Method for producing organic amines
(57) Abstract:The inventive organic amines obtained by condensation of hydroxiapatite with ammonia or an amine in the presence of a hydrogenating catalyst is a mixture of oxides of Nickel and titanium, promotianal palladium and copper oxide. The catalyst formed in the form of Raschig rings with a diameter of 5 to 10 mm and a wall thickness of 1,5 - 2 mm, 1 table. The invention relates to methods of producing amines by condensation of hydroxyl-containing organic compounds with ammonia or amines in the presence of a hydrogenating catalyst with getting as cyclic and aliphatic amines used as catalysts obtaining polyurethane foam (PUF) as reagents in flotation of ores, the manufacture of bandages for orthopedic and other purposes.Cyclic amines, such as formalin (IOE), piperazine (PIP) and their derivatives, are used as chemicals for rubber, corrosion inhibitors, emulsifiers, antigelmintnyj drugs to combat ascariasis, etc.A method of obtaining a wide range of amines as aliphatic and cyclic on the catalysts, representing the phosphates of rare earth elements (cerium, neodymium, lanthanum). The process wasp is by the necessity of using high temperatures, which leads to excessive energy consumption, and the use of rare earth elements.The objective of the invention is to devise a method of obtaining amines with high selectivity.To solve this problem it is suggested to conduct the process of obtaining amines on the catalyst composition is Nickel oxide, titanium dioxide, promoted copper oxide and palladium, are molded in the form of Raschig rings with a diameter of 5-10 mm and wall thickness of the rings of 1.5-2 mmThe study of the process of obtaining amines at the example of a PESTILENCE, Amor, DMDA showed that the number of products decreases as crushing the tablets of the catalyst. Apparently this is due to the reaction at a major catalyst grain in interdiffuse region and the deletion of the diffusion inhibition by crushing of the catalyst.Thus, optimum results are achieved with the implementation of the process on the catalyst in the form of Raschig rings with wall thickness of 1,5-2 mm and a diameter of 5-6 mm With increasing wall thickness more than 2 mm comes diffusion braking, and when the thickness is smaller, the catalyst becomes fragile. The diameter of 5-6 mm is optimal for the hydrodynamics of the process.To obtain amino is Kehl and copper, as well as titanium dioxide, followed by evaporation, drying and calcining the resulting mixture, and processing the catalyst mass with a solution of palladium chloride, drying and forming of the catalyst in the form of Raschig rings. The reaction between the hydroxyl-containing compound and the amino group takes place on the catalyst in the gas phase at atmospheric pressure (0.01 to 0.05 MPa) and relatively low temperature (180-250aboutC).Reaction conditions, in particular the ratio of components may vary depending on the volatility of the parent compounds. In the case of high volatility of amino compounds, such as methylamine, these compounds are taken in great abundance, reaching 5-10 moles per 1 mole of hydroxyl compounds. Conversely, when using a high-boiling amine, and gidroksosoedinenii volatile, the excess is taken last. In all cases, the reaction mixture should be in the gaseous state, contact with the catalyst of the reactants in the liquid state is invalid.P R I m e R 1 (comparative). In the contact tube 20 mm in diameter load 100 cm3the catalyst obtained as described in the prototype and having the following composition, % : (NiO 70; NiO225; CuO 0,2; Pd 0,2). The catalyst is heated to 200-210aboutWith the ACI hydrogen 18 l/H. Receive produce the following composition, % : Amor 22; ethanol 29; 31 MOR; MOR 1,5, 2-methoxyethanol 2,5; 3 methylmorpholin 1,5; water the rest. Produce share, as described in example 5.P R I m m e R 2. 530 wt. including basic Nickel carbonate 2.24 wt. including basic copper carbonate are stirred in 1380 wt. including aqueous ammonia and then make 230 wt. including titanium dioxide. The mixture is evaporated, dried and calcined at 380-400aboutC.The calcined powder is suspended in a solution of 1.61 wt. including palladium chloride in 900 wt. including water, acidified with 2 wt. including an aqueous solution of hydrochloric acid. To the suspension, add 7 wt. including an aqueous solution of ammonia and 15 wt. including 40% solution of formaldehyde in water. The mixture is heated with stirring to 95aboutC, kept at this temperature for 0.5 h, evaporated and dried. The dried catalyst mass is loaded into the mixer, add 100 wt. including water, 15 wt. including graphite and mix thoroughly to obtain a homogeneous mass, which granularit in the form of Raschig rings with a diameter of 5 mm and a wall thickness of 1.5 mm, dried at 90-150aboutC. Obtain a catalyst of the following composition, % : NiO 57; TiO238; CuO Is 0.3; Pd 0,18; graphite else.This catalyst conduct process as follows.
aboutC. Daggett served with a speed of 18 g/H. the reaction Products are condensed in a receiver cooled with water and analyzed on the GC. The results of the analysis on the content side 2-methoxyethanol and 3-methylmorpholine presented in the table.P R I m e R 3. The reaction is carried out under the conditions of example 2, but instead of ammonia take methylamine. MOR of catalyzate allocate rectification. Conversion of deg in MOR is 85% , unreacted deg returns in the process of contacting, the output of MOR on reacted deg is 75% .P R I m e R 4. The catalyst obtained according to example 2, but differing composition, % : NiO 71,5; TiO224,6; CuO - 0,2; Pd 0,3) when the diameter of the ring 10 mm and wall thickness 2 mm get MOR of the research and methanol. The reaction is carried out under the conditions of example 2, but in a stream of hydrogen (without ammonia) vapor mixture of the research and methanol were taken in a molar ratio of 1: 2. 18 g/h of a mixture serves 9-18 l/h of hydrogen. Conversion of the research leaves 90-95% , the output of MMAR 87% .P R I m e R 5. The reaction is carried out under the conditions of example 4, but use a catalyst with a diameter of 8 mm and a wall thickness of 1.5 mm instead of methanol take ethanol. The floor is real
The resulting mixture is subjected to separation: distilled alcohol and azeotrope Amor with water. Alcohol and unreacted morpholine return in the process, and the azeotropic mixture Amor with water, dehydrated with benzene and allocate Amor high efficiency distillation column with a yield of 73% morpholine and purity 99.8% .P R I m e R 6. The reaction is carried out under the conditions of example 5, but in a stream of hydrogen is vaporized mixture of deg and research, taken in a molar ratio of 1: 2, the hydrogen is supplied in the amount of 15 moles per one mole deg. Get a mixture of the following composition, % : DMDA 26,0 MDEA 3.4 Amor 3.6 MMOL 1,3 MOR 52,0 deg 9,6
The mixture is subjected to separation. At atmospheric pressure of distilled MOR, Amor, PESTILENCE and water and share obtained zipper in terms of the allocation of Amor described in example 5 and the resulting morpholine return in the process.Of the remaining cubed mixture under vacuum distilled unreacted deg content MMDAA to 10% and return this wrap in the process of contacting.The mixture MDEA and DMDA share on rectification column with obtaining commercial DMDA 97% purity. MDEA can be returned into the process of contacting or used as a catalyst in the production of polyurethane foam. The output of the sum M is the conditions of example 6, but in a stream of hydrogen is vaporized mixture of ethylene glycol and PESTILENCE, taken in a molar ratio of 1: (3-5). Get catalysate, containing 30% of demoralisation (DME), which is marked by distillation. Unreacted ethylene glycol, MOR, 2-hydroxyethyl MOR and 2-amino-ethyl MOR return in the process. The output of the DME on the reacted ethylene glycol 73% .P R I m e R 8. The reaction is carried out under the conditions of example 7, but in a stream of hydrogen is vaporized mixture of ethylene glycol and piperazine (PIP), taken in a molar ratio of 1: (3-5). Given the low volatility of the resulting piperazineethanol, the process is carried out in a large excess of hydrogen from 15 to 39 moles per mole of glycol. Get catalysate, containing 35% of piperazineethanol, which is marked by distillation.Unreacted ethylene glycol and intermediate products 2-hydroxyethylpiperazine and 2-AMINOETHYLPIPERAZINE return on engagement. So Kip. piperazineethanol 164-165aboutWith 15 mm RT. Art. , so pl. 97aboutWith, yield 68% .P R I m e R 9. The reaction is carried out, using as raw material amerosport - ethanolamine, vaporizing it in a stream of hydrogen supplied in an amount of 5 to 15 moles per 1 mole of ethanolamine. When submitting 10 moles of hydrogen per 1 mol of ethanolamine and a load of 0.3 m 11 Piperazine 9 2-Hydroxyethyl - piperazine 21 Triethylenediamine 31 Ethanolamine 7 Water the Rest
Effective rectification of a mixture allocate morpholine, piperazine, triethylenediamine with a total yield of 69% came in the reaction of ethanolamine.2-Hydroxyethylpiperazine return to the contacts, an intermediate fraction by repeated rectification.Thus the proposed method allows to obtain a wide range of amines limited; to provide a high selectivity to the target product; to simplify the extraction technology of the target product from the reaction mixture; get a range of useful products at the same time.The reaction between Dagon and ammonia (56) U.S. Patent N 4582907, CL 547-194, 1984. METHOD for producing ORGANIC AMINES by condensation of hydroxiapatite with ammonia or an amine in the presence of a hydrogenating catalyst, characterized in that as the catalyst, a mixture of oxides of Nickel and titanium, promoted palladium and copper oxide formed in the form of Raschig rings with a diameter of 5 to 10 mm and a wall thickness of 1.5 - 2 mm.
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: selective oxidation of carbon monoxide in hydrogen-containing stream.
SUBSTANCE: invention relates to method for selective oxidation of carbon monoxide to carbon dioxide in raw material containing hydrogen and carbon monoxide in presence of catalyst comprising platinum and iron. Catalyst may be treated with acid. Certain amount of free oxygen is blended with mixture containing hydrogen and carbon monoxide to provide second gaseous mixture having elevated ratio of oxygen/carbon monoxide. Second gaseous mixture is brought into contact with catalyst, containing substrate impregnated with platinum and iron. Carbon monoxide in the second gaseous mixture is almost fully converted to carbon dioxide, i.e. amount of carbon monoxide in product stream introduced into combustion cell is enough small and doesn't impact on catalyst operation characteristics.
EFFECT: production of hydrogen fuel for combustion cell with industrial advantages.
13 cl, 1 tbl, 4 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.
EFFECT: increased heat conductivity and selectivity.
2 cl, 2 tbl, 2 ex
FIELD: petrochemical processes catalysts.
SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.
EFFECT: increased selectivity and productivity.
2 cl, 3 tbl, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention provides a method for preparing improved oxirane hydroformylation catalyst, improved oxirane hydroformylation catalyst, and single-stage process for production of 1,3-diol in presence of such catalyst. Preparation of catalyst comprises preparing complex A by contacting ruthenium(0) compound with di-tertiary phosphine ligand and preparing complex B via redox reaction of complex A with cobalt(0) carbonyl compound. Single-stage 1,3-diol production process involves reaction of oxirane with synthesis gas under hydroformylation conditions in inert solvent in presence of aforesaid catalyst, where recovery of product is preferably accomplished through separation of product-rich phase.
EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.
10 cl, 3 dwg, 6 tbl, 21 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.
EFFECT: increased catalytic activity.
12 cl, 3 dwg, 1 tbl, 2 ex
FIELD: catalysts of selective hydrogenation of alkynes of C4 fractions.
SUBSTANCE: proposed catalyst contains 1-30 mass-% of copper used as first active component, 0.001-5 mass-% of palladium used as second active component, at least 0.001-6 mass-% of one metal selected from Al, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as co-catalyst; the remainder being one carrier selected from aluminum oxide, silicon dioxide and titanium oxide. Method of production of catalyst includes impregnation of carrier calcined preliminarily with solutions of active components depending on their content in catalyst. Alkynes are removed from C4 fractions enriched with alkynes by means of selective hydrogenation with the use of said catalyst.
EFFECT: enhanced selectivity and stability of catalyst.
31 cl, 2 tbl, 13 ex
FIELD: production of catalytic neutralizers.
SUBSTANCE: high-efficiency catalytic neutralizer has internal and external layers on inert carrier which contain noble metals of platinum group deposited on materials of base and oxygen-accumulating components. Inner layer of proposed catalytic neutralizer contains platinum deposited on first base and first oxygen-accumulating component and its external layer contains platinum and rhodium deposited on second base only; this second layer contains additionally second oxygen-accumulating component. Production of catalytic neutralizer includes application of coat on carrier made from composition containing powder-like materials including first material of base and first oxygen-accumulating component followed by drying, calcining, immersing the carrier with coat in solution of platinum precursor; coat is calcined and external layer is applied over previous layer. Specification describes two more versions of production of catalytic neutralizer.
EFFECT: enhanced ability of catalytic neutralizer for reduction of catalytic activity after aging due to discontinuation of delivery of fuel.
24 cl, 1 dwg, 11 tbl, 5 ex, 3 ex
FIELD: gas treatment.
SUBSTANCE: catalyst contains alumina-supported palladium oxide, 0.80-2.54%, copper salt, 3.09-11.79%, promoter represented by phthalocyanine complex with iron or cobalt, 0.10-1.00%, and 0.50-3.00% of polyatomic alcohol.
EFFECT: enhanced efficiency of removing carbon monoxide as well as accompanying sulfur-containing impurities.
1 tbl, 21 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.
EFFECT: increased CO conversion.
2 tbl, 8 ex
FIELD: gas treatment catalysts.
SUBSTANCE: invention provides catalyst consisted of inert carrier and catalytic coating containing platinum, rhodium, and oxide substrate, wherein catalytic coating includes: (i) at least one first substrate material selected from group consisted of first active aluminum oxide enriched with cerium oxide; mixed oxide, which is cerium oxide/zirconium dioxide; and zirconium dioxide component; provided that catalytic component in at least one first substrate material is first portion of the total quantity of catalyst platinum, wherein concentration of the first portion of the total quantity of catalyst platinum lies within a range of 0.01 to 5.0% of the total mass of catalyst-containing materials; and (ii) a second substrate material containing second portion of total quantity of platinum and rhodium as catalytic component, said second substrate material being second active aluminum oxide, wherein concentration of platinum plus rhodium on the second substrate material lies within a range of 0.5 to 20% of the total mass of the second substrate material. Method for preparing above catalyst is also provided.
EFFECT: increased catalytic activity and reduced catalyst preparation expenses.
17 cl, 3 dwg, 5 tbl, 3 ex