The catalyst for the oxidation of carbon monoxide
(57) Abstract:The invention relates to the purification of gases containing carbon monoxide. As catalyst for the oxidation of carbon monoxide used calcined manganese cake, which is obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical production of hydroxide cobalt (III). The technical result - the use of waste materials and industrial products hydrometallurgical production. table 1. The invention relates to the purification of gases from environmentally hazardous components and can be used for purification of exhaust gases of an internal combustion engine, for neutralization of exhaust gases of industrial enterprises, power plants, asphalt plants and other process industries and aggregates containing in its composition and carbon monoxide.Known copper-manganese and zinc-copper-chromium catalysts, cement-based [Kuznetsov, I. E. Shmat K. I., Kuznetsov, S. I. Equipment for sanitary cleaning gases. Kyiv. "Technology", 1989, S. 236].The disadvantages of the catalyst are relatively high cost and complexity of manufacture.The disadvantage of the catalyst is the necessity of its manufacture, cost of materials and production.Object of the invention is the use of waste materials and industrial products hydrometallurgical production of hydroxide cobalt (III) as catalyst for the oxidation of carbon monoxide.The technical result that can be achieved by carrying out the invention, lies in the high degree of purification of exhaust gases from environmentally hazardous components with simultaneous effectiveness of the process.This technical result is achieved by the fact that in the known catalyst for the oxidation of carbon monoxide, comprising manganese dioxide as a catalyst for the oxidation of carbon monoxide used calcined manganese cake obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical hydroxide cobalt (III).The essence of the catalytic effect of calcined manganese cake is that as a result of chemical and phase preframe oxidation of carbon monoxide.Examples of practical application.As the catalyst used is manganese cake obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical hydroxide cobalt (III) of JSC "MMC "Norilsk Nickel".For cleaning solutions in which the content of cobalt is significantly higher than the manganese content, apply chlorine method for selective oxidation of manganese from cobalt solutions of chlorine by the reaction:
MnSO4+Cl2+2H2O= MnO2+H2SO4+2HCl (1)
When the content of cobalt in the solution is 50 to 100 times the concentration of manganese, the reaction:
CoSO4+Cl2+6H2O= 2Co(OH)3)+2H2SO4+2HCl (2)
For the production of solutions of cobalt containing 0.3-0.6 g/DM3manganese deposition of Mno2formed by reactions 1 and 3, is carried out at a pH of 1.5 to 2.5, forming a manganese cake with weight ratio of cobalt to manganese is From:MP(2,53,0):1.In a production environment with a small admixture of manganese precipitated his GUI SO4when the active chlorine concentration of 30-40 g/DM3and the ratio of chlorine to alkali (3-5):1. Consumption of hypochlorite set of 4 kg of chlorine per 1 kg of manganese. The deposition of lead from dilute solutions. Very active oxidant manganese is also chlorine gas cleaning which is carried out at air stirring solution and the feed to the reactor soda.The first manganese cake with attitude:MP=(410):1 after filtering and washing from cobalt is treated with a solution containing 25-30 g/DM3H2SO4when heating it with steam to 50-60oIn the presence of sulphurous anhydride. From the resulting solution is again precipitated manganese and receive secondary manganese cake with attitude:MP=(21):1. The solution from the second filter cake contains a significant amount of cobalt and Nickel and its return to the head, i.e. the clearing of iron.The second manganese cake is dissolved and the solution of alkali precipitated hydrates of monooxide metals. The precipitation of the hydroxide (II) is conducted by using a solution of caustic alkali (60-80 g/DM3NaOH), at the end of the precipitation the pH is 7.5. After deposition of the hydroxide (II) obtained a solution containing up to 1 g/DM3With and 2-7 g/DM3MP. This process is a solution of cobalt to manganese 5:1 are dissolved and sent to the beginning of the process.Thus, the deposition process is multi-staged and performed with great loss of cobalt in the deposition. It is also connected with the fact that active chlorine in solution oxidizes, along with manganese, and cobalt, which results in these conditions to substantial precipitation and coprecipitation last.According to x-ray phase analysis is used as the catalyst manganese cake contained, wt.%: Noon 20,72; UNSD 46,53; MP(OH)22,81; Co(OH)26,14; IGOs 4,60; Soo 6,39; (Co, MT) O(HE) 12,81.According to x-ray phase analysis of calcined at 250oC for 30 min manganese cake contained, wt.%: Noon 14,31; UNSD 56,62; MP(OH)24,11; Co(OH)26,09; IGOs 4.26 Deaths; Soo 6,70; (Co, MT) O(HE)to $ 7.91.Cleaning the gas phase from the carbon monoxide was carried out by the method of "perfect push.For the generation of carbon monoxide used stove, which burned wood particle material by the incomplete combustion of fuel. From the furnace the obtained gas mixture was passed through an absorption flask with concentrated sulfuric acid, and then through the condenser-absorber with 10% aqueous NaOH solution through britholite with glass balls and collected in rubber the piping set with a diameter of 15 mm with a catalyst, which were placed in a sand bath with electric. The gas mixture was controlled by the content of carbon monoxide at the entrance to the U-shaped tube (before catalyst) and the output of which (after catalyst) detector brand APA-121. Temperature control in a sand bath, the catalyst and out of the tubes cleaned gas was performed using a mercury thermometer.The powder of manganese oxide, calcined at 250oC for 30 min, a weight of 2 g were placed in each of six series-connected between a U-shaped tubes with control of the CO content in the gas stream passing through each of the tubes.The velocity of the gas was regulated so that the gas and powder created a "fluidized bed" in one of the bends of the tubes and thus created the maximum possible contact between the catalyst surface and the cleaned gas. Due to the high density of the powder and low-speed gas flow catalyst carryover minor and controlled by the filter, filled with glass wool.The table below gives the results of purification of the gas phase from the carbon monoxide method "perfect push.The velocity of the gas flow 0,35-0,50 DM3With the degree of purification of gas WITH greater than 50%, with increasing temperature of the catalyst for purification of gas WITH increases and at a temperature of 175-250oWith reaches 90-99%.According to x-ray phase analysis was used as the catalyst manganese cake contained, wt.%: Co3O453,19; (Co, Mn)(CoMn)2O436,70; Noon 10,11. This phase structure shows that in the process increases the efficiency of the use of manganese oxide as an oxidation catalyst.Compared with the prototype using calcined manganese oxide in an inexpensive and efficient catalyst for the oxidation of carbon monoxide does not require additional expenses for its manufacturing. If necessary, manganese cake can be easily pressed into tablets. The use of calcined manganese oxide obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical production of hydroxide cobalt (III), as catalyst for the oxidation of carbon monoxide.
SUBSTANCE: invention relates to chemistry and can be used in removing sulphur oxides from recycle gases in the presence of a catalyst. The catalyst contains an active part, containing magnesium and calcium oxides, deposited on an alumina support. The active part additionally contains manganese oxide in the following ratio of components, wt %: magnesium and calcium oxide 6.0 to 20.0, manganese oxide 0.03 to 1.00, carrier - the rest to 100. Aluminium oxide trihydrate, annealed at temperature ranging from 750 to 900°C and saturated with active components at pH 0.5 to 2.5, is used as the carrier.
EFFECT: invention simplifies technology of producing catalyst, reduces damaging effect on the environment, reduces cost of catalyst.
3 cl, 4 ex
SUBSTANCE: invention relates to catalytic cracking of hydrocarbons. Described is method of obtaining light olefins by catalytic cracking of hydrocarbons with 4 or more than 4 carbon atoms, with boiling point 30-200°C, in presence of catalyst, characterised by the fact that 0.01-5.0 wt % of MnO2 and 1-15 wt % of P2O5 are simultaneously added to catalyst components, where catalyst components contain 1-50 wt % of zeolite, 21-70 wt % of clay and 1-40 wt % of inorganic oxide and where both MnO2 and P2O5 are introduced into (modify) each of catalyst components, such as ZSM-5 zeolite, clay and inorganic oxide.
EFFECT: increase of product outcome.
10 cl, 1 dwg, 6 tbl, 9 ex
FIELD: oil and gas industry.
SUBSTANCE: invention relates to the catalyst, containing the hexaaluminate, in which there is the hexaaluminate containing phase, including cobalt in the amount from 2 up to 15 moll. % and at least one other element, selected from the group consisting of lanthanum, barium and strontium in the amount from 2 up to 25 moll. %, and the amount of aluminium is from 70 up to 90 moll. %. Besides the hexaaluminate containing phase in the catalyst, there is from 0 up to 50 wt % of the accessory oxide phase. The proposed catalyst production method contains according to the invention the aluminium source preparing, preferably alumina and/or aluminium hydroxide (boehmite), in the form of dispersible primary particles ≤with the size 500 nm; placing into contact of the fine aluminium source to the fusible or soluble cobalt containing compound, and at least one soluble or fused salt of the metal, selected from the group consisting the barium, lanthanum and strontium; careful mixing of the aluminium source with dissolved, or, respectively, molten metal salts; the mixture drying; the mixture low-temperature calcination; moulding, or respectively shaping. Besides, the invention relates to the gas reforming method, containing more than 70 vol. % of hydrocarbons, preferably methane and in the presence of carbon dioxide, with the hexaaluminate catalyst, which is heated at the contact with gas to be reformed at the temperature above 700°C, preferably above 800°C, more preferably above 900°C in the reactor, the pressure higher than 5 bar, preferably higher than 10 bar, more preferably above 15 bar, the space velocity of the reforming gas, placed into contact to the catalyst, is in the range from 500 to 20,000 h-1, and the catalyst containing hexaaluminate, contains the cobalt and at least one other metal, selected from the group, consisting of barium, strontium and lanthanum.
EFFECT: catalyst with the low lanthanum content, with high coking resistance and high catalytic activity, using over the long periods of time in extremely hard process conditions.
15 cl, 4 dwg, 6 tbl
SUBSTANCE: invention relates to the methods for producing oxide catalysts on a metal support substrate that can be used in oxidation reactions of CO to CO2, which take place in the high-temperature processes for cleaning process and exhaust gases, in particular in the energy and automotive industries. The proposed method includes anodizing an aluminium substrate in a galvanostatic mode at the current density of 10-15 mA/cm2 for 20-60 min in 3% aqueous solution of oxalic acid C2H2O4, washing and drying, after which the intermediate porous alumina layer formed on the aluminium substrate is treated with a 1% solution of phosphoric acid heated up to 35°C, washed, dried, and applied to the treated aluminium substrate, ultrafine manganese dioxide, which is formed by impregnation with a 5% solution of potassium permanganate KMnO4 followed by annealing in air at 220-230°C for 10 minutes, while the operation of applying manganese dioxide can be carried out three times.
EFFECT: simplification and cheaper technology while expanding the range of composite catalytic materials containing a metal substrate with supported transition metal oxides.
2 cl, 4 dwg, 2 ex
FIELD: chemical industry.
SUBSTANCE: the invention is pertinent to the field of chemical industry, in particular to production of a catalysts and processes of oxidation of ammonia in production of a weak nitric acid. The invention offers an ammonia conversion catalyst on the basis of the mixture of oxides of unitized structure and a method oxidation of ammonia in production of weak nitric acid. The catalyst represents a mixture of oxides of the over-all formula (AxByO3Z)k (MmOn)f, (NwPgvOv)r where: A - cation of Ca, Sr, Ba, Mg, Be, Ln or their mixtures; B - cations of Mn, Fe, Ni, Co, Cr, Cu, V, A1 or their mixtures; x=0-2, y=1-2, z=0.8-l.7; M - A1, Si, Zr, Cr, Ln, Mn, Fe, Co, Cu, V, Ca, Sr, Ba, Mg, Be or their mixtures; m=l-3, n=l-2; N - Ti, Al, Si, Zr, Ca, Mg, Ln, W, Mo or their mixtures, P - phosphorus, O - oxygen; w=0-2, g=0-2, v=l-3; k, f and r - mass %, at a ratio (k+f)/r=0-l, f/r=0-l, k/f = 0-100. The catalyst is intended for use in a composition of a two-stage catalytic system generated by different methods, also in a set with the trapping platinoid screens and-or inert nozzles. The technical result ensures activity, selectivity and stability of the catalyst to thermocycles at its use in two-stage catalytic system with a decreased loading of platinoid screens.
EFFECT: the invention ensures high activity, selectivity and stability of the catalyst to thermocycles at its use in two-stage catalytic system with a decreased loading of platinoid screens.
8 cl, 1 tbl, 5 ex
FIELD: cleaning waste gases from hydrocarbons; oil refining industry, petrochemical industry and other industries.
SUBSTANCE: proposed method includes oxidation with atmospheric oxygen at elevated temperature in presence of catalyst performed at temperature of 270-280°C in presence of cement-containing catalyst at the following composition of components, mass-%: copper oxide (CuO), 30-50; zinc oxide (ZnO), 19-30; manganese oxide (Mn3O4), 0.5-16; the remainder being technical calcium aluminate.
EFFECT: high degree of cleaning waste gases from hydrocarbons.
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: petroleum processing and petrochemistry.
SUBSTANCE: invention relates to hydrotreatment of different petroleum fractions with high content of straight-chain paraffins to yield product with high content of isoparaffins. Catalyst is prepared on the base of crystalline elemento-alumino-phosphates having specified structure via (i) preparing aqueous reaction mixture containing aluminum source, concentrated phosphoric acid, and one or two sources of substituting element selected from magnesium, zinc, silicon, cobalt, manganese, nickel, chromium, and also organic structuring compound constituting di-n-pentylamine or mixture thereof with other di-n-alkylamines and having following composition (in molar parts): R/Al2O3 0.5-2.0, P2O5/Al2O3 0.8-1.2, MOx/Al2O3 0.05-1.5, and H2O/Al2O3 15-200 followed by (ii)crystallization of thus prepared mixture.
EFFECT: increased activity and selectivity of catalyst with regard to formation of desired reaction products and preserved catalyst activity regarding hydrogenation of aromatics.
4 cl, 1 dwg, 14 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention is dealing with catalyst applicable in saturated hydrocarbon ammoxidation process resulting in corresponding unsaturated nitrile. Catalyst composition of invention comprises complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel and magnesium, and at least one of lithium, sodium, potassium, rubidium, and thallium and is described by following empirical formula: AaBbCcFedBieCofCegSbhMomOx, wherein A represents at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, and mixtures thereof; B represents at least one of Li, Na, K, Rb, Cs, Ti, and mixtures thereof; C represents at least one of Ni, Mg, and mixtures thereof; a varies from 0 to 4.0, b from 0.01 to 1.5, c from 1.0 to 10.0, d from 0.1 to 5.0, e from 0.1 to 2.0, f from 0.1 to 10.0, g from 0.1 to 2.0, h from 0.1 to 2.0, m from 12.0 to 18.0, and m is a number determined by requirements of valences of other elements present. Ammoxidation processes for propylene, ethylene, or their mixtures to produce, respectively, acrylonitrile, methacrylonitrile, or their mixtures in presence of above-defined catalytic composition is likewise described.
EFFECT: increased olefin conversion.
9 cl, 1 tbl