The method of obtaining acetic acid by the oxidation of ethylene to solid metal complex catalyst for implementing the method
(57) Abstract:The inventive method of obtaining acetic acid involves the oxidation of ethylene with oxygen in the gas phase in the presence of water and a heterogeneous metal complex catalyst in a molar ratio of ethylene, oxygen and water, equal 1:(1,5-2):(3-6), high temperature and high pressure. The solid catalyst contains elements in the proportions of f-Le: (a)Pd (b)M Ti (c)P (x)O, where M is chosen from the group of cadmium, alkaline and alkaline-earth metals: the numerical coefficients: a 0,000,5-0,2; b 0-3a; c 0,5 2,5; x
is the sum of the valences of the other present in the catalyst elements. In addition, the catalyst comprises a crystalline TiP2O7formed during the calcination of the catalyst. 2 S. p. and 12 C.p. f-crystals, 1 table. The invention relates to a catalyst used for oxidation of ethylene to acetic acid, as well as to the way such oxidation using a specified catalyst.The purpose of the invention to develop a new, superior properties of the catalyst based on palladium metal with the carrier for the production of acetic acid by oxidation of ethylene with molecular oxygen, in addition to CLASS="ptx2">These goals are achieved according to the method for producing acetic acid, which consists in the implementation of the interaction of ethylene and molecular oxygen in the reaction zone in the presence of a solid catalyst containing the elements and the proportions of them, defined by the empirical formula I
PbaMbTiPcOxwhere M is chosen from a Cd, Au, Zn, Tl, alkali metals and alkaline earth metals, "a" is from 0.0005 to 0.2, "b" has a value from zero up to 3A, "C" is 0.5-2.5 and x represents an amount sufficient to satisfy the valences of the other elements present, and where the catalyst contains crystalline TiP2O7.In the formula I "and" is usually 0.005 to 0.05, typically from 0.002 to 0.04 "with" not less than 0.8 and not more than 2, more often not more than 1,25.When using the M "b" is usually not less than 0,0001.It is established that the crystalline TiP2O7, titanium pyrophosphate, is not only effective and mechanically durable physical medium for palladium components of the catalyst, but also contributes to the catalytic activity. Thus, the catalyst obtained with the use of Pb, H2PO4and SiO2the quality is compared to the output, achievable with the use of the catalyst of this invention (see table, example 27 and comparative examples 6 and 7). Another aspect of the invention concerns the development of a method for oxidation of ethylene with molecular oxygen in the presence of a specified catalyst. The reaction of oxygen and ethylene performed to obtain acetic acid, does not require the introduction of water into the reaction zone, although the reaction produces a certain amount of water as a result of undesirable combustion certain number of ethylene. In the practical implementation of the process usually impose some amount of water in the reaction zone along with the ethylene and oxygen, because, as it turns out, she promotiom conversion of ethylene to acetic acid. Many specific examples of water included in the composition of raw materials.Oxygen included in the composition fed to the reaction zone feedstock, can be a pure gaseous oxygen or, alternatively, the oxygen-containing gas mixture such as air or air enriched with oxygen. In addition to these materials the initial gaseous mixture is participating in this process may contain other solvents, such as carbon dioxide, carbon, nitrogen or acetic acid, and which may be almost pure, or, alternatively, may be pure in the sense that it may contain a fairly large number WITH1-C3saturated hydrocarbon gases or vapors as diluents, up to 90 mol. or higher.Presents specific examples of the invention are merely illustrative and do not limit the substance and scope of the claims. The empirical formula of each catalyst is given at the beginning of each example. Examples of catalysts of the invention include crystalline TiP2O7, titanium pyrophosphate.Upon receipt of the catalysts of the invention should be sufficiently heated or ignited composition to form the necessary crystalline phase TiP2O7. It is not formed at temperatures of annealing to 200aboutWith, it is formed in the specific embodiments of the invention, when the calcination is carried out at temperatures 400-850aboutC. What is not known is the lowest temperature at which can be formed TiP2O7,in the range below 400aboutC and above 200aboutWith, but this can easily be checked by routine trial and error, by annealing at different temperatures in the course is nenovsky rays to determine the presence of compounds with a crystalline structure.Comparative example 1. 2 wt. Pb/15 wt. H3RHO4/SiO2.2.6 g of Pd(NO3)2dissolved in 100 ml of distilled water was added 9.2 grams of 85% phosphoric acid and 122,3 g Zola silicon dioxide brand NaIco A (34 wt. SiO2). The mixture was boiled for 1 h and then boiled away to a thick paste. The residue was dried at 110aboutWith during the night, to grind and sifted. The fraction that passes through a sieve with openings 20 mesh but retained on a sieve with openings 35 mesh, probalily 400aboutWith over 16 PMComparative example 2. 2 wt. Pd/44% H3PO4/SiO2.The methodology used is the same that in comparative example 1, except that used to 27.0 g of phosphoric acid and 82.3 g Zola silicon dioxide.P R I m e R 1. TiPd0,03POx.To 200 ml of distilled water was added palladium acetate [Pd(OOCCH3)2]3(3,71 g). This suspension was heated under stirring at a temperature of about 60-80aboutC for 30 minutes By the end of this period, the suspension became a dark brown and part acetabularia dissolved. To this suspension was added to 57.8 g of 85% phosphoric acid, and then to 40.0 g of titanium dioxide. Then this WM the 0aboutWith and dried over night. After drying the residue to grind and sifted. Fraction lying in the range from 20 to 35 mesh, probalily in the air at 400aboutWith over 20 amComparative example 3. TiPd0,03POx.The palladium acetate (9,276 g) was resuspendable in 500 ml of distilled water and the resulting suspension was heated at 80aboutC for 30 minutes To the suspension was added phosphoric acid (85% H3RHO4, 144,5 g), and then 100 g of titanium dioxide. The mixture is boiled away to a thick paste, and then dried in an oven ( 110aboutWith the air) during the night. The residue was grind and screened, resulting in a selected fraction passing through the sieve hole size 10 mesh, but stays on the sieve with openings 35 mesh. Annealing was not performed.P R I m m e R 2. TiPd0,03POx.The palladium acetate (11,13 g) was resuspendable in 500 ml of distilled water and the suspension was heated for 30 min at 80aboutC. To the suspension was added phosphoric acid (85% H3RHO4, 173,4 g), and then 120 g of titanium dioxide. The mixture is evaporated to a thick paste, and then dried in a drying Cabinet ( 119aboutWith the air) during the night. The residue was grind up through a sieve with openings 25 mesh, but stays on the sieve with openings 35 mesh.P R I m e R 3. TiPd0,03POx.Part of the product from example 2 was probalily additionally at 600aboutWith over 16 PMP R I m e R 4. TiPd0,03POx.Part of the product from example 2 was probalily additionally when 1000aboutWith over 16 PMP R I m e R 5. TiPd0,04P1,33Ox.Reagents: 3,71 g of palladium acetate, of 57.8 g of 85% phosphoric acid and 30.0 g of titanium dioxide were combined as described in example 1. However, this sample was probalily 400aboutC in air for 16 hoursP R I m e R 6. TiPd0,03POx.The technique is the same as in example 5, except that he used to 40.0 g of titanium dioxide.P R I m e R 7. TiPd0,024P0,8Ox.The technique is the same as in example 5, except that he used to 50.0 g of titanium dioxide.P R I m e R 8. TiPd0,02P0,67Ox.The technique is the same as in example 5, except that used by 60.0 g of titanium dioxide.P R I m e R 9. TiPd0,075POx.In 150 ml of distilled water was mixed 11,58 g of palladium nitrate, of 57.8 g of 85% phosphoric acid and 40 g is the night when 110aboutWith, to grind and sift the fraction of 20/35 mesh has probalily 400aboutC in air for 16 hoursP R I m e R 10. TiPd0,05P0,98Ox.The technique is the same as in example 9, except that he used to 6.19 g of palladium acetate, 56,6 g of 85% phosphoric acid and 40.0 g of titanium dioxide.P R I m e R 11. TiPd0,04POx.The methodology is identical to that in example 5, except that the used of 4.95 g of palladium acetate, 57,2 g of 85% phosphoric acid and 40.0 g of titanium dioxide.P R I m e R 12. TiPdx0,03POx.< / BR>The methodology is identical to that in example 9, except that used 3,71 g of palladium acetate, of 57.8 g of 85% phosphoric acid and 40.0 g of titanium dioxide.P R I m e p 13. TiPd0,02P1,01Ox.< / BR>The methodology is identical to that in example 9, except that used 2,47 g of palladium acetate, 58,4 g of 85% phosphoric acid and 40.0 g of titanium dioxide.P R I m e R 14. TiPd0,01P1,02Ox.< / BR>The methodology is identical to that in example 9, except that used 1.24 g of palladium acetate, 59.0 g of phosphoric acid and 40.0 g of titanium dioxide.P R I m e R 15. TiPd0,03POx.To 200 ml of distilled water was added to the acetate is in. After this period, the suspension became a dark brown, and part of palladium acetate was dissolved. To this suspension was added to 57.8 g of 85% H3RHO4and then of 40.0 g of titanium dioxide. After that, the resulting suspension was heated and boiled away to a thick paste. This paste was placed in a drying oven set at 110aboutWith, and dried over night. Next, the remainder to grind into small pieces and probalily in air at 800aboutC for 16 hours After calcination (annealing) the remainder to grind to a particle size 20/35 mesh.P R I m e R 16. TiPd0,003POx.To 200 ml of distilled water was added the following reagents: 0,3345 g of palladium acetate, with 52.0 g of 85% phosphoric acid and to 36.0 g of titanium dioxide. The mixture was heated at 70aboutC for 30 minutes the temperature was Then raised and the suspension is boiled away to a thick paste. This paste was dried overnight at 200aboutWith, then grind and sifted. The product fraction with a particle size 20/35 mesh has probalily at 700aboutC in air for 16 hoursP R I m e R 17. TiPd0,03POx.The palladium acetate (3,714 g) was dissolved in 200 ml of glacial acetic acid, which was heated at 80aboutC for 30 minutes will fetter the temperature (hot bar), the suspension is boiled away to a thick paste. This paste was dried at 110aboutWith air during the night. Then the rest to grind and sift the fraction with a particle size 10/35 mesh was progulivali for 8 h at 800aboutC.P R I m e R 18. TiPd0,03K0,07POx.< / BR>To 120 ml of distilled water was added palladium acetate (2,23 g). This suspension was heated under stirring at a temperature of about 60-80aboutC for 5 minutes and Then the suspension was added 2,07 g of potassium nitrate and heating was carried out for 30 minutes after the specified period of suspension has acquired a dark brown color and part of palladium acetate was dissolved. To this suspension was added to 34.7 g of 85% H3RHO4and then of 24.0 g of titanium dioxide. This suspension was heated and dried to a thick paste. The resulting paste was placed in a drying oven set at 110aboutWith and dried over night. Then the remainder was split into pieces and probalily in air at 800aboutC for 8 hours After calcination residue to grind to a particle size within 10/35 mesh.P R I m e R 19. TiPd0,01K0,03POx.To 200 ml of distilled water was added palladium acetate (1,114 g). This suspension was heated under stirring at a temperature of about 60-80 is e 30 minutes After this period, the suspension became a dark brown and a part of palladium acetate was dissolved. To this suspension was added with 52.0 g of 85% H3RHO4and then to 36.0 g of titanium dioxide. After that, the suspension is brought to the boil and dried to a thick paste. This paste was placed in a drying oven set at 200aboutWith, and dried over night. The obtained residue was grind and sifted, the fraction with a particle size 20/35 mesh has probalily in air at 700aboutWith over 16 PMP R I m e R 20. TiPd0,03K0,07Cd0,03POx.The methodology is identical to that in example 18, except that immediately after the addition of potassium nitrate to the suspension was added 1.80 g of cadmium acetate.P R I m e R 21. TiPd0,03Ca0,07POx< / BR>To 200 ml of distilled water was added palladium acetate (3,71 g) and calcium nitrate (6,58 g). This suspension was heated under stirring at a temperature of about 60-80aboutC for 30 minutes the resulting suspension was added to 57.8 g of 85% H3RHO4and then of 40.0 g of titanium dioxide, then the suspension is boiled and dried to a thick paste. This paste was placed in a drying oven set at 200aboutWith, and dried over night. Then the OS is in the air at 800aboutWith over 16 PMP R I m e R 22. TiPd0,03Na0,12POx.< / BR>The methodology is identical to that in example 21, except that instead of calcium nitrate used of 5.05 g of sodium nitrate.P R I m e R 23. TiPd0,03Ca0,007POx.The methodology is identical to that in example 21, except that the used of 2.23 g of palladium acetate, 120 ml of distilled water, 0,396 g of calcium nitrate (hydrated), to 34.7 g of 85% phosphoric acid and 24.0 g of titanium dioxide. The annealing was performed in air at a temperature of 700aboutWith over 16 PMP R I m e R 24. TiPd0,03Ca0,0007POx.The methodology is identical to that in example 21, except that used 0,039 g of hydrated calcium nitrate. The annealing was performed in air at a temperature of 700aboutWith over 16 PMComparative example 5. TiPOx.To 200 ml of distilled water heated to 60-80aboutWith added of 57.8 g of 85% phosphoric acid, and then to 40.0 g of titanium dioxide. This suspension was boiled away at a high temperature (hot plates) to a thick paste. The sample was dried in air at a temperature of 110aboutC. Sample to grind and sift the fraction of particles with a size of 10/3 is the Ktsia with a particle size 20/35 mesh.Conditions of the experiments on the synthesis of acetic acid are presented in the table. These experiments on the oxidation was performed in a tubular reactor made of stainless steel, comprising a fixed layer specified crushed catalyst. The reactor was provided with a case for thermocouple inside which you can place thermocouple at various points to determine the temperature of the catalytic layer in the reaction conditions. The reactor was equipped with a jacket heated. The flow of gas entering the reactor was controlled by means of electronic controllers, mass flow, liquid raw material was pumped into the reactor using a pump liquid chromatograph Waters Model 590. Until contact with the catalytic layer, it has evaporated. The raw material is passed through the reactor from the top down. The pressure in the reactor was controlled by means of valve Tescom back pressure. The catalyst for the experiments were taken in the form of particles crushed to a size of 0.35-1,68 mm in diameter (the fraction that passed through a sieve with openings 10 mesh, but was retained on a sieve of 40 mesh). The reaction stream is passed through a scrubber with distilled water, which was cooled with ice to dissolve all liquid products. The remaining gaseous PTA, nitrous oxide and carbon dioxide. The sample liquid from the scrubber analyzed for the content of acetaldehyde, ethanol, ethyl acetate, vinyl acetate and acetic acid using capillary column with Poperechnaya methylsilicone in a gas chromatograph Hewlett-Packard. The amount of acetic acid was determined by titration method using Brinkman instruments 665 Dosimat and titrator Titrporocessor 686.Although specific values of temperature and pressure does not affect the essence of the invention, it should be noted that used the pressure from zero to 28.1 kg/cm2and temperatures up to and above 250about(In one test case 560aboutC). These examples are for professionals only guide. For example, as soon as the temperature and especially the pressure increases, it becomes increasingly difficult to regulate the exothermic nature of the reaction, up to the point where the reaction becomes uncontrollable. In this case, the add item-moderator M or a decrease in the concentration of Pd in the catalyst composition, or both reception usually contribute to the possibility of using higher pressures in the reaction zone when the warning condition is unregulated increase of temperature in sonovista temperature and at atmospheric or elevated pressure in the presence of solid metal complex catalyst, including palladium, titanium and phosphorus, characterized in that the reaction mixture of ethylene and oxygen in addition enter the water and use a solid catalyst containing the elements in the proportions in empirical formula 1
where M is chosen from the group of cadmium, alkaline and alkaline earth metals;
a= 0,0005 0,2; b=0 from 0 to 3a; c=0,5 2,5; x is determined by the magnitude of the sum of the valences of the other present in the catalyst elements,
and, in addition, the catalyst contains crystalline TiP2O7formed during the calcination of the catalyst.2. The method according to p. 1, characterized in that the use of the catalyst of the empirical formula 1, where a=0,005 0,05.3. The method according to p. 2, wherein the used catalyst, in which c in the formula 1 is equal to at least 0.8.4. The method according to p. 1, wherein the used catalyst, in which the value of c in the formula 1 is at least 0.8 and is in the range of 0.8 to 1.33.5. The method according to p. 1, characterized in that the use of the catalyst of the empirical formula 1, where M is chosen from the group of sodium, potassium, calcium, and a 0.01 to 0.03; b 7 10-4oC 0,12; c 1.6. The method according to p. 5, characterized in that ,03K0,07Cd0,03POx,
where x is the specified value.7. The method according to p. 2, characterized in that c does not exceed 2.8. The method according to p. 2, wherein c is in the range from 0.8 to 2.9. Solid metal complex catalyst for acetic acid by oxidation of ethylene, including palladium, titanium and phosphorus, characterized in that the catalyst contains the elements in the proportions indicated in empirical formula 1
where M is chosen from the group of cadmium, alkaline and alkaline earth metals; a= 0,0005 0,2; b=0 to 3a; c 0,5 2,5; x is determined by the magnitude of the sum of the valences of the other present in the catalyst elements, and the catalyst contains crystalline pyrophosphate titanium TiP2O7.10. The catalyst p. 9, wherein in the formula 1 a=0,005 - 0,05.11. The catalyst according to p. 10, wherein in the formula 1 c is equal to at least 0.8.12. The catalyst p. 9, wherein in the formula 1 c is equal to at least 0.8 and is in the range of 0.8 to 1.33.13. The catalyst p. 9, characterized in that the catalyst is responsible formsfor by p. 13, characterized in that it additionally contains cadmium and has the following composition:
where x is the specified value.
FIELD: petroleum chemistry, organic chemistry, chemical technology.
SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.
EFFECT: improved preparing method.
7 cl, 1 tbl, 2 ex
FIELD: catalysts in petroleum processing and petrochemistry.
SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.
EFFECT: intensified diesel fraction desulfurization.
9 cl, 3 tbl, 19 ex
FIELD: catalysts in petroleum processing and petrochemistry.
SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.
EFFECT: intensified diesel fraction desulfurization.
7 cl, 2 tbl, 13 ex
SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.
EFFECT: increase of conversion degree of sulphur, microcarbon residue.
23 cl, 3 ex
SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.
EFFECT: high catalyst activity.
14 cl, 8 tbl, 17 ex
SUBSTANCE: invention relates to a method of producing hydrogen cyanide through catalytic oxidation of starting material in ammonia medium. The oxidation method is carried out in ammonia medium of alcoholic starting material such as methanol, or nitrile starting material such as propionitrile, or mixture thereof. To form hydrogen cyanide, modified Mn-P catalyst is used, having the following empirical formula: MnaPlAbOx, where A is one or more elements K, Ca, Mo, Zn, Fe or combination thereof; a varies from 1 to 1.5; b varies from 0.01 to 1.0 and x is the total number of oxygen atoms, which is determined from the oxidation state of present elements. The invention also includes a catalyst for oxidation in ammonia medium.
EFFECT: catalyst has high activity.
13 cl, 2 tbl, 5 ex
SUBSTANCE: invention relates to catalysts of hydrorefining Diesel distillates, method of obtaining catalyst and method of hydrorefining Diesel distillates in order to obtain ecologically pure Diesel fuels and can be used in oil-refining industry. Described is catalyst for the process of hydrorefining Diesel fractions, which contains as carrier composition of aluminium oxide and zeolite β, which includes, wt %: 0.25-0.85 of magnesium compounds counted per MgO, 5-15 of silicon compounds counted per SiO2, aluminium oxide - the remaining part; and as active component catalyst contains, wt %: tungsten oxide WO3 - 20-25, nickel oxide - 3.8-4.1, phosphorus oxide - 1-1.5, carrier - the remaining part, with molar ratio tungsten/nickel W/Ni - 1.9-2.1 and phosphorus/tungsten P/W - 0.09-0.1. Described is method of catalyst preparation and method of hydrorefining of Diesel fractions, containing up to 30 wt % of catalytic cracking gas oil for which hydrorefining is carried out in reactor of hydropurification, loaded in layers with catalyst described above catalyst and CoMo/Al2O3 - catalyst, the latter is located in the first layer in the direction of movement, which are taken in ratio from 1:3 to 1:1.4, at temperature 340-370°C, hydrogen pressure 3.5-7.0 MPa.
EFFECT: high efficiency of hydrorefining of Diesel fraction with higher content of polycyclic aromatic hydrocarbons, nitrogen-containing and stable sulphur-containing compounds.
4 cl, 11 ex, 1 tbl
SUBSTANCE: invention relates to producing a catalyst and a process of obtaining hydrocarbons via catalytic hydrodeoxygenation of products of processing plant biomass, including microalgae biomass. Described is a catalyst for hydrodeoxygenation of organooxygen products of processing plant biomass, which is a complex composite containing Ni in a reduced form and other transition metals, wherein the catalyst contains up to 15 wt % P which is in the reduced catalyst in form of phosphides with general formula where: Mi is a transition metal in phosphide form, other than nickel or boron, 2≤n≤5, with atomic ratio from 0.01-99, mainly from 7 to 99, and a stabilising additive. Described is a hydrodeoxygenation process, which is carried out in a single step at hydrogen pressure of 0.5-20 MPa, temperature of 250-320°C in the presence of the catalyst.
EFFECT: high catalyst activity.
4 cl, 39 ex, 5 tbl
SUBSTANCE: invention relates to a method of decontaminating nitrous oxide, including low-concentration emissions of nitrous oxide, for example in exhaust gases from production of nitric acid, using a catalyst based on an iron-containing zeolite. Described is a method of preparing a catalyst for decomposing nitrous oxide by mixing a zeolite having a structure selected from the following: MFI, MEL, BEA, FER, MOR and having the composition: y·El2On·SiO2, where y = 10-5-5·10-2 , El is at least aluminium and one element from periods 2, 3, 4 and 5 of the periodic table of elements, n is valence of the element, with iron-modified binder, the binder being aluminium oxide with additives selected from the following oxides: silicon oxide, titanium oxide, zirconium oxide, iron oxide, cobalt oxide, copper oxide, lanthanum oxide, phosphorus oxide, with weight ratio of aluminium oxide to any of the listed oxides ranging from 0.01:100 to 10:100, with weight ratio of the zeolite to binder ranging from 1:9 to 9:1, where the modifying iron in the catalyst is x·Fe2O3, where x=10-5-5·10-2; modification is carried out by adding to the binder a dry or hydrated salt and/or solution of an iron salt with subsequent formation and activation of the catalyst to obtain a catalyst, wherein at least 0.5-50% of the contained iron and not less than 5·1017 iron atoms per gram catalyst are in reduced form in the form of special complexes of α-centres which are detectable and measurable using a special technique, involving determination of the amount of surface oxygen deposited from nitrous oxide at temperature of 100-300°C on the surface of the catalyst. A method of decontaminating gaseous emissions is also described.
EFFECT: simple method of producing a highly efficient catalyst for decomposing nitrous oxide.
6 cl, 1 tbl, 19 ex
SUBSTANCE: invention relates to oil refining and petrochemical industry, particularly to methods of producing catalysts for converting a straight-run gasoline fraction into a high-octane gasoline component with low benzene content. Described is a catalyst which contains the following, wt %: H-ZSM-5 type high-silica zeolite with silica modulus SiO2/Al2O3 = 30-50 - 94.0-99.0, cobalt molybdo-bismuthate or molybdo-phosphate 1.0-6.0, formed during heat treatment. Described is a method of producing a catalyst, which involves hydrothermal crystallisation of a reaction mixture at 120-180°C, which contains sources of silicon, aluminium and alkali metal oxides, hexamethylenediamine and water, followed by drying and calcining, mechanochemical treatment in a vibration mill, moulding with further saturation of the H-form of the H-ZSM-5 type high-silica zeolite with silica modulus SiO2/AI2O3=30-50 with chloride solutions of corresponding heteropoly compounds: cobalt molybdo-bismuthate or cobalt molybdo-phosphate, as a modifying additive, followed by mechanochemical treatment in a vibration mill for 0.1-24 hours, moulding the catalyst mass into granules, drying and calcining at 540-550°C for 0.1-12 hours. Described is a method of converting a straight-run gasoline fraction into high-octane gasoline component with low benzene content in the presence of the catalyst described above at 350-425°C, volume rate of 1.0-2.0 h-1 and pressure of 0.1-1.0 MPa.
EFFECT: high activity and selectivity of the catalyst.
3 cl, 1 tbl, 7 ex
FIELD: organic chemistry, chemical technology, catalysts.
SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.
EFFECT: improved preparing method.
14 cl, 1 tbl, 6 ex
FIELD: industrial inorganic synthesis.
SUBSTANCE: process is accomplished by continuously feeding methanol and/or reactive derivative thereof and carbon monoxide into carbonylation reactor filled with reaction mixture containing iridium carbonylation catalyst, methyl iodide cocatalyst, water in limited concentration, acetic acid, and methyl acetate, liquid reaction mixture further including at least one promoter selected from ruthenium, osmium, rhenium, and tungsten. Carbonylation of methanol to produce acetic acid involves reaction with carbon monoxide in liquid reaction mixture. When recovering acetic acid from liquid reaction mixture, concentration of water is maintained therein not exceeding 4.5%. During reaction, partial pressure of carbon monoxide in reactor is maintained within a range between 0 and 6 bar.
EFFECT: accelerated carbonylation reaction, diminished by-product formation, and simplified acetic acid recovery operation.
6 dwg, 3 tbl
FIELD: vinyl acetate production by ethane catalytic acetoxylation with acetic acid obtained as intermediate.
SUBSTANCE: claimed method includes: a) bringing gaseous raw material, containing ethane as a main component, into contact in the first reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the first product stream including acetic acid and ethylene; b) bringing the said first product stream in second reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the second product stream including vinyl acetate; c) separation the second product stream from stage b) to recovery of vinyl acetate. In the first reaction zone catalyst of general formula MOaPdbXcYd is used, wherein X is at least one element selected from Ti, V, and W; Y is at least one element selected from Al, Bi, Cu, Ag, Au, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Sb, Si, and Sn; a, b, c, and d are gram-atom ratio, and a = 1; b = 0.0001-0.01, preferably 0.0001-0.005; c = 0.4-1, preferably 0.5-0.8; and d = 0.005-1, preferably 0.01-0.3. Gaseous raw material from step a) preferably includes ethane and molecular oxygen-containing gas in volume ratio of ethane/oxygen between 1:1 and 10:1, and 0-50 % of vapor as calculated to total volume of starting raw material. Ratio of selectivity to ethylene and selectivity to acetic acid in the first product stream is 0:95-95:0.
EFFECT: integrated technological cycle with controllable product yield while changing technological parameters of the process.
6 cl, 11 ex, 2 tbl, 1 dwg
FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.
SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.
EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.
44 cl, 3 ex, 6 dwg
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for removing higher organic iodides from organic media. Method for removing organic iodides containing 10-16 carbon atoms from non-aqueous organic media containing organic iodides with 10-16 carbon atoms is carried out by contacting indicated organic media with silver- or mercury-exchange cationic, ion-exchange substrate at temperature from 50°C to 150°C. Invention proposes a method for removing iodides having 10-16 carbon atoms from acetic acid or acetic anhydride by providing flow of acetic acid or acetic anhydride containing organic iodide having 10-16 carbon atoms. Indicated flow is contacted with macroporous strong acid ion-exchange resin wherein at least 1% of active sites acquire form of silver or mercury at temperature in the range 50°C - 150°C. Indicated silver- or mercury-exchange ion-exchange resin removes effectively at least 90 wt.-% of indicated organic iodides from indicated flow of ready acetic acid or acetic anhydride. Also, invention proposes a method for removing organic iodides containing 10-16 carbon atoms from acetic acid or acetic anhydride involving contact of acetic acid or acetic anhydride comprising dodecyl iodide with silver- or mercury-exchange cationic ion-exchange substrate at temperature in the range 50°C - 150°C. Method provides the complete removing higher organic iodides from flow of acetic acid and/or acetic anhydride.
EFFECT: improved method for removing.
29 cl, 5 dwg, 13 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing acetic acid solution. Method involves the following procedures. Capacity with the parent raw is filled with water in the amount providing preparing acetic acid semihydrate and then water is poured in another capacity in the amount providing preparing 72-80% of acetic acid solution from semihydrate prepared in the first capacity. Then semihydrate is pumped off from the first capacity to the second one in the amount to obtain 17-50% acetic acid solution and prepared solution is stirred for 5-7 min. Sample is taken for control of mass part of acetic acid in the range 17-50%. Semihydrate is pumped off from the first capacity in the second one again under layer of liquid up to its filling and bottom layer of solution is stirred for 1-5 min. Sample is taken from the top layer for control of mass part of acetic acid in the range 17-50% and from the bottom layer in the range 72-80%. Then the bottom layer is pumped off in the amount equal to the amount of semihydrate charged at the second step. Method provides reducing fire hazard of technological process and diminishing concentration of acetic acid vapors in air of working zone.
EFFECT: improved method for preparing.
2 tbl, 1 dwg, 4 ex
FIELD: chemical engineering.
SUBSTANCE: objective of invention is how to store inflammable 60-80% aqueous acetic acid solutions under winter conditions. Problem is solved by adjusting concentration of acetic acid solution to a value at which crystallization temperature of solution is the same as average temperature in storehouse for a given winter month, for which purpose aqueous acid solution is circulated through a circuit, whereupon volume, temperature, concentration of solution, and amount of acetic acid in natural form and 100% form are determined. When indicated concentration is exceeded in storehouse, required amount of water is added while circulating solution to achieve desired concentration. Further, aqueous acetic acid solution is pumped out into transportation container. After transportation, solution is pumped into shop container, wherein above-listed parameters are redetermined and presence or absence of solid phase in the storehouse is checked. In case of equality of concentrations in shop container and in storehouse, there is lack of solid phase in the storehouse. When concentration in shop container is less than in storehouse, solid phase is available in storehouse and then, for next admittance, calculated amount of water is introduced into storehouse with circulation through circuit to obtain average acid concentration in storehouse, at which crystallization temperature of solution is the same as average temperature in storehouse for a given winter month. At subsequent withdrawal of aqueous acetic acid solution from storehouse all the operations are repeated.
EFFECT: enabled storage of aqueous acetic acid solutions during winter period without need of warming.
1 dwg, 2 ex
FIELD: analytical methods.
SUBSTANCE: invention relates to assessing acetic acid vapors in working zone air of linoleum, acetylcellulose, and alkyl acetate manufacture enterprises. Method comprises sampling air, detecting and recording analytical signal followed by calculation of acetic acid concentration. Sample is placed in detection cell with piezoquartz resonator whose electrodes are preliminarily modified with acetone solution of polyethylene glycol adipate sorbent such that mass of sorbent after removal of solvent were 10-30 μg. Recording of analytical signal is accomplished in the form of response of modified electrodes of piezoquartz resonator 15 sec after introduction of sample into detection cell. Calculation of acetic acid concentration is performed according to equation of calibration curve: ΔF = 1.4CM, where ΔF is response of modified electrodes of piezoquartz resonator, Hz, and CM is acetic acid concentration is air sample, mg/m3. Advantages of method are following: excluded sample preparation stage; reduced assessment time from 7-9 h to 0-45 min (taking into account time used for modifying electrodes and subsequent regeneration of detection cell); increased number of assessments without replacement of sorbent; reduced sorbent restoration time; and reduced assessment error.
EFFECT: accelerated assessment and increased assessment accuracy.
2 tbl, 7 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to technology for manufacturing acetic acid by the carbonylation reaction of methanol with carbon monoxide. Method is carried out in the continuous regimen in the carbonylation reactor wherein methanol and carbon monoxide are fed and catalytically active rhodium-comprising catalyst medium is maintained wherein this medium comprises the following components: water, 0.1-14 wt.-%; methyliodide, 1-20%; alkaline metal iodide salt, 2-20%; methyl acetate and acetic acid, 0.5-30%. The total pressure value in reactor is 15-40 atm. Flow of the reaction products is subjected for rapid evaporation and fed to the distillation stage comprising up to two distillation columns wherein purified acetic acid is separated and some flows recirculating into reactor. Removal of iodide impurities from the final product is carried out by contacting the flow with anion-exchange resin at temperature 100°C, not less, followed by purification stage with sulfocation-exchange resin in form of silver or mercury salt comprising 1% of active sites, not less, at temperature 50°C, not less. The level of aldehyde impurities in the flow recirculating into reactor is regulated by the distillation off method. The content of iodides in acetic acid is less 10 parts/billion. Method provides decrease of energy consumption and preparing acetic acid of high purity degree.
EFFECT: improved producing method.
28 cl, 3 tbl, 7 dwg, 12 ex