5 ml of water was dissolved 28,89 g LaNO36H2O and of 5.68 g NaNO3.With a slight heating of the mixture of these solids dissolved. Added 14,85 g of Si(OEt)4and when neznacitC for 20 h, and the reaction mixture was hot in accordance with the cycle.P R I m e R s 11-51. The materials obtained, as shown in examples 1-10, was subjected to tests to determine their catalytic activity in accordance with the following method. Granules with a size of 20-40 mesh. loaded in a quartz reactor (catalytic volume = 2 ml) and kept under a stream of nitrogen while the temperature was increased to 300aboutC. Then filed a methane/air mixture. Commonly used flow rate had the following values: methane 22 NML/min and air at the required flow rate to obtain the desired CH4/ABOUT2the attitude. The data below.The results obtained are presented in table.4.Additional examples A, B and stoichiometric calculations:
The General formula for the calculation can be written as follows:
A1B1-2C1-3, where A is Ti, Zr or Si;
B - La, or Y;
With - Na, Li, K, Mg or CA.The atom A.For each mol And 2 mol of oxygen. The General formula AO2.Atom CenturyFor each mol to 1.5 mol of oxygen. The General formula IN1,5.Atom With.If - alkali metal (Li, Na,nd metal, then for each mol s - 1 mol of oxygen, then the General formula WITH.Examples of stoichiometric calculations
Ti(La/Na = 1/1/1
1 mol Ti - 2 mol OF
1 La mole to 1.5 mole ON
1 mol Na - 0.5 mol OF
Ti LaNaO4< / BR>Zr/La/Ba = 1/1/2,5
1 mol Zr - 2 mol OF
1 La mole to 1.5 mole ON
2.5 mol BA - 2.5 x 2 = 5 mol OF
ZrLaBathe 2.5O8,5< / BR>P R I m e R A. the Catalyst Zr; Y; Sr 1/1/3 obtained as follows.Ammonium carbonate (15.6 g) was dissolved in 150 ml of water and there admixed ZrO2.Then add 5,6 n of yttrium nitrate and 12.7 g of strontium nitrate, dissolved in 250 ml of water.The liquid is filtered off, washed for some time, dried and calcined as described above.P R I m e R C. the Catalyst Zr; La; Ba 1/1/2,5 was obtained as follows.Ammonium carbonate (45 g) was dissolved in 300 ml of water and there admixed ZrO2,
Then add a 32.5 g of uranyl nitrate lanthanum and 39.2 g of barium nitrate dissolved in 500 ml of water.The liquid is filtered off, washed for some time, dried and calcined as described in the application.P R I m e R S. In accordance with the process of example In the catalyst Zr:La: Cs 1/1/1 obtained using 1.9 grams ZrOThe results are shown in table.5. CATALYST FOR CONVERSION of METHANE INTO HIGHER HYDROCARBONS containing an element selected from the group of titanium, zirconium or silicon, an element selected from the group of lanthanum or yttrium and an element selected from the group of sodium, lithium, potassium, cerium, magnesium, calcium, strontium or barium, in combination with oxygen, wherein the catalyst composition corresponds to the following empirical formula:
where a is titanium, zirconium or silicon;
In - lanthanum or yttrium;
With sodium, lithium, potassium, cesium, magnesium, calcium, strontium or barium;
x is the number of oxygen atoms determined by the valence state of items in the Inbox.
FIELD: heterogeneous catalysts.
SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.
EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.
55 cl, 4 dwg
FIELD: physical or chemical processes and apparatus.
SUBSTANCE: method comprises saturating the initial gas mixture that is comprises agents to be oxidized with vapors of hydrogen peroxide. The photocatalyst is made of pure titanium dioxide that contains one or several transition metals.
EFFECT: expanded functional capabilities and enhanced efficiency.
7 cl, 2 dwg, 1 tbl, 11 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.
EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.
13 cl, 1 tbl, 24 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.
EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.
17 cl, 3 tbl, 25 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention provides catalyst composed of heteropolyacid: phosphorotungstic acid and/or phosphoromolybdenic acid, at least one precious metal deposited on essentially inert inorganic amorphous or crystalline carrier selected from group including titanium dioxide, zirconium dioxide, aluminum oxide, and silicon carbide, which catalyst retains characteristic structure of heteropolyacid confirmed by oscillation frequencies of the order 985 and 1008 cm-1 recorded with the aid of laser combination scattering spectroscopy and which has specific surface area larger than 15 m2/g, from which surface area in pores 15 Å in diameter is excluded. Method of converting hydrocarbon feedstock containing C4-C24-paraffins in presence of above-defined catalyst is likewise described.
EFFECT: increased catalyst selectivity and enhanced hydrocarbon feedstock conversion.
5 cl, 7 tbl, 7 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.
EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.
9 cl, 1 dwg, 3 tbl, 7 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: process is effected in reactor containing compacted bed of supported catalyst including group VIII metal, in particular cobalt, said metal being partially present in its metallic form. Supported catalyst has, on its outside surface, catalytically active metal. Compacted bed is characterized by having hollow volume more than 50 vol % and specific surface area more than 10 cm2/cm3, which is calculated as total outside surface of particles divided by bed volume.
EFFECT: improved economical efficiency of process.
8 cl, 3 tbl, 7 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.
EFFECT: increased catalyst activity.
5 cl, 2 tbl, 6 ex
FIELD: catalyst preparation methods.
SUBSTANCE: catalyst containing crystalline anatase phase in amount at least 30% and nickel in amount 0.5 to 2% has porous structure with mean pore diameter 2 to 16 nm and specific surface at least 70 m2/g. When used to catalyze photochemical reaction of isolation of hydrogen from water-alcohol mixtures, it provides quantum yield of reaction 0.09-0.13. Preparation of titanium dioxide-based mesoporous material comprises adding titanium tetraalkoxide precursor and organic-nature template to aqueous-organic solvent, ageing reaction mixture to complete formation of spatial structure therefrom through consecutive sol and gel formation stages, separating reaction product, and processing it to remove template. Invention is characterized by that water-alcohol derivative contains no more than 7% water and template consists of at least one ligand selected from group of macrocyclic compounds, in particular oxa- and oxaazamacrocyclic compounds containing at least four oxygen atoms, and/or complexes of indicated macrocyclic compounds with metal ions selected from group of alkali metals or alkali-earth metal metals, or f-metals consisting, in particular, of lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, and cerium used in amounts from 0.001 to 0.2 mole per 1 mole precursor. Sol is formed by stirring reaction mixture at temperature not higher than 35°C. Once formation of spaced structure completed, mixture is held at the same temperature in open vessel to allow free access of water steam and, when template is removed from the mixture, mixture is first treated with nickel salt solution and then with alkali metal borohydride solution until metallic nickel is formed.
EFFECT: increased sorption and photocatalytic properties of catalyst and enabled reproducibility of its property complex.
7 cl, 68 ex
FIELD: catalyst preparation methods.
SUBSTANCE: invention proposes combination of protective layer against chlorine compounds and copper-containing catalyst bed. Protective layer is formed from molded members prepared from particles of led carbonate and/or basic led carbonate with weight-average particle size less than 10 μm. Catalytic reaction in presence of above-defined combination is also described.
EFFECT: prevented deactivation of copper-containing catalyst operated with process gas containing chlorine compounds.
11 cl, 3 tbl, 7 ex
FIELD: oxidation catalysts.
SUBSTANCE: SO2-into-SO3 conversion catalyst contains following active components: vanadium oxide, alkali metal (K, Na, Rb, Contains) oxides, sulfur oxides, and silica framework formed from natural and/or synthetic silica and having pores with radii up to 65000 , among which fraction of pores with radii larger 10000 does not exceed 50%, while content of sulfuric acid-insoluble vanadium compounds (on conversion to V2O5) does not exceed 4.0% by weight. Fraction of pores with radii 1000-10000 does not exceed 35% and that less than 75 at most 9%.
EFFECT: improved performance characteristics of catalyst operated in reactor zones at medium and maximum temperature due to under conditions activity at 420-530оС.
3 cl, 1 tbl, 8 ex
FIELD: chlororganic chemistry.
SUBSTANCE: invention relates to hydrochlorination catalyst containing aluminum η-oxide, doped with cesium chloride. Also method for methanol hydrochlorination in vapor phase using claimed catalyst is disclosed.
EFFECT: decreased selectivity to dimethyl ether and inhibited coke deposition on working catalyst.
16 cl, 6 tbl, 1 dwg, 20 ex
FIELD: chemical and petrochemical industries; isomerization of olefins.
SUBSTANCE: the invention is dealt with of the field of deposition on carbon materials of catalysts of the basic nature being of interest for processes of isomerization of olefins. There is a description of a catalyst of isomerization of olefins containing metal sodium deposited on a composite porous carbon material, which represents a three-dimensional porous carbon die with the following structural characteristics: d002 =0.343-0.350 nm, the average size of the crystallite in a direction of "a"-La=l-14 nm, the average size of the crystallite in a direction of "c"-Lc=2-12 nm, real density of 1.8-2.1 g/cm3, with distribution of pores by sizes having a maximum in the range of 20-200 nm and an additional maximum in the range of 1-20 nm. Also there is a description of a method of preparation of the catalyst providing for deposition of metal sodium on the composite porous carbon material and a method of isomerization of olefins with use of this catalyst. The technical result is a possibility to conduct the process of isomerization at low temperatures, increased catalytic activity and selectivity, decreased output of by-products.
EFFECT: the invention ensures a possibility to conduct the process of isomerization at low temperatures, increased catalytic activity and selectivity, decreased output of by-products.
6 cl, 10 ex, 2 tbl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.
EFFECT: increased activity and selectivity of catalyst.
3 cl, 2 dwg, 4 tbl, 7 ex