The method of obtaining 2,6-phenols dimethylsiloxane
(57) Abstract:Usage: 2,6-DIMETHYLPROPANE phenols, obtaining catalytic methylation with methanol in orthopaedie. The inventive 2,6-dimethylsiloxane phenol receive a vapor-phase Automatisierung phenol, ortho -, meta - or paracresol methanol catalysts, which are molded with a binder or put on broad porous silica gel, and then activate at 200 - 400oWith the use of reductant type of hydrogen or methanol and calcined. Get the catalyst with an atomic ratio of iron:vanadium: manganese, equal(0,5 - 1) : (1 - 0,5) : (0,05 - 0,5), the content of the active component is more than 30 wt. %. The catalyst has large pores with a radius of more than 15 nm and a pore volume of 0.5 - 1.5 cm3/year table 2. The invention relates to a process for the catalytic methylation of phenols having two hydrogen atoms in anthopology, with the formation of 2,6-dimethylpropionic phenols in the presence of zhelezovanadievyj oxide catalysts.Methylpropane phenols are very valuable substances and have an extensive range of applications in organic and inorganic synthesis. They are used as antioxidants and stabiliseerumine nonionic surfactants, construction materials, plant protection products, pharmaceuticals, vitamin E, etc.Currently, the main method of obtaining methylpropionic phenols is catalytic methylation of phenol in the liquid and the vapour phase  In the process of methylation is formed methyl ether and the various isomeric METHYLPHENOL. As catalysts are used for various acids, salts, individual oxides and oxide composition. It is shown that the conditions of alkylation and composition of the resulting products significantly depend on the used catalysts. From the published patent literature, the most effective in the reaction of methylation of phenols in anthopology are catalysts based on iron oxides and vanadium [2, 3] Proposed to metilirovanie phenols containing at least one hydrogen atom in anthopology, in the presence of oxide catalysts containing iron and vanadium, as well as additives of the third component  is Set intervals compositions of the catalysts and the reaction mixture, which is mainly methylation of benzene ring in orthopaedie. Selectivity for the amount of mono - and dimethylphenol on these catalysts is 97-otka more efficient way to obtain 2,6-dimethylpropionic phenols.In the result, found that the selective methylation of phenol, o-, m - and p-cresol with the selectivity of the formation of 2,6-dimethylpropionic to 85-97% can be achieved zhelezovanadievyj oxide catalysts containing components within the atomic ratio Fe: V:Mn(0,5-1):(1-0,5):(0-0,5). The catalysts should be in the crystalline state and having, after calcination in the temperature range 500-800aboutWith large pores with a radius of more than 15 nm and 0.5-1.5 cm3/, in Addition, to reduce design time, typical catalysts of this type, and improving the selectivity of the catalysts before reaction it is necessary to activate the processing of substances-reducing agents, such as hydrogen, methanol, etc. at temperatures of 200-400aboutC.To prepare zhelezovanadievyj oxide catalysts can be used any soluble salts of these elements, preferably nitrates of iron and manganese and vanadium oxalate. The catalysts obtained from a solution of salts of the starting components in the respective molar ratios one way: co-precipitation, followed by filtration and drying, spray drying of a solution with a binder, followed by granulation of pasta by extrusion through a die plate of a given shape and size, any of it to prepare tablets also certain size. The obtained granules or tablets of the catalyst is dried and calcined in the temperature range 500-800aboutC.In addition to the massive in this process are encouraged to apply and catalysts on carriers. It is shown that the most effective - ness of the broad porous carrier is silica gel with pore 30-4000 nm and 0.5-1.0 cm3/, cook it For use Aerosil, which first plastificator, granularit, and then the granules are subjected to thermoprotei autoclave at a temperature of 250-350aboutC. the Catalyst is prepared by impregnation of silica gel for moisture capacity solution mixture of salts of the components are taken in a specific atomic ratio, followed by drying and calcination.The reaction of methylation of phenols is carried out in a flow reactor with a fixed catalyst bed. In the reactor with an inner diameter of 1.8 cm was placed a portion of the catalyst from the top to fall asleep layer (4-5 cm) of crushed quartz with a particle size of 3-5 mm, serves as the evaporator of the reaction mixture. The catalyst was calcined in the reactor in a stream of nitrogen (1-15 l/s) at a temperature of 350-550aboutC for 1 h Then it is treated of vosstanovit, not stopping the flow of nitrogen into the reactor serves a mixture of phenol, methanol and water. The molar ratio between the components of the reaction mixture varies f: M: B 1:(1-10):(1-10). The reaction is carried out at a temperature of 300-400aboutC. the reaction Products are collected in a cooled trap and analyze method getaccountinfo chromatography. The contact time varies by changing the feeding speed of the reaction mixture and the amounts of catalyst.According to the results of chromatographic analysis of phenolic parts and products of the reaction determine the degree of conversion of phenol and selectivity of methylation. The degree of transformation (X,) is defined as the ratio of the numbers of moles of unreacted phenol and missed, the selectivity of the formation of methylated phenol (S) is defined as the ratio of the number of moles formed methylated phenol and unreacted phenol.P R I m e R 1. In a reactor equipped with a mixer, poured 1.2 l of distilled water and bring the temperature up to 70-90aboutWith, and then dissolved under stirring in her 300 g of oxalic acid. Then to this solution was added 100 g of V2O5after dissolving , the solution is cooled. To the resulting solution was added 444,2 g Fe(NO
P R I m e R 17. The catalyst is prepared analogously to example 1. Test activity carried out analogously to example 1. Activation of the catalyst is carried out in pairs of methanol in the course of the activity carried out analogously to example 1, instead of phenol used o-cresol (o-Cu), the ratio of the o-Cu:M:B 1:5:3. The volumetric feed rate of the nitrogen-steam mixtures 1250 h-1.In table. 1 shows the stationary characteristics of the activity of the catalysts of examples 1-18.P R I m e R 19. The catalyst is prepared analogously to example 1. Test activity carried out analogously to example 1, instead of phenol used m-cresol (m-Cu), the ratio of the components in the reaction mixture m-Cu:M:B 1:5:3, the volumetric feed rate of the nitrogen-steam mixtures 1330 h-1.P R I m e R 20. The catalyst is prepared analogously to example 1. Test activity carried out analogously to example 19, the volumetric feed rate of the nitrogen-steam mixtures 1570 h-1.P R I m e R 21. The catalyst is prepared analogously to example 1, the test activity carried out analogously to example 19, the ratio of the components in the reaction mixture m-Cu: M: B 1:8:3, the volumetric feed rate of the reaction mixture 1600 h-1.The results of examples 19-21 are given in table. 2.P R I m e R 22. The catalyst is prepared analogously to example 1. Test activity carried out analogously to example 1, instead of phenol used p-cresol (p-CR), the ratio of the components of the p-CR:M:B 1:5:3, the volumetric feed rate of the nitrogen-parthi carried out analogously to example 22, the volumetric feed rate of the nitrogen-steam mixtures 1660 h-1.The results of examples 22 and 23 are given in table. 3.As can be seen from the above results, the proposed method for the methylation of phenols with hydrogen atoms in anthopology, in the presence of macroporous zhelezovanadievyj catalyst increases the activity and selectivity for 2,6-methylpropionyl phenols in comparison with known methods. In addition, the proposed pre-activation of the catalysts in the presence of substances-reducing agents significantly reduces the period of development of such catalysts. The METHOD of OBTAINING 2,6-DIMETHYLSILOXANE PHENOL vapor-phase Automatisierung phenols in the presence of the oxide zhelezovanadievyj catalysts, wherein the catalysts used pre-activated at 200 - 400oWith the environment reductant solid or deposited on a broad porous silica gel zhelezovanadievyj or zhelezomargantsevye catalysts with the active component at least 30 wt. %, the atomic ratio of the metals Fe and V is 0.5 - 1 : 1 - 0.5 or Fe : V : Mn 0,5 - 1 : 1 - 0,5 : 0,05 - 0,5, when this catalyst has large pores with a radius of b is
FIELD: waste water treatment.
SUBSTANCE: invention relates to biological waste water treatment methods that can be used at enterprises of power, petroleum processing, petrochemical, chemical, paper-and-pulp, food processing, and other industries as well as for treatment of household sewage. Biocatalytic waste water treatment is performed by oxidation in air tanks or on biofilters in presence of catalytically acting substance and activated sludge. In case of air tanks, catalytically acting substance consists of one (multifunctional) or three (one multifunctional and two selective) heterogeneous catalysts for oxidation of inorganic and/or organic compounds and containing active component: variable-valence metal oxides and/or hydroxides, or spinels, and, additionally, modifying additive, in particular organic bases and/or heteropolyacids, active component being deposited on polymer carrier (polyethylene or polypropylene). Content of active component is 15-20% and that of modifying additive 0.5-20%. For oxidation of organic, sulfur, and nitrogen compounds, multifunctional catalyst is used containing active component consisting of variable-valence metal oxides and hydroxides. For nitrification process (ammonium nitrogen oxidation), selective catalyst is used containing active component consisting of variable-valence metal spinels and oxides. In case of denitrification process (reducing nitrites and nitrates into molecular nitrogen), selective catalyst is used containing active component consisting of variable-valence metal spinels and hydroxides. Oxidation process is accomplished at catalyst-to-water ratio 1:75 at consumption of air not higher than 9.0 m3/m3. Invention also discloses biocatalytic treatment of waste waters via oxidation on biofilters in presence of activated sludge and catalytically acting substance consisting of active component (15-50%): one or several variable-valence metal compounds, flux (50-10%): silicon-containing compound, modifying additive (0.5-20%): carbon-containing material, and carrier: clay.
EFFECT: increased productivity and reduced power consumption on existing treatment plants, reduced investment and operational expenses, and deepened waste water treatment.
8 cl, 5 tbl, 10 ex
FIELD: industrial organic synthesis and catalysts.
SUBSTANCE: catalyst is constituted by polyoxometallate of general formula Ax[XM'12-nM"nOk]y-, where X represents B, Si, or P; M' = Mo or W; M" = Ce or Co; n=1-6, k=39-41, A cation selected from series: H+, Na+, K+, or mixture thereof, y charge of polyanion, and x number of cations. Invention also discloses a process of oxidation of formaldehyde with oxygen and/or air at atmospheric pressure in presence of polyoxometallate catalyst and initiator in aqueous solution at temperature not exceeding 100°C.
EFFECT: increased selectivity of catalyst regarding formic acid and thereby increased conversion of formaldehyde, reduced process expenses, and simplified oxidation process resulting in improved environmental condition.
9 cl, 1 dwg, 3 tbl, 23 ex
SUBSTANCE: invention describes method of obtaining aggregated catalyst for hydrogen treatment of oil fractions. The catalyst is a composition of components in the form of compounds of one VIII group metal and two VIB group metals. Method involves mixing and chemical interaction of components, producing active complex by mechanic and chemical activation of components, which remain in solid state during the whole process performed in aggregates of mechanic and/or hydrodynamic effect, preferably in planetary centrifugal mill, at room temperature for 5-30 minutes, with free pass distance of milling bodies equal to 4.0-5.0 cm, relative collision speed of milling bodies equal to 17-34 m/s, reaction layer thickness for component mix on the surface of milling bodies equal to (0.4-2.6)·10-2 cm, with further drying, tempering and sulfidation. Active complex is dried for 10-15 minutes.
EFFECT: high-grade purification of oil products from sulfur.
1 cl, 1 tbl, 2 dwg, 5 ex
SUBSTANCE: invention relates to improved method of carrying out heterogenous catalytic partial oxidation in gas phase of acrolein into acrylic acid, during which reaction gas mixture, containing acrolein, molecular oxygen and at least one inert gas-thinner, is passed through having higher temperature catalytic still layer, whose catalysts are made in such way that their active mass contains at least one oxide of multimetal, containing elements Mo and V, and in which during time, temperature of catalytic still layer is increased, partial oxidation in gas phase being interrupted at least once and at temperature of catalytic still layer from 200 to 450°C acrolein-free, containing molecular oxygen, inert gas and, if necessary, water vapour, as well as, if necessary, CO, gas mixture of G oxidative action is passed through it, at least one interruption being performed before increase of catalytic still layer temperature constitutes 2°C or 4°C or 8°C or 10°C during a long period of time, temperature increase constituting 2°C or 4°C or 8°C or 10°C over a long period of time occurring when in plotting factual course of temperature of catalytic still layer during time on laid through measurement points equation curve according to elaborated by Legendre and Gauss method of the least sum of error squares 2°C or 4°C or 8°C or 10°C temperature increase is achieved.
EFFECT: ensuring spread of hot point with time which is less than in previous methods.
21 cl, 3 dwg, 1 ex
SUBSTANCE: invention relates to improvement of the method of producing (meth)acrylic acid or (meth)acrolein through gas-phase catalytic oxidation of at least one oxidisable substance, chosen from propylene, propane, isobutylene and (meth)acrolein, molecular oxygen or a gas, which contains molecular oxygen, using a multitubular reactor, with such a structure that, there are several reaction tubes, with one (or several) catalytic layer (catalytic layers) in the direction of the axis of the tube, and a coolant can flow outside the said reaction tubes so as to regulate temperature of reaction, in which temperature of the said reaction of gas-phase catalytic oxidation is increased by varying temperature of the coolant at the inlet for regulating temperature of the reaction, while (1) temperature of coolant at the inlet for regulating temperature of the reaction is varied by not more than 2°C for each variation as such, and (2) when variation is done continuously, the time interval from the variation operation, directly preceding the present, is not more than 10 minutes, and, in addition, the difference between the maximum value of peak temperature of reaction of the catalyst layer of the reaction tube and temperature of the coolant at the inlet for regulating temperature of reaction is not less than 20°C.
EFFECT: method in which sharp increase of temperature is suppressed even after changing reaction conditions with aim of increasing temperature for improving efficiency, thus preventing catalyst deactivation, and achieving stable output.
3 cl, 5 dwg, 5 ex
SUBSTANCE: invention relates to a method for prolonged heterogeneously catalysed partial oxidation of propene to acrylic acid in gaseous phase, in which the initial gaseous reaction mixture 1, containing propene, molecular oxygen and at least one inert gas, where molecular oxygen and propene are in molar ratio O2:C3H6≥1, is first passed through a fixed catalyst bed 1 at high temperature at the first stage of the reaction, where the active mass of the catalysts is at least one multimetal oxide, containing molybdenum and/or tungsten, as well as at least one element from a group consisting of bismuth, tellurium, antimony, tin and copper, so that, conversion of propene in a single passage is ≥93 mol % and associated selectivity of formation of acrolein, as well as formation of acrylic acid by-product together is ≥90 mol %, temperature of the product gaseous mixture 1 leaving the first reaction stage is reduced if necessary through direct and/or indirect cooling, and if necessary, molecular oxygen and/or inert gas is added to the product gaseous mixture 1, and after that, the product gaseous mixture 1, acting as initial reaction mixture 2, which contains acrolein, molecular oxygen and at least one inert gas, where molecular oxygen and acrolein are in molar ratio O2:C3H4O≥0.5, is passed through a second fixed catalyst bed 2 at high temperature at the second reaction stage, where the active mass of the catalysts is at least one multimetal oxide, containing molybdenum and vanadium so that, conversion of acrolein in a single passage is ≥90 mol % and selectivity of the resultant formation of acrylic acid at both stages is ≥80 mol % in terms of converted propene, and temperature of each fixed catalyst bed is increased independently of each other. Partial oxidation in gaseous phase is interrupted at least once and at temperature of fixed catalyst bed 1 ranging from 250 to 550°C and temperature of fixed catalyst bed 2 ranging from 200 to 450°C, gaseous mixture G, which consists of molecular oxygen, inert gas and water vapour if necessary, is first passed through fixed catalyst bed 1, and then, if necessary, through an intermediate cooler and then finally through fixed catalyst bed 2, in which at least a single interruption takes place before temperature of the fixed catalyst bed 2 increases by 8°C or 10°C, wherein prolonged increase of temperature by 8°C or 10°C, is possible when virtual passage of temperature of the fixed catalyst bed in the period of time on the leveling curve running through the measuring point using the Legendre-Gauss method of the least sum of squares of errors, temperature increase of 7°C or 10°C is achieved.
EFFECT: method increases service life of catalyst.
24 cl, 1 ex, 3 dwg
SUBSTANCE: invention relates to chemistry. According to the method, the hydrocarbon conversion catalyst contains nickel oxide, lanthanum oxide, boron oxide and aluminium oxide, with the following ratio of components, wt %: nickel oxide 11-25, lanthanum oxide 1-12, boron oxide 0.3-0.9 and aluminium oxide - the rest. The catalyst is obtained by preparing a mixture which contains alumina and boric acid, binder in form of a mixture of paraffin, wax and oleic acid, moulding a support through slip casting, curing in air and calcining the obtained support at temperature 1480-1520°C, followed by saturation with a solution of nitrates of nickel and lanthanum or nickel, aluminium and lanthanum, drying and calcination of the saturated alumina support at temperature 510-590°C while raising temperature at a rate of not more than 1°C/min. Synthetic gas is obtained by converting hydrocarbons on a catalyst of the said composition in form of a sphere with parallel cylindrical channels with the following characteristics of the layer: specific surface area 400-650 m2/m3, porosity 0.5-0.7 m3/m3.
EFFECT: invention increases catalyst activity, lowers its hydraulic resistance, increases efficiency of producing synthetic gas.
5 cl, 1 tbl, 8 ex
FIELD: process engineering.
SUBSTANCE: invention relates to hydraulic treatment catalysts and methods of their production. Proposed method comprises: (I) using, at least, on of the following components: (A) one calcinated porous carrier; (B) catalytically active metals used in hydrocarbon hydraulic treatment, at least, one metal of VIB group of periodic table, and, at least one component including, at least, one metal of VIII group of periodic table; (C) at least, one chelate; (D) water in amount sufficient for producing solution or dispersion containing said catalytically active metals and at least, one said chelate; (II) interaction of said components (1)(A) with said solution or dispersion containing (1)(B) and (1)(C) during time interval and at temperature sufficient for mix production and impregnation of said carrier with said components (1)(B) and (1)(C) (III) to make the volume of said solution or dispersion equal to or exceeding water porosity of said carrier by separating said impregnated carrier from solution or dispersion volume that exceeds water porosity volume; and (IV) heating said impregnated carrier to above 200°C, and lower temperature and time period that may cause notable destruction of, at least, one said chelate.
EFFECT: chelated hydraulic treatment catalyst with low moisture content.
18 cl, 8 tbl, 5 ex
SUBSTANCE: method involves: a) heterogeneously catalysed vapour-phase partial oxidation of a starting organic compound selected from propylene, propane, isobutylene, isobutane, acrolein or methacrolein with molecular oxygen in a parallel-functioning system of oxidation reactors containing catalysts, which results in formation of two gas streams respectively containing the desired compound and respectively formed in one of two systems of oxidation reactors, and b) subsequent extraction of the desired product from two streams of the obtained gas to form at least one stream of crude desired product according to which c) before extraction of two from two streams, the obtained gas is mixed with each other into a mixed stream. In case of change in selectivity of formation of the desired product and/or by-products during operation the entire amount or partial amount of catalyst is replaced in parallel with fresh catalyst not in all parallel-functioning systems of oxidation reactors in which end products contained in the mixed stream are formed.
EFFECT: improved method of obtaining acrolein, acrylic acid, methacrolein or methacrylic acid as the desired product.
2 cl, 4 tbl, 2 ex
SUBSTANCE: invention relates to an improved method for heterogeneous catalytic gas-phase partial oxidation of at least one initial organic compound selected from propylene, isobutene, acrolein, methacrolein, propane or isobutane with molecular oxygen on a fixed catalyst bed freshly put into a reaction space, in which, for partial oxidation, a reaction gaseous mixture containing at least one initial organic compound and molecular oxygen is passed through the fixed catalyst bed, and reaction heat is removed via indirect heat exchange with a liquid heat carrier directed outside the reaction space, and as the quality of the fixed catalyst bed falls with operation time, not all, but part of the fixed catalyst bed is replaced with part of a replacement fixed catalyst bed in order to restore the quality of the fixed catalyst bed, where the specific volume activity of the replacement part of the fixed catalyst bed is lower than that of the replaced part of the fixed catalyst bed in its fresh state.
EFFECT: deterioration of the quality of the fixed catalyst bed with operation time is compensated for by replacing part of the fixed catalyst bed with a replacement part of the fixed catalyst bed, where the rate of deactivation of the catalyst is lowest in the disclosed method.
10 cl, 2 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of phenols alkylated at ortho-position as parent substances used in preparing organic compounds. Method for preparing o-alkylphenols is carried out by interaction of phenol with alkanol at increased temperature in gaseous phase in the presence of metal oxide as a catalyst. Process is carried out for at least two stages in the molar ratio alkanol : phenol about ≤0.4, preferably, from 0.2 to 0.4 at each stage. Methanol is used as alkanol usually using aluminum gamma-oxide as a catalyst and process is carried out at temperature 300-400°C. Reaction products are separated by distillation. Invention provides increasing yield the end product due to enhancing selectivity with respect to o-alkylphenol.
EFFECT: improved method for preparing.
9 cl, 4 tbl, 2 ex
SUBSTANCE: invention relates to chemistry of adamantane derivatives and specifically to a method of producing 2-(adamantyl-1)-4-bromophenol, which is an intermediate product in the synthesis of adapalene - 6-[3-(adamantyl-1)-4-methoxyphenyl]-2- naphthoic acid, which is widely used in dermatology as an effective anti-acne agent. The method of producing 2-(adamantyl-1)-4-bromophenol involves reacting 4-bromophenol with 1-adamantanol and 1-bromoadamantane in molar ratio of 2:1:0.1, respectively, in the presence of 0.01 ml water or without water at temperature of 110-130°C for 2 hours.
EFFECT: simple, ecologically clean method of producing 2-(adamantyl-1)-4-bromophenol without using a catalyst and a solvent.
SUBSTANCE: invention relates to a method for the production of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate, comprising an interaction under reaction conditions between 5-tert-butyl-3-methylcatechol (BMC) and triethylamine and a member selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid derivative, where the derivative of the aromatic carboxylic acid is an aromatic acyl halide, an aromatic anhydride, an aromatic carboxylate salt or any combination thereof; and where the aromatic carboxylic acid is benzoic acid; and forming a composition comprising 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD). Synthesis pathways for a precursor to 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate are provided. The precursor is 5-tert-butyl-3-methylcatechol.
EFFECT: simple and cost-effective method with high yield.
10 cl, 2 dwg, 6 ex