Reactor for production of the chlorinated allyl
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
The invention relates to the technology of basic organic synthesis, more specifically, to a technology for halogenorganics compounds, in particular to the reactor for the method of obtaining the chloride allyl direct gas-phase high-temperature chlorination of propylene.
Chloride allyl is produced in large volumes to obtain epichlorohydrin and glycerol and to a lesser extent - for allyl alcohol.
Industrial process of obtaining allyl chloride based on the direct reactions of gas-phase high-temperature chlorination of propylene, under certain conditions, the flow of which is formed mainly of allyl chloride (3-monochloropropane) by the equation
Byproducts of the process are 1,3 - and 2,3-dichloropropene (further substitution chlorination of allyl chloride)
and 1.2 dichloropropane (1,2-DHP) (parallel additive chlorination of propylene)
The latter at high temperatures undergoes pyrolysis with the formation of the target chloride and allyl side 1 - and 2-monochloropropane. However, the speed of the reactions of their formation small.
In addition to these three reactions proceed the reaction of formation of a number of other side products is mswb, in particular, 1-, 2-monochloropropane, the highest chloropropanol and chloropropanol, soot and other. In existing producing allyl chloride output side is about 20 wt.%, of these, the proportion of 1,2-DHP account for up to 75% (15 abs.%). In noticeable quantities of soot is present.
All of the chlorination reaction is exothermic. The reactor generally is adiabatic.
Best for synthesis of allyl chloride accepted temperature range (420-530)°and the molar ratio of propylene feedstock and chlorine equal to (3,0-4,0):1. The average time of stay in the industrial tubular reactor is (0,6-1,0)C. At temperatures below 400°With the reaction rate of the formation of side-1,2-DHP according to reaction (3) exceeds the rate of formation of the target allyl chloride according to reaction (1), and at temperatures above 420°With the rate of the reaction (3) is significantly less than the rate of reaction (1).
Thus, in this process there are three main problems: to provide a quick (≈ 0,C) heating the reaction mixture from the temperature at the inlet of the source of propylene and chlorine to temperatures above 400°to reduce the output of the main by-product 1,2-dichloropropane, to ensure rapid mixing of the source of chlorine with propylene to reduce the rate of formation of soot, which often leads to zabivka input nodes chlorine and even vs the reactor, and to reduce the temperature gradient along the length of the reactor to carry out the process at the optimal temperature. These three tasks must be solved for the condition: average residence time of the reactants should be (0,6-1,0)C.
The purpose of the invention using the proposed design of the reactor to increase the selectivity of the process of obtaining chloride allyl direct gas-phase high-temperature chlorination of propylene to (85-95) wt.% due to the rapid heating of the initial reaction mixture from the initial temperature of the initial propylene and chlorine to temperatures above 400°due to the rapid and effective mixing of the propylene feedstock and chlorine to the circulating reaction gases and due process is practically isothermal.
The known method and the reactor obtain allyl chloride gas-phase chlorination of propylene [1. U.S. patent No. 3054831 from 18.09.1962 r. Samples R.H., Hilbert LE, Halo-genation of organic compounds over a narrow temperatures range U.S. Patent No. 6004517 from 21.12.1999,], according to which chlorine is injected through the nozzle, the output of which, capturing the mixture of reaction gases and feedstock introduced into the reactor of ideal mixing (FIG) tangentially and perpendicularly to the axis of the nozzle input of chlorine, is fed to the inlet of the Venturi tubes, the output stream of the gas mixture which enters the same ideal mixing reactor. The disadvantage of this sposoby reactor is that FIGURE is provided by insufficient mixing of the propylene from the reaction gases and, consequently, with chlorine, thus reducing the selectivity of the process on the target allyl chloride and increased sazheobrazovanie.
The known method and the reactor obtain allyl chloride gas-phase chlorination of propylene [Tirtowidjojo M.M., Beckett P.C., Baker, J.F., Process to make allyl chloride and reactor useful in that process], according to which the reactor includes two sequentially arranged reaction zones: the ideal mixing reactor (FIG) and the reactor ideal displacement (REEVE). Propylene and chlorine is introduced into RICE through tubes located at an angle of 90°. This reactor has the same drawbacks as the reactor [first analog]: insufficient mixing and heating of the raw materials and, consequently, reduced selectivity for chloride allyl, high sooting and the output of the high-boiling by-products, as well as uneven temperature profile of the reactor.
The known method and the reactor obtain allyl chloride gas-phase chlorination of propylene [RF Patent №2150453 dated 02.07.1998, Abdrashitov AM, Matalino VI, Gizatullin P.C., Berlin E.R., Japryncev, Y.M. Way to get allylchloride and reactor for its implementation], according to which the synthesis is carried out in a closed reactor, equipped with a device on the Ohm forced circulation, and reagents injected through the perforated sections of the circuit that are before (propylene) and after (chlorine) device forced circulation. The disadvantage of this solution is that as the forced circulation device uses a mechanical rotating machine (fan), which is technically difficult to perform in high temperature process, and the introduction of chlorine through the perforated pipe under conditions of relatively low velocity of the circulating gases leads to insufficient mixing and abundant sazheobrazovanie a result of getting significant portion of the source of chlorine in the boundary layer where the velocity of the gases close to zero.
Closest to the claimed technical solution is known a method and reactor for the production of allyl chloride [U.S. Patent 6011186 from 04.01.2000, Wang N., Peenstra J., Rek P.J.M., Tromp P.J.J., Van Mourik A Process for manufacturing allylhalide and equipment to be used therefore], according to which the reactor is a closed loop circulation, the circulation of the reaction gas which is generated by the energy source of propylene, flowing from the nozzle, and chlorine is injected through several groups of holes distributed along the length of the circuit, through tubes located perpendicular to the direction of the circulating flow of the reaction gases. Disadvantages izvestno the method is that separate nozzle input propylene and tube input chlorine does not provide an effective and rapid mixing of propylene and chlorine among themselves and with the reaction gases, which inevitably leads to abundant sazheobrazovanie. In addition, the input of chlorine through hole, located near the fitting conclusion of the reaction gas from the circulation loop reactor, leads to its breakthrough with the reaction gases.
The challenge which seeks the invention is to increase the selectivity of the process of chlorination of propylene to allyl chloride due to the rapid and effective mixing of the propylene feedstock and chlorine and heated to temperatures close to the temperatures of the process, and by ensuring considered horizontally isothermal surface process to ensure complete conversion of chlorine in the reactor.
The technical result in the implementation of the known method of producing allyl chloride gas-phase chlorination of propylene under pressure at a temperature of (400-530)°and a molar ratio of the propylene feedstock and chlorine equal to (2,5-5,0):1, in the reactor, which represents the closed loop circulation of the reaction gases and provided with a device input propylene and chlorine, the forced circulation device and the output device of the reaction gases is achieved by the osobennosti reactor (see 1), which is that as the device forced circulation, high efficiency heater and mixer initial reagents used jet pump (injector) 1, including a nozzle input propylene 2 and 3 chlorine, the input receiving chamber 4 of the original propylene and chlorine and recirculating the reaction gases, the mixing chamber 5 and the diffuser 6, where workers injects threads are propylene source 7 and 8 chlorine, and the injected flow is the flow of the circulating reaction gas 9 is supplied through the pipe circuit 10, connecting the outlet of the diffuser with the input receiving cell jet pump (injector) and containing the output flow of the reaction gases 11. Such reactor hereinafter will be called a flow-circulation reactor with jet pump circulation (PCR).
Theory calculation of the injector described in [Abramovich, G.N. Applied gas dynamics. - Moscow: GOS. publishing house of technical and theoretical literature, 1953. - 736 S. Sokolov DEATH, singer N.M. Jet devices, ed. 2-E. - M.: Energy, 1970. - 288 S.]. With respect to PCR, this calculation is supplemented by the condition that the differential pressure developed by the injector, should compensate for the resistance of the entire circuit of the reaction gases for the selected ratio of circulation, which is defined as the ratio of the mass flow circulara the General reaction gases F r9 to the sum of the mass flows of the propylene feedstock F1 07 and chlorine F2 08 (see Fig 1)
and may be chosen based on requirements to provide the desired temperature of the heating source of propylene and chlorine at the outlet of the injector, the selected geometry of the circuit, which is determined by the average residence time of the reactants in the circuit section from the diffuser to the device output flow of the reaction gases F313.
In the proposed design flow-circulation reactor stimulate circulation of the reaction gases is injector 1, in which flowing out of the respective working nozzles initial propylene and chlorine with speeds respectively (240-290) m/s and (160-190) m/s capture ("podsushivayut") in the input chamber, the circulating flow of the reaction gases, creating a much turbulizing the flow of the mixture in the input cone (confuser) 12 and the mixing chamber 5 (Re=106-107), providing a multiplicity of circulation, equal to 5-10.
Due to the high turbulence is fast, (0,01-0,04), mixing the original popeline, chlorine and circulating the reaction gases and quick heating of the initial reagents due to their mixing with the hot reaction gases to the temperature of the mixture, which is determined by thermal balance of the mixturep> F1 0.cp1At. t1+F2 0Cp2At. t2+FrCprAt. tr=(F1 0+F2 0+Fr).cRSM.T.cm
or, taking into account the expression (4),
Here T1and T2- temperature flowing out of the nozzles flows propylene F1 0and chlorine F2 0Fr.the recirculating flow of the reaction gases, cpi- heat capacity.
Consider further that in steady mode
and use the value of the input temperature of the initial reagents T, numerically equal to the temperature of the mixture
Then from equation (5) we can obtain the formula for calculation of the temperature of the mixture of the raw materials and circulating the reaction gases
where the value T is calculated by the formula (6). So for T=180°S, Tr=450°S, U=10, we obtain Tcm≈425°C. If U=5 get Tcm=405°C.
While working the nozzle of the propylene feedstock as most injects flow is the main and is located on the axis of the mixing chamber of the injector and the nozzle/nozzle entering the chlorine source is located (located on the circumference) coaxial nozzle propylene, forming together the combined nozzle" inject the gas tank. Marked the location of the nozzles enter propylene and chlorine has the advantage that the flow of chlorine introduced is as if squeezed between the circulating stream of hot reaction gases moving at relatively low speed, and flow over the cold source of propylene, which expires from the nozzle at a very high speed and catches cold chlorine and hot reaction gases containing about 60% vol. propylene (and as it passes through the layer of chlorine), promoting rapid mixing and heating a mixture of reagents that prevents the formation of side-1,2-dichloropropane and soot and accordingly increases the selectivity of the process on the target allyl chloride. When this circuit is favorable ideal displacement, so that when the molar ratio of the propylene feedstock and chlorine equal to (2,5-4,0):1, the process temperature (410-450)°C, the pressure of 2.3 absat and time (0.7 to 0.9)with chlorine reacts completely. In this variation of temperature in the circuit does not exceed ±10°C. the Selectivity to the allyl chloride at a temperature (400-405nm)°is (80-82) wt.%, at T=(425-435)° - (85-86) wt.%, at T=(450-460)° - (90-92) wt.%.
PCR described construction has been tested and 20.12.2004 were included in the pilot operation. The reactor is easy to control the situation, easy starts, stops, restarts. Easily maintained the desired temperature of the process.
Diagram of flow-circulation reactor for the production of allyl chloride vapor with high temperature chlorination of propylene with injection pump circulation is shown in the drawing.
1. Characteristics of the reactor.
The composition of the reactor:
jet pump (injector) with original fittings propylene and chlorine, performing the functions of: receiving a source of propylene and chlorine, the pump circulation of the reaction gases, a fast and highly efficient mixer source of propylene and chlorine and circulating the reaction gases and fast and efficient heater initial reagents due to their mixing with reaction gases
- tube circuit main reaction zone perfect displacement associated with exit and entrance of the injector,
the fitting conclusion of the reaction gases from the reactor.
Configuration: closed on injector pipe circuit.
The turns of the circuit is made in the form of smooth bends.
The volume of the reactor: Vp=10 m3.
The composition of the jet pump (injector):
the Central nozzle input propylene - 1 piece,
- nozzle input of chlorine, located on two circles coaxial to the Central nozzle input propylene is a - 24 pieces,
- input receiving chamber containing a nozzle input propylene and chlorine and associated with the output circuit,
the mixing chamber,
- the diffuser is connected to the input of the circuit.
Working injects threads: threads are the source of propylene and chlorine.
The injected stream: stream circulating reactive gases.
Consumption of propylene F1=3500 nm3/PM
Chlorine consumption F2 0=1000 nm3/PM
The multiplicity of circulation U=8.
The propylene pressure at the inlet of the reactor - 3.7 Absam.
The temperature of the propylene to the reactor inlet - 232°C.
The pressure of chlorine at the inlet of the reactor - 3.7 Absam.
The temperature of the chlorine at the inlet of the reactor 20°C.
The pressure in the reactor - 2,3 Absam.
The flow rate of propylene from a nozzle - 253 m/S.
The flow rate of chlorine from the nozzle - 176 m/S.
The temperature of the reaction gases after the diffuser injector - 419°C.
The temperature of the reaction gases in the circuit- 430(+9, -11)°C.
2. The composition of the synthesized chlororganic, wt.%:
chloride allyl - (85,40-85,68),
2-monochloropropane - (4,10-4,25),
2-chloropropene - (1,5-4,0),
1.2-dichloropropan - (8,01-6,07),
1.3-dichlorophen-TRANS - (0,12-0,00),
2,3-dichloropropan - (0,76-0,00),
1,2,3-trichlorpropane - (0,12-0,00).
The reactor for the production of allyl chloride, intended for the method of obtaining chlorine is East of allyl direct gas-phase chlorination of propylene, including closed circuit circulation of the reaction gases, input source of propylene and chlorine, the device forced circulation of the reaction gases and the output device to another part of the reaction gases, characterized in that the closed loop circulation of the reaction gases of the reactor to form the jet pump (injector), which includes serially connected input receiving chamber containing the nozzle as the input device, the source of propylene and chlorine, the mixing chamber and the diffuser, and ensure the implementation of the combined functions of input streams source of propylene and chlorine, which are working injects flows, pump forced circulation with multiplicity 5-10 flow of the reaction gas, which is injected into the flow high speed mixer and heater initial reagents in the mixing chamber due to the strong turbulence within 0,01-0,s created by combining nozzle injects gases at the location of the nozzles/nozzle chlorine coaxial main nozzle propylene located on the axis of the mixing chamber, and the pipe circuit, closing the exit of the diffuser with the respective input of the reception chamber of the injector and which is the main reaction zone perfect displacement with time of 0.7-0.9 s, in which the dispersion of the temperature does not exceed ± 10°C.
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: 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: 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: chemical industry.
SUBSTANCE: vacuum reactor comprises tower (1), distributors of chlorine (2) and ethylene (3), circulation pipe (5), perforated plates (6), condenser (7), pump (8), vacuum-pump (9), and hydraulic valve (10).
EFFECT: improved quality of the product.
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to a process of liquid-phase chlorination of ethylene wherein reaction heat is removed by means of vaporization of reaction medium. Process is conducted at vacuum-mediated reduction of reaction medium boiling temperature below 60°C, vacuum being developed because of condensation of vapors formed in external condenser accompanied by removal of non-condensed gases by vacuum pump.
EFFECT: enhanced selectivity of process and decreased yield of by-products (higher chlorine derivatives of ethane).
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. Method involves maintaining the optimal ratio of heat eliminated based on evaporation and heat eliminated based on cooling a liquid medium in a heat exchanger in the process. One-sixth part of heat formed in reactor is eliminated based on evaporation of synthesized compound in boiling and 5/6 part of formed heat is eliminated based on circulation of liquid working medium in external heat exchanger. The temperature gradient in the reaction zone is maintained equal 52°C. Invention provides enhancing selectivity of process and reducing amount of by-side products of reaction (higher chlorine-derivate of ethane).
EFFECT: improved method of synthesis.
3 dwg, 1 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. The process is carried out by direct feeding gaseous reagents chlorine and ethylene in liquid reaction medium of reactor. Before feeding into reactor chlorine and ethylene are heated preliminary in heat-exchangers to temperature equal to that of liquid in reactor. Method provides enhancing selectivity of process and reducing formation of by-side substances representing higher chlorine-derivatives of ethane.
EFFECT: improved method of synthesis.
4 dwg, 1 ex
FIELD: chemical industry; designs of the bubble-type reactors for production of 1.2-dichloroethane.
SUBSTANCE: the invention is pertaining to the design of the bubble-type reactors for production of 1.2-dichloroethane by the method of the liquid-phase chlorination of ethylene with the reaction heat removal at boiling of the working medium. As the contact device the reactor uses two layers of the metallic nozzle. The liquid 1.2-dichloroethane is fed from above to the nozzle, into the space between the layers of the nozzle feed the gaseous chlorine with nitrogen, and under the lower layer of the nozzle feed the gaseous ethylene with nitrogen, that allows to reduce the diameter of the reactor in 1.5-2 times due to the increased effectiveness of stirring and formation of the developed contact surface of the phases. At that the heat of the reaction is removed by evaporation of 1.2-dichloroethane in nitrogen. At that the temperature of the liquid is maintained below the boiling temperature. The technical result of the invention is the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
EFFECT: the invention ensures the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
1 ex, 4 dwg