The method of purification of alkyl compounds of non-transition elements of groups ii - vi of the periodic system from the admixture of alkyl halide by distillation and distillation column for its implementation
(57) Abstract:The invention relates to the field of deep purification of organic compounds, in particular to the purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from the admixture of alkyl halide by rectification and improvement of distillation columns for its implementation. The method is carried out by continuous processing alkyl compounds in the process of rectification of metallic magnesium. Distillation column for purification of the above alkyl compounds from admixture of alkyl halide includes cube, rectificatory section, a cylinder, a condenser and contains an additional section, filled with a nozzle made of magnesium metal, which irreversibly binds to the admixture of alkyl halide in the non-volatile alkylsalicylate. 2 S. p. f-crystals, 1 Il., 3 table. The invention relates to the field of deep purification of substances, in particular to the purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from primacy alkyl halide.Alkyl compounds are formed non-transition elements of groups II-VI and are widely used for the growth and doping of semiconductor structures I purity: they severely limited the concentration of metal impurities ( 104-10-6wt.%), as well as oxygen and halogenated substances ( 10-2- 10-4wt.%).Binding reagent in the synthesis of all alkyl compounds is an alkyl halide. For complete alkylation and enhance the yield of the target products this halogen-containing reagent is taken in excess. Ultimately, this leads to contamination of alkyl halide compounds with alkyl and makes necessary further purification of this mixture.A known method of purification of alkyl compounds from alkyl halide by treatment containing this admixture product metal magnesium . The method is implemented by heating of trimethylaluminum with magnesium flakes to a temperature of 40oC. this contained in the alkyl halide is bound magnesium in low volatile alkylhalogenide magnesium (Grignard reagent):
RX + Mg __ MgX, (1)
R is an alkyl radical (CH3C2H5and so on);
X is halogen (Cl, Br, J).The target product is easily separated from the formed Grignard reagent in the process followed by simple distillation.However, the described reaction proceeds effectively only at a high concentration of alkyl halide. As% approaches zero.Low degree of purification is the main disadvantage of this method.There is a method of deep cleaning alkyl compounds by distillation . Rectification is carried out on Packed columns of periodic action. To protect alkyl compounds from oxidation and thermal decomposition of their rectification is carried out in an atmosphere of inert gas under reduced pressure.On the basis of significant differences in volatility halide Akilov and obtained on the basis alkyl compounds expected high efficiency of this method. However, in practice this is implemented only for alkyl compounds, group IV (e.g., tetramethyl - or tetraethyl - tin or lead). These substances are fairly easy to clean by rectification method from the admixture of the corresponding halide Akilov (iodotope methyl or ethyl) to the content of 10-3- 10-4wt.%. Alkyl same compound II and VI groups III and V groups form with metal-halide alkilani molecular complexes:
RhE + RX __ RhE RX (2)
E - the element II-VI groups of the Periodic system;
h - stoichiometric ratio.These complexes are thermally unstable and reversible rotting in prte throughout the process of evaporating device ( 10-1wt.%). As a result, the concentration of the alkyl halide is reduced very slowly and only at the end of the selection of the main fraction is possible to obtain a small amount of product with the content of this impurity level 1 - 510-2wt.%.Low cleaning efficiency is the main disadvantage of this known method, selected as a prototype of the present invention as the most close to him on purpose and technical nature.The problem solved by the invention is to increase the depth of the distillation purification of alkyl compounds from admixture of alkyl halide and improvement of distillation columns for its implementation.The problem is solved in that in the known method of purification of alkyl compounds by distillation alkyl compound in the process of rectification continuously treated with metallic magnesium. For this purpose the upper part of the distillation column fill nozzle, made of magnesium (magnesium shavings or pellets). The admixture of alkyl halide is more volatile than the base material, and is concentrated in the upper part of the distillation column. Here she is actively vzaimodeistvuyushchego binding of additional quantities of alkyl halide with magnesium depth cleaning alkyl compounds of this impurity increases as compared to distillation purification by a known method (prototype), and compared to treatment with magnesium initial mixture in a known manner (similar).Purification of alkyl compounds from admixture of alkyl halide according to the invention, carried out on a column, which is different from the known Packed distillation columns have additional sections filled with magnesium nozzle. Additional section is placed in the upper part of the column between the head of the capacitor and the primary rectificarse section. Diagram of a distillation column according to the invention shown in the drawing. Column consists of the lower cube 1, rectificarse section 2, filled prismatic mass transfer nozzle of nichrome, additional sections 3, filled with magnesium nozzle in the form of a spiral shavings, head of the capacitor consisting of the refrigerator 4 and valve phlegmy 5 and otbornye distillate 6 and cranes 7-12. Cube ratificirebisa and an additional section of the column is equipped with a resistive heater type 13-15. To control the hydrodynamic regime at the top and bottom placed counters drops of phlegmy 16, 17, and to maintain the temperature of thermocouple 18, 19. The pressure in the column was measured by the pressure gauge 20 and podderjivaet">The technique works on the column was as follows: the column was pumped booster pump to a pressure of 0.1 mm RT.article Then in the cube columns were filled alkyl compound to be cleaned from the alkyl halide. The column was filled with an inert gas to the operating pressure, which is determined by the physico-chemical properties of the purified alkyl compounds (boiling point, and heat resistance). After that, he joined the electrical heating Cuba, rectificarse and additional sections through the refrigerator head condenser was supplied with running water and the column was introduced into a working mode. Within 3-5 h column worked in bestporno the mode in which the distillate from it was not shown. At this time, all of the condensate is returned to the column and interact therein alkyl halide with magnesium nozzle. This is followed by the selection of the pure product, which is collected in the receiving vial.The method of purification of alkyl compounds from primacy alkyl halide by distillation with continuous processing of the product metal magnesium, and distillation column for its implementation, contains an additional section, filled with magnesium density - continuous processing of the purified alkyl compounds in the process of rectification of metal magnesium and an introduction to the additional column sections, filled with magnesium nozzle, where this processing, are essential features of the invention, for enhancing the purity of the target product by admixture of alkyl halide.The following are specific embodiments of the invention.Example 1. Purification of trimethylaluminum from impurities iodotope bromide.Distillation purification of trimethylaluminum was carried out on a column whose schema described above. Height rectificarse section of the column was 150 cm, and the height of the additional sections - 50 cm Diameter of these sections was 25 mm Main ratificirebisa section columns filled prismatic nozzle, collapsed from nichrome wire. The element size of the nozzle was 3 3 3 mm. Additional section filled with magnesium shavings with the size of the individual elements 3 3 1 mm Cube of the column is filled to 2/3 of its volume and has a capacity of 3 liters of purified substances. The column efficiency, determined in a model mixture of benzene-dichloroethane, was 30 theoretical stages of separation.Rectification of trimethylaluminum was carried out in an atmosphere of inert gas (argon) at a pressure of 760 mm RT.article and temperature 115-128oC. the so, to all the nozzle is uniformly moistened with phlegm and the rate of irrigation in the lower part of the column was 60 drops/min, and in the top - 40 drops/min Selection of distillate was started after 5 h of the column at the rate of 2 to 3 drops/minThe impurity content iodotope bromide in the source trimethylaluminum and the product purified according to the model, the prototype, and in accordance with the invention, are shown in table 1.From the table it is seen that the invention provides a 20 - 30 times to reduce the impurity content iodotope bromide in comparison with the known purification methods.Example 2. Cleaning diethylzinc from impurities iodine ethyl.Cleaning of diethylzinc carried out as in example 1, but the process of rectification is carried out at a pressure of 150 mm RT.article and a temperature of 65 - 75oC.The impurity content in the resulting product are shown in table 2.From the table it is seen that the invention provides a 10 - 20 times to reduce the impurity content of iodine in ethyl diethylzinc compared with known methods.Example 3. Purification of tetraethyl lead from the admixture of ethyl chloride.Cleaning of tetraethyl lead was performed as in examples 1 and 2, but the process rectify the CSOs ethyl in the resulting product are shown in table 3.The table shows that for tetraethyl lead, which is derived from the IV group, good results and conventional rectification (the prototype), since these compounds do not form complexes with metal-halide alkilani. However, in this case, the invention allows 5 times to increase the purity of tetraethyl lead in comparison with the prototype.Thus, the invention can significantly improve the purity of the alkyl compounds according to their content of impurities alkyl halide. 1. The method of purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from the admixture of alkyl halide by distillation, characterized in that in the process of rectification alkyl connection continuously treated with metallic magnesium.2. Distillation column for purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from impurities alkyl halide, including cube, rectificatory section and the head of the capacitor, characterized in that it contains an additional section, filled with a nozzle made of magnesium metal, which is placed between rectificarse section and a cylinder capacitor.
SUBSTANCE: plate comprises base with openings that receive valves made of plates provided with holes. The caps underlie the holes. The height of the caps increases toward the plate opening. The caps point to the direction opposite to that of the plate opening.
EFFECT: enhanced efficiency.
FIELD: oil-processing industry; methods of trapping of ejections of foul gases from rectors of a carbonization.
SUBSTANCE: the invention is pertaining to the field of the oil-processing industry and may be used at trapping the harmful gases ejections from the reactors of carbonization. The method provides for the preliminary separation of the products of the heating-up of the reactors, the coke steaming and cooling in the additional rectifying column with extraction of the intermediate fractions guided into the basic rectifying column, the water condensate and the gas. At that for separation into the additional rectifying column they feed the products of the heating-up with the flow temperature below 240°С and the products of the steaming and cooling with the flow temperature of 150-240°С, and as the intermediate fractions gate out the low quality fractions at -180°С, 110-180°С and +180°С. The products with the flow temperature of above 240°С may be guided directly to the basic rectifying column, and the products with the flow temperature below 150°С - in the separator. It is preferable to conduct separation in the separator at the temperature of 80-140°С and duration of 1-3 hours. The method allows to raise the quality of separations of the trapped harmful ejections, in particular, to reduce the share of petroleum in the water condensate and to decrease the petroleum products losses and to increase efficiency of the process of trapping, as well as improve the ecological indexes of the process of the retard carbonization.
EFFECT: the invention ensures the improved quality of separation of the trapped harmful ejections, reduction of the share of petroleum in the water condensate, the decrease of the petroleum products losses, the increased efficiency of the process of trapping, the improved ecological indexes of the process of the retard carbonization.
8 cl, 1 ex, 1 tbl, 1 dwg
SUBSTANCE: proposed heat exchange column contact plate comprises a casing attached to the plate base and defoamer made from permeable material, for example, a screen closing the overflow device casing inlet, the said defoamer being fitted inside the overflow device casing. Note here that defoamer lower edge is attached to the casing wall below the plate base level so that a defoaming space is arranged between the casing wall and defoamer surface facing the incoming flow. Defoamer upper edge is arranged above the level of gas-liquid mix on the said plate and defoamer upper part has a gas outlet. Contact plate is also proposed made of a base with overflow device of the afore-described design.
EFFECT: expanded liquid loads range at higher efficiency of heat-and-mass transfer on contact plate and in apparatus.
12 cl, 5 dwg
FIELD: technological processes.
SUBSTANCE: invention may be used to produce pure compounds of niobium and tantalum. Device for production of pure niobium pentachloride consists of electric furnace 1, cube-evaporator 2, equipped with unit of continuous loading of initial raw materials 6, enameled shell section 3, quartz rectification tower 4, L-shaped reflux column with reflux separator 5, to which the second rectification tower 7 is connected with heated cube-evaporator 8, which is made of quartz sand and is equipped with unit for extraction of pure niobium pentachloride 9. Raw materials are continuously supplied to cube-evaporator 2 of the first tower via unit of continuous loading 6. Condensate enriched with low-boiling components and containing niobium pentachloride, is separated in reflux column 5 into three parts. One part of condensate is returned to quartz rectification tower 4. Accumulated high-boiling components, containing tantalum, are periodically drained from cube-evaporator 2. The second part of condensate enriched with low-boiling components is extracted as intermediate product from reflux column 5. The third part of condensate is sent to the second rectification column 7 for purification from low-boiling components. Pure niobium pentachloride is sent to quartz cube-evaporator 8 and is continuously drained via extraction unit 9.
EFFECT: invention makes it possible to provide for purification of niobium pentachloride to the level of stable content of tantalum in the main fractions of not more than 0,0015% during the whole process of rectification.
2 cl, 3 dwg, 2 ex
FIELD: oil and gas production.
SUBSTANCE: bottom valve (1) for a plate column comprises a port (2) in a plate (10) for steam passage and a valve body (3) matched with an edge (20) of the sluice port. The valve body consists of a pressure plate (4) and guide lugs (5) provided on the edge of said plate and oriented vertically downwards. Said guide lugs are provided with grabs (6) for anchoring the valve body on the port edge. Barring the cone-shaped down-directed cambers (40), if any, the plate edge lays on a plate plane. The external surface of each guide lug has a lift zone (50) perpendicular to the plate plane. A material and shaping of the valve body considering its installation in the sluice port (2) are specified so that installation involves elastic and probably partially plastic deformation of the valve body. Such possible deformation on the mounted valve body can be eliminated by force impact on the pressure plate, thereafter being observed as insignificant residual deformation only. The pressure plate can contain hitches, e.g. in the form of flutes, grooves or apertures to facilitate deformation. There are available a plate column with the plates (10) containing a considerable number of bottom valves (1), and a method for mounting the valve bodies (3) in such bottom column.
EFFECT: simplified mounting and dismounting of the bottom valve.
10 cl, 9 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to separators of vapor (gas)-fluid systems and may be used in mass exchange processes in chemical, petrochemical and food industries. Proposed plate consists of horizontal sheet with bubbling elements, overflow devices including intake pocket, overflow and drain banks. Integral independent overflow device is rigidly secured in plate sheet opening. Intake pocket is additionally closed from below by guide plate. Overflow device deflector is downed into intake pocket to form clearance with guide plate whereto rigidly secured is drain bank so that its top edge located below deflector lower end form fluid passage, its cross section area making at least that of said clearance. Intake pocket sidewalls allows fluid overflow on, primarily, column walls. Functionally relates elements of independent overflow device create a static hydraulic lock.
EFFECT: higher efficiency, reduced labor input, higher reliability.
5 cl, 3 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to mass-and-heat exchange hardware, particularly, to rectifiers and absorbers and may be used in petrochemical and chemical, oil and gas industries. Proposed rectifier tower comprises body with process unions, trays with vapor and overflow branch pipes, and height-adjustable bubble-cap trays. Top end of every overflow branch pipe is secured in tray to radially relative to the latter while its bottom end is furnished with perforated disc and barrel concentric with overflow branch pipe to make hydraulic lock therewith.
EFFECT: higher efficiency of tower operation.
FIELD: process engineering.
SUBSTANCE: invention relates to perfected contact stages for bringing steam in contact with fluid. Invention relates to contact stage 12 for bringing steam in contact with fluid that comprises: pair of rows 24 of entrainment traps spaced apart and including multiple separate entrainment traps 40, joint flanges 74 extending above top surfaces 45 of the latter. Also it comprises pair of accumulation pans 26 arranged at alternating said rows 24, drain barrel 22 arranged between said rows 24 to make along with inlet surfaces 42 of entrainment traps 40 and pair of channels 56 for cocurrent flows on opposite side of barrel 22. Also it comprises connection angle-pieces 75 extending above top parts of said angles 74 of entrainment traps 40. Note here that connection angles 75 cover joint flanges 74 and adjacent sections 72 of drain barrel 22 to attach top parts of entrainment traps 40 to drain barrel wall 22. Note also that lower parts 97 of entrainment traps 40 are secured to pans 26. Invention covers also device and method for cocurrent contact between steam and fluid.
EFFECT: simplified assembly, notable increase in stiffness, higher efficiency, lower probability of fluid leaks.
13 cl, 13 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to mass-and-heat exchange hardware, particularly, to rectifiers and absorbers and may be used in petrochemical and chemical, oil and gas industries. Proposed rectifier tower comprises body with process unions, trays with vapor and overflow branch pipes, and height-adjustable bubble-cap trays. Horizontal edges of cap cutouts are equipped with vanes arranged radially outside in horizontal plane.
EFFECT: higher efficiency of mass exchange.
SUBSTANCE: invention relates to an improved method of producing para-tert-butylphenol by alkylation of phenol with isobutylene on a heterogeneous sulphocationite catalyst, separating the reaction mass containing phenol, para-tert-butylphenol, ortho-tert-butylphenol, 2,4-di-tert-butylphenol and high-boiling impurities by vacuum rectification in two columns with collection of phenol and ortho-tert-butylphenol in distillate form. The reaction mass is subjected to rotory-film evaporation to separate high-boiling impurities therefrom; the commercial product is separated in an additional rectification column in distillate form; absorption trapping of uncondensed para-tert-butylphenol vapour is carried out on a vacuum line; the bottom residue of the commercial product separating column, which contains 2,4-di-tert-butylphenol and para-tert-butylphenol, is recycled to the step for alkylating phenol with isobutylene. The invention also relates to an apparatus for realising the method of producing para-tert-butylphenol.
EFFECT: method enables to obtain a product with high purity and high output.
2 cl, 1 dwg
FIELD: chemistry of organometallic compounds, chemical technology.
SUBSTANCE: invention relates to the improved method for preparing the chelate compound bis-(1-vinylimidazole)zinc diacetate (I) representing the medicinal preparation of acizol that is the effective antidote and antioxidant. Method for preparing the compound (I) is carried out in the absence of organic solvents at temperature 20-35°C in the mole ratio 1-vinylimidazole : zinc diacetate in the range from 10:1 to 3:1. Method provides exclusion fire hazard and explosion hazard solvent from the technological process and enhancement of the yield of highly pure acizol satisfied for Pharmacopoeia requirements.
EFFECT: improved method for preparing.
2 cl, 4 ex
FIELD: luminescent materials.
SUBSTANCE: invention provides novel electroluminescent material comprised of injecting layer, metal chelate complex-based active luminescent layer, hole-transition layer and hole-injecting layer. Luminescent substance is selected from oxyquinolate metallocomplexes of zinc 8-hydroxy-2-methoxyquinolate and zinc 8-hydroxy-2-methylquinolate. Electroluminescent material shows emission in green spectrum region.
EFFECT: increased heat resistance and widened choice of stable green-emitting materials.
2 cl, 3 ex
FIELD: organic chemistry, medicine, oncology.
SUBSTANCE: invention relates to photosensitizing agents used in photodynamic therapy of neoplasm and some other diseases. Invention describes tetraazachlorines of the general formula: wherein R1R2 mean -C6H4; R3 = R4 = R5 mean -CH3; M means HH (H2TBTAC); R1R2 means 1,2-C10H6; R3 = R4 = R5 mean -CH3; M means Zn(Zn-1,2-TNTAC); R1 = R2 mean -C6H5; R3 = R4 = R5 mean -CH3; M means HH (H2TACPh6); R1 = R3 mean hydrogen atom (H); R2 =R4 mean -C6H5; R5R5 mean -CH2N(CH3)CH2; M means HH (H2PyrTACPh4); R1R2 mean 4-C(CH3)3C6H3; R3 = R4 mean hydrogen atom (H); R5R5 mean -CH2N(CH3)CH2; M means HH (H2TBtTACPyrN-Me) used as photosensitizing agents in the near IR-region of spectrum for carrying out the photodynamic therapy. These photosensitizing agents possess the intensive absorption in spectral region 710-750 nm and can be used in treatment of deep tumor tissues by the photodynamic therapy method.
EFFECT: valuable medicinal properties of compounds.
1 cl, 4 ex
FIELD: production of high temperature superconductors.
SUBSTANCE: invention relates to electrochemical synthesis of metal β-diketonates, in particular acetylacetonates. Synthesis of Cu(II) and Zn(II) acetylacetonates in carried out by electrolysis of acetylacetone solution and base electrolyte in acetonitryl in ratio of (1:10):0.5:100, with electrodes made of metal presenting in produced acetylacetonate, at current density not more mA/cm2 by using pulse current. Pulse time is controlled by pulse forming unit connected in parallel to elecrtolyzer. As base electrolyte preferably lithium perchlorate or lithium chloride is used.
EFFECT: controlled process for production of metal acetylacetonates.
5 cl, 2 ex, 1 dwg