The reactor for the production of allylchloride
(57) Abstract:The reactor includes a feed area of the initial reagents, tubular zone, connected to the feeding zone of the initial reagents, input the initial reagents and the exhaust device. The feeding zone of the initial reagents and the tubular reactor form a closed circuit in the form of a vertical cylindrical apparatus of the type "pipe in pipe". In the cavity of the lower portion of the inner cylinder has a device for forced circulation with the location in which is formed a closed loop input device propylene to the forced circulation device, the input device of chlorine after the input device, propylene, prom device that is made in the form of a series of holes in the wall of the outer cylinder, covered on the outside of the ring collector in the form of a shirt with a branch pipe before input device propylene. The use of this invention provides increased selectivity of the process, increasing the yield of the target product allylchloride. 1 C.p. f-crystals, 1 Il. The invention relates to a technology for chlorohydrocarbons by the chlorination of olefins, in particular to a device for receiving allylchloride used in the form of ª of allylchloride used in industry method of high-temperature gaseous chlorination of propylene gaseous chlorine. The chlorination process, usually carried out at a temperature 400-530oC without removal of heat of reaction, at a temperature of the propylene feedstock 260-400oC and at a molar ratio of propylene and chlorine of not less than 1.2:1.0 in.Known reactor obtain allylchloride interaction of propylene and chlorine, with more than one insertion openings of propylene and more than one hole for the separate input of chlorine, the relative position of which is determined by the equation
0,5 L/(dp+dc) 20,
where dp is the diameter of the insertion openings of propylene;
dc - diameter of the insertion openings of propylene;
L is the distance between the centers of the holes of both types.Use nozzles in which the channels for supplying the reagents located on two circles - the outer (propylene) and internal (chlorine) in parallel to the Central axis. The nozzles have a flat or conical cut, and the flow direction defined by the configuration of the apertures may overlap and form an angle in the range of 30oand the angle formed by the direction of flow and the axis of the nozzle equal 0-60o/U.S. patent 5.367.105, 22.11.94./.Chlorination of propylene in the described reactor is carried out at a linear speed of passage through the openings DL is P>2.The disadvantage of the reactor is the presence of areas of high concentrations of chlorine in the reaction space, leading to pereplanirovki propylene to high products and coke.Known reactor to obtain allylchloride made in the form of a vertical metal tube with a ratio of height to diameter 15:1-30:1, is provided in the lower part of the system ogladania and continued top nozzle ejector type, inside the shape of a truncated cone, extending from top to bottom. The reactor consists of three zones: zone a - truncated cone - highly turbulent zone, limited downwards by the intersection of imaginary extensions forming a cone with the walls of the tube; zone b - zone mixing with intensive recycling; zone From the remainder of the tube, which is the area of the mixing piston type. Above zone a is the input system of reagents or three concentric cylinders surrounded by a water jacket, through duzu in the reactor comes chlorine, and through the annular section between duty and the external cylinder - propylene. /Romanian patent N 57828, 25.12.74/.Chlorination of propylene in the specified reactor is carried out at a temperature of 450-530oC and a pressure of 1-3 kg/cm2.I chlorination process. Which leads to additional energy consumption for preheating of propylene and high education high products and coke.The closest reactor of the same purposes of the claimed device according to the totality of symptoms is the reactor that includes a feed area of the initial reagents, tubular zone, connected to the feeding zone of the initial reagents, input the initial reagents and outlet for the reaction products /WO 96/37450/.Getting allylchloride in the specified reactor is realized by the interaction of propylene and chlorine when a molar ratio of at least 2.5:1 and at a temperature of 400-525oC.For reasons that impede the achievement of specified following technical result when using the known reactor, taken as a prototype, is that in the known reactor receiving allylchloride carry out the interaction of propylene with chlorine at a temperature of 400-525oC and at this temperature the mixture, i.e., a large concentration of chlorine in the mixing zone of the source reagents at high temperatures preclude optimal conditions considered horizontally isothermal surface process. The result is a large number the of conditions considered horizontally isothermal surface process and ensure a relatively low concentration of chlorine in the reaction mass by mixing reagents.The technical result in the use of the invention is expressed in increasing the selectivity of the process to increase the yield of the target product lilliard.This technical result in the implementation of the invention is achieved in that in the known reactor peculiarity lies in the fact that the flow of reagents and the tubular reactor form a closed circuit in the form of a vertical cylindrical apparatus of the type "pipe in pipe", in the cavity of the lower portion of the inner cylinder which has a device for forced circulation with the location in which is formed a closed loop input device propylene to the forced circulation device, the input device of chlorine - after input devices propylene, the discharge device made in the form of a series of holes in the wall of the outer cylinder, covered on the outside of the ring collector in the form of a shirt with a branch pipe, before input device propylene. In addition, the peculiarity lies in the fact that the input device of chlorine made in the form of radially perforated pipes fixed on the floor, for the passage of chlorine, the shaft of the device for forced circulation.In the study otnay design when implementing the process of obtaining allylchloride.The design of the reactor shown in the drawing.The reactor for the production of allylchloride is a vertical type device "pipe in pipe", which formed the outer 1 and inner 2 cylinders. The outer cylinder 1 ends with elliptical bottoms. On the walls of the upper floor are the reflectors 8. In the center of the bottom plate is a pipe 7 through which passes coaxially rotating shaft 5. At the end of the shaft 5 is located impeller 4 t with blades. Over the shoulder blades on the inner wall of the cylinder is fixed straightener apparatus 3.The rotating shaft 5, the impeller 4 blades and a rectifying device 3 form a device for forced circulation, which provides circulation of the reaction gases in a closed circuit formed by the internal volume of the cylinder and the space between the inner and outer cylinders.The rotating shaft 5 is made hollow. On the shaft under the blades of the impeller, mounted radially perforated branch pipes 7a, communicating with the internal space of the shaft 5. The hollow shaft 5 and the nozzles 7a to form the input device of chlorine with the location of it when the input device propylene.Enter propylene in the reactor oscom 7 and the rotating shaft 5.The lower part of the inner and outer cylinder, an input device of chlorine, the connection of the input of propylene and device for forced circulation form the feed area of the initial reagents.The inner cylinder and the space between the inner and outer cylinders forming the tubular reactor.The conclusion of the reaction gases from the reactor is carried out on the lower part of the outer cylinder, covered with annular manifold 6b in the form of a shirt with a branch pipe 6.The reactor operates as follows.Propylene, preheated to a temperature of 200-400oC, is fed into the reactor through pipe input propylene. In the feed area of the source reagents propylene is mixed with the circulating gases with a temperature of 420-470oC at a volume ratio of circulating gases to the total number of initial reagents (multiplicity circulation), equal to 5:20, with the relatively cool propylene removes excess exothermic heat of reaction. Through the input device of chlorine serves chlorine with a temperature of 20-50oC. the Volume ratio of the initial reagents is 2-4: 1, respectively. In a tubular reactor process for the chlorination of propylene is carried out at a temperature of 420-the m the reactor of this design allows for the chlorination of propylene in a narrow temperature as close as possible to the optimal one. Improving conditions considered horizontally isothermal surface is provided by the high rate of circulation of the reaction gases through the device for forced circulation.2. That mixture of propylene with chlorine is carried out at low concentrations of chlorine in the feed area of the initial reagents, and it is provided both by dilution of the initial reagents circulating reaction gases, and due to the large ratio of circulation, which ultimately leads to increased yield of the target product.3. In reducing energy consumption for recycling propylene. 1. The reactor for the production of allylchloride, including the feeding zone of the initial reagents, tubular zone, connected to the feeding zone of the initial reagents, input the initial reagents and outlet for the reaction products, wherein the feeding zone of the initial reagents and the tubular reactor form a closed circuit in the form of a vertical cylindrical apparatus of the type "pipe in pipe", in the cavity of the lower portion of the inner cylinder which resoloved propylene until a forced circulation, input devices chlorine - after input devices propylene, the discharge device made in the form of a series of holes in the wall of the outer cylinder, covered on the outside of the ring collector in the form of a shirt with a branch pipe before input device propylene.2. The reactor under item 1, characterized in that the input device of chlorine made in the form of radially perforated pipes fixed on the floor, for the passage of chlorine, the shaft of the device for forced circulation.
FIELD: chemical industry, in particular method for production of value products from lower alkanes.
SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.
EFFECT: method of increased yield.
3 cl, 4 ex
FIELD: organic chemistry, chemical technology, petroleum-chemical synthesis.
SUBSTANCE: invention relates to a method for preparing liquid chloroparaffins. Liquid chloroparaffins are prepared by the hydrochlorination reaction of olefin with hydrogen chloride in the presence of a catalyst wherein α-olefins of (C18-C28)-fraction are used as olefins and water is used as a catalyst taken in the amount 0.02-0.03 wt.-%. The hydrochlorination reaction is carried out at temperature 20-25°C and the volume feeding rate of hydrogen chloride 21-24 h-1 followed by chlorination of the prepared reaction mass with chlorine in the presence of zeolite CaX taken in the amount 2-3 wt.-% at temperature 80-90° and the volume feeding rate of chlorine 19-22 h-1. Using this process promotes to increasing conversion of HCl and chloroolefin, enhances the yield of products, simplifying and reducing cost of the process.
EFFECT: improved preparing method.
2 cl, 7 tbl, 7 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to processes for the oxidative halogenation reaction of hydrocarbons, in particular, for synthesis of haloidmethanes, their following processing to value chemical compounds. Method involves contacting methane, halogenated methane or their mixture with halogen source and oxygen source in the presence of catalyst to yield halogenated C1-hydrocarbon having more amount of halogen substitutes as compared with the parent hydrocarbon, Process is carried out at temperature above 200°C but less 600°C and under pressure 97 kPa or above but less 1.034 kPa and at the volume rate of raw feeding above 0.1 h-1 but less 100 h-1. Catalyst comprises rare earth metal halide or oxyhalide no containing iron and copper. The atomic ratio of rare-earth element to iron or copper exceeds 10:1 under condition that if catalyst comprises cerium in the amount less 10 atomic percent of the total amount of rare-earth components then catalyst comprises also one additional rare-earth element. Reacting hydrocarbon is chosen from the group consisting of methane, chloromethane, bromomethane, iodomethane, dichloromethane, dibromomethane, diiodomethane, chlorobromomethane and their mixtures. The molar ratio of hydrocarbon to halogen is above 1;1 but less 20:1 and that to oxygen is above 2:1 but less 20:1. The reaction mixture comprises additionally a diluting agent as nitrogen, helium, argon, carbon monoxide or dioxide or their mixtures. Formed methyl chloride or methyl bromide can be fed to the hydrolysis step to yield methyl alcohol or used in process of catalytic condensation to form light olefins and/or gasolines. It is possible contacting methyl halide with the condensation catalyst to form ethylene and the following preparing vinyl halide monomer, for example, vinyl chloride or acetic acid under carbonylation conditions. Invention provides enhancing output of the process at the expense of using the effective modified catalyst based on rare-earth elements.
EFFECT: improved halogenation method.
33 cl, 1 tbl, 1 ex
FIELD: chemical industry; apparatuses for production of the chlorinated allyl.
SUBSTANCE: the invention presents the reactor for production of the chlorinated allyl intended for realization of the method of production of the chlorinated allyl by the direct gaseous phase chlorination of the propylene. The reactor includes the closed circuit of circulation of the reaction gases, the devices of injection of the source propylene and chlorine, the device of the forced circulation of the part of the reaction gases and the device of withdrawal of the other part of the reaction gases. At that the closed circuit of the reaction gases circulation forms the jet pump, which includes in series connected the reception chamber, the mixing chamber and the diffuser, and the pipe of the circulation circuit connecting the outlet of the diffuser with the appropriate inlet of the reception chamber of the injector and acting as the main reaction zone of the ideal displacement with the presence time of 0.7-0.9 s, in which the scatter of the temperatures does not exceed ±10°С. The reception chamber contains the nozzles used as the devices for injection of the source propylene and chlorine. The jet pump ensures fulfillment of the concerted functions: introduction of the streams of the source propylene and chlorine, which are the working injecting streams; the forced circulation pump with the repetition factor of 5-10 of the reaction gases stream, which is the injected stream; the high-velocity mixer and the preheater of the source reactants in the mixing chamber due to the strong turbulence during (0.01-0.04)s, which is formed by the combination of the nozzles of the injected gases at the arrangement of the nozzle/ nozzles of the chlorine coaxially to the main nozzle of the propylene arranged on the shaft of the mixing chamber. The technical result of the invention is, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.
EFFECT: the invention provides, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.
1 ex, 1 dwg
FIELD: chemical industry; methods of production of the chloroform.
SUBSTANCE: the invention is pertaining to the method of production of the chloroform by chlorination of methylene chloride in the liquid phase at the temperature of 35-50°С at photoinitiation with the subsequent separation of the chloroform by rectification. At that before the chlorination methylene chloride is saturated with chlorine, and for chlorination feed the solution of chlorine in methylene chloride. The methylene chloride is saturated in the darkness, the saturation is conducted by the electrolysis chlorine with separation of the volatile components - hydrogen, nitrogen, oxygen present in the electrolysis chlorine, from the solution of the chlorine in methylene chloride at the temperature being within the limits from minus 10 up to plus 5°С, in the counter-currentmode at sprinkling of the absorption column by the cooled methylene chloride or in the bubbling mode in the conditions of bubbling by the electrolysis chlorine through the cooled methylene chloride. The technical result of the invention is suppression of the inhibition of the process of chlorination of the methylene chloride at usage of the electrolysis chlorine, the increase of conversion of chlorine and selectivity for chloroform.
EFFECT: the invention ensures suppression of the inhibition of the chlorination process of methylene chloride at usage of the electrolysis chlorine, the increased conversion of chlorine and selectivity for chloroform.
5 cl, 4 ex, 1 tbl
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for conversion of hydrofluorocarbons, such as HFC-227, HFC-236, HFC-245, HFC-125, HFC-134, HFC-143 and HFC-152 and their corresponding isomers to a perhalogenated compound. The process is carried out by substitution of one or some hydrogen atoms in hydrofluorocarbon with halogen atom of a halogenating agent to yield perhalogenated compounds. The substitution occurs at temperature 150-400°C in the mole ratio of halogenating agent and hydrofluorocarbon = 0.16-22 in the presence of a solid substrate wherein a halogenating agent comprises one atom among Br, Cl and J, and one of components of solid substrate can represent activated carbon, Fe, Cu, Al, clay and metal oxides. Method for conversion of hydrofluorocarbons can involve additionally interaction of perhalogenated compound with a cleaving reagent to form fluoromonomer, such as hexafluoropropene, pentafluoropropene, tetrafluoroethylene, difluoroethylene and trifluoropropene. Invention provides admissible degree of conversion and selectivity.
EFFECT: improved method of conversion.
13 cl, 15 tbl, 11 ex
SUBSTANCE: invention concerns method of obtaining methyl chloride by selective catalytic chlorination of methane, involving throughput of a source reaction gas mix containing at least methane and chlorinating agent in the form of either elementary chlorine or a mix of chlorine hydride with oxygen, through at least one catalyst layer. At that, the catalyst features additionally active centres with increased acidity and deuterium/hydrogen exchange depth not less than 10% at the temperature of 350-355°C in the deuterium and hydrogen mix containing 0.6% of hydrogen, 0.6% of deuterium, 0.05% Ar and 98.75% nitrogen, at the volume deuterium-hydrogen mix feed rate of 20000 hours-1 in the thermal regulated reaction mode at the heating rate of 10 K/minute. Active catalytic component is either platinum or copper, or silver. Catalyst carrier is microfibre of diametre of 1 to 20 micron, which can be structured in either non-woven or pressed material similar to wad or felt, or fibre of diametre of 0.5-5 mm, or woven material with lattice similar sateen, canvas, or openwork, with weave diametre of 0.5-5 mm.
EFFECT: high activity and selectivity of methane chlorination to methyl chloride at lower temperatures without production of polychlorinated hydrocarbons.
6 cl, 6 ex
SUBSTANCE: proposed method of producing chloromethanes involves gas-phase thermal chlorination of methane, condensation of obtained chloromethanes, removal of methyl chloride from the condensate, obtaining a mixture of chloromethanes, distillation of this mixture with separation of the light fraction, liquid-phase chlorination of the light fraction with photochemical initiation, combination of vat fractions with products of liquid-phase chlorination, and separation of individual chloromethanes using known methods.
EFFECT: reduced formation of tetrachloromethane and increased selectivity on chloroform.
2 cl, 1 tbl, 4 ex