A method of obtaining a nickel hydrogenation catalyst
(57) Abstract:The invention relates to methods for Nickel catalysts for the hydrogenation of oxides of carbon, oxygen and aromatic hydrocarbons. The inventive method comprises the mixing of the basic Nickel carbonate with alumina carrier in the presence of an aqueous solution of ammonia, followed by drying, calcination, grinding, mixing with graphite and pelletizing. As alumina carrier, a mixture of high and low temperature forms of alumina in a ratio of from 0.05:0.95 to 0.50 to: 0,50 (in terms of Al2O3and as a low-temperature forms of alumina take boehmite, pseudoboehmite, hydro-argillite, -Al2O3or-Al2O3and as a high temperature form - a-Al2O3or-Al2O3. The invention provides for obtaining a Nickel hydrogenation catalyst with high activity. table 1. The invention relates to the production of Nickel hydrogenation catalysts, in particular to methods of producing catalysts for the hydrogenation of oxides of carbon, oxygen and aromatic hydrocarbons. A method of obtaining Nickel catalystframework anhydride, followed by drying at 100oC for 10 h, annealed in air at 450oC for 10 h, the mixture with graphite and pelletizing 
The main disadvantage of this method is the use of chromic anhydride, which, as you know, belongs to a class of highly toxic substances that cause the need for additional measures for compliance with health and safety which, in turn, leads to a rise in the cost of the catalyst.Closest to the invention to the technical essence is a method of obtaining a Nickel catalyst that does not contain chromium, consisting in mixing the alumina powder with ammonium complex of the basic Nickel carbonate, followed by calcining in air at 350-500oC, chopping, mixing with graphite and pelletizing. However, the Nickel catalyst obtained in this way has not a high activity 
The present invention provides an increase in the activity of the Nickel hydrogenation catalysts. This technical effect is achieved by using a mixture of high and low temperature forms of alumina.The invention consists in obtaining a Nickel catalyst ecoterritory forms of aluminum oxide) in the presence of patinator aqueous solution of ammonia, followed by drying at 100-120oC and calcining at 350-500oC, chopping, mixing with graphite and pelletizing.Our research ecumenically catalysts (ANC) by the methods of x-ray phase analysis (XRD), derivatographic and temperature-programmed reduction (TPR) indicates the presence of two forms of Nickel, recovering at 300-400oC (I) and 500-650oC (II). Catalytic tests microprotol installed in the reaction of hydrogenation of benzene to cyclohexane showed that the dependence of activity on the ratio of these forms is an extreme character: most activity have samples with a ratio of forms I and II is about 1:1.Found that the original form (state) of Al2O3affects the total amount of recovered Nickel and the ratio of forms I and II. It is established that the high-temperature form ( and q-Al2O3) contribute to the formation of form I and low temperature (boehmite, pseudoboehmite, hydro-argillite, g -, r-Al2O3) II. Thus, by varying the ratio of high and low temperature forms of alumina can be controlled phase composition of the ANC and thus to optimize kataliticheskaya on the circulation-flow-through unit (CPU) at a temperature of 200oC and a pressure of 0.1 MPa according to standard methods described in the technical specifications "Catalysts mahanirvana (TU 113-03-2003-92, p. 4.12), as well as in the reaction of hydrogenation of benzene to cyclohexane at microprotol installation flow (PU) type at a pressure of 1.0 MPa, the rate of hydrogen supply 15 l/h and flow rate of feed of raw material 3 h-1. Before conducting the experiments, the samples were activated in a stream of hydrogen at 200oC for 6 hours as a criterion of activity took is the conversion of benzene at a temperature of 140oC.Example 1. To 65 kg of a powder mixture of a-Al2O3and g-Al2O3(at a ratio of 0.50:0.50 and in terms of Al2O3) add a 58.3 kg of basic Nickel carbonate (NiO content 60%) and stirred for 0.5 h until a homogeneous mixture, then poured 100 ml of 25% aqueous ammonia and stirred for 1 h to obtain a homogeneous mass. Then the mass with stirring is heated to 100-120oC and stirred for 4-6 h to obtain a dry powder. The resulting powder was calcined in a stream of air at a temperature of 350oC 4 h Calcined product additionally crush, add water in an amount of 10 l and 4 kg of graphite and stirred for 0.5 h to obtain homogeneous the iO 35 wt. Al2O3the rest of it.Activity: CPU 2.5 cm3CO/g
Example 2. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and r-Al2O3(at a ratio of 0.50:0.50 and in terms of Al2O3).The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.Activity: CPU 2.4 cm3CO/g
Example 3. Similarly to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and boehmite (at a ratio of 0.50:0.50 and in terms of Al2O3).The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.Activity: CPU 2.3 cm3CO/g
Example 4. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and pseudoboehmite (at a ratio of 0.50 to 0.50 in terms of Al2O3).The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.Activity: CPU 2.3 cm3CO/g
Example 5. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of a-Al2O3and hydrargillite (at a ratio of 0.50:0.50 and in terms of Al2cm3CO/g
Example 6. Analogously to example 1, except that instead of a mixture of a-Al2O3and g-Al2O3took a mixture of q-Al2O3and g-Al2O3(at a ratio of 0.50:0.50 and in terms of Al2O3).The composition of the catalyst: NiO 35 wt. Al2O3the rest of it.Activity: CPU 2.6 cm3CO/g
Example 7. Analogously to example 1, except that instead of 65 kg of a mixture of a-Al2O3and g-Al2O3with a ratio of 0.50:0.50 in (in terms of Al2O3) took 50 kg of a mixture of a-Al2O3and g-Al2O3at a ratio of 0.05:0.95 and instead of 58.3 kg basic Nickel carbonate took 83,3 kgThe composition of the catalyst: NiO 50 wt. Al2O3- the rest.Activity: PU 70%
Example 8 (prototype). In the Z-shaped mixer load 2.5 kg shredded aluminium oxide g-Al2O3) and 2.3 kg of basic Nickel carbonate (NiO content 60%) and under stirring to the mixture is added 2.5 l of a 25% aqueous solution of NH4OH. Stirring is effected at ambient temperature for 1 h, followed by stirring at a temperature of 100-120oC for 4-6 h (to remove ammonia). The resulting mass (in the form of a dry powder), annealed at asmerom 5 x 5 mmThe composition of the catalyst: NiO 35% Al2O3the rest of it.Activity: CPU 1.9 cm3CO/ g, PU 35%
Comparative data on activity obtained in examples 1-8 and industrial analogues: a catalyst for hydrogenation of carbon oxides (process mahanirvana) NYC-1 (TU 113-03-2003-92) and Nickel-chromium" catalyst for the hydrogenation of aromatic compounds (OST 113-03-4001-90) are summarized in table.The table shows that the results obtained by the proposed method samples (examples 1-7) are superior in activity industrial analogues synthesized sample prototype (example 8).Thus, the proposed method allows to obtain a Nickel hydrogenation catalysts with increased activity. A method of obtaining a Nickel hydrogenation catalyst comprising a mixture of a basic carbonate of Nickel alumina carrier in the presence of an aqueous solution of ammonia, followed by drying, calcination, grinding, mixing with graphite and pelletizing, characterized in that as the alumina carrier, a mixture of high and low temperature forms of alumina in a ratio of from 0.05 to 0.95 to 0.50 0,50 (in terms of Al2O3and in l2O3and as high-temperature form -- Al2O3or-Al2O3.
FIELD: composition and structure of composite metal semiconductor meso-porous materials; titanium-dioxide-based catalyst for photo-chemical reactions.
SUBSTANCE: proposed catalyst is meso-porous titanium-dioxide-based material containing crystalline phase of anatase in the amount no less than 30 mass-% and nickel in the amount no less than 2 mass-%; material has porous structure at average diameter of pores from 2 to 16 nm and specific surface no less than 70 m2/g; as catalyst of photo-chemical reaction of liberation of hydrogen from aqua-alcohol mixtures, it ensures quantum reaction yield from 0.09 to 0.13. Method of production of such catalyst includes introduction of precursor - titanium tetraalkoxyde and template of organic nature, holding reagent mixture till final molding of three-dimensional structure from it at successive stages of forming sol, then gel, separation of reaction product and treatment of this product till removal of template; process is carried out in aqua-alcohol solvent containing no more than 7 mass-% of water; at least one of ligands is introduced into solvent as template; ligand is selected from group of macro-cyclic compounds containing no less than four atoms of oxygen and/or from complexes of said macro-cyclic compounds with ions of metals selected from alkaline or alkaline-earth metals or F-metals containing lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium; mixture is stirred before forming of sol maintaining its temperature not above 35°C till final molding of three-dimensional structure from reagent mixture; mixture is held in open reservoir at the same temperature at free access of water vapor; after removal of template from three-dimensional structure, mixture is first treated with nickel salt solution during period of time sufficient for withdrawal of nickel ions from solution by pores of structure, after which is it kept in hydrogen-containing medium during period of time sufficient for reduction of nickel ions in pores of structure to metallic nickel.
EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.
7 cl, 68 ex
FIELD: chemical technology, catalysts.
SUBSTANCE: invention relates to a nickel-containing catalyst and to a method for the oligomerization reaction of ethylene to a mixture of olefin products with high degree of linearity. Invention describes a composition of catalyst comprising product prepared by interaction of the following components in a polar organic solvent in the presence of ethylene: (a) bivalent nickel simple salt with solubility at least 0.001 mole per liter in indicated polar organic solvent; (b) boron hydride-base reducing agent; (c) water-soluble base; (d) ligand chosen from o-dihydrocarbylphosphinobenzoic acids and their alkaline metal salts; (e) trivalent phosphite wherein the molar ratio of ligand to phosphite is in limits from about 50:1 to about 1000:1. Also, invention describes a method for preparing the catalyst composition and a method for synthesis of a mixture of olefin products showing the high degree of linearity. Invention provides preparing the economically effective catalyst useful in synthesis of olefin substances showing the high degree of linearity.
EFFECT: improved and valuable properties of catalyst.
10 cl, 2 tbl, 3 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to determining polymerizing activity of catalysts that can be used for hydrogenation of unsaturated compounds contained in liquid pyrolysis products. As a variable reflecting polymerizing activity of hydrogenation catalysts, optical density value of liquid mixture is used, said mixture containing unsaturated compounds and being kept in contact with catalyst at elevated temperature for a predetermined period of time. Determination of polymerizing activity is accomplished by comparing optical density of liquid mixture containing unsaturated compounds before and after its contact with catalyst. In order to measure optical density of liquid mixture, standard laboratory equipment (photocolorimeter and spectrophotometer) may be utilized.
EFFECT: enabled comparison of polymerizing activity of catalysts directly with respect to industrial feedstock.
3 cl, 2 dwg, 3 tbl, 38 ex
FIELD: gas treatment.
SUBSTANCE: invention relates to improved method for removing acetylene compounds from hydrocarbon streams, which method comprises bringing hydrocarbon stream containing a first concentration of acetylene compounds and olefins with catalyst being consisted either of supported non-sulfided metallic nickel or the same modified with metals such as Mo, Re, Bi, or mixture thereof, said non-sulfided nickel being present on support in quantity by at least 5% superior to quantity required for selective hydrogenation of acetylenics. Hydrogenation is carried out in first reaction zone at temperature and pressure as well as hydrogen concentration favoring hydrogenation of acetylenics, after which hydrocarbon material is discharged containing second concentration of acetylenics inferior to its first concentration.
EFFECT: improved acetylenics removal selectivity and increased yield of target olefin compounds.
20 cl, 10 dwg, 1 tbl, 6 ex