WO2018214642A1 - 塔式连续光氯化法制氯苄 - Google Patents

塔式连续光氯化法制氯苄 Download PDF

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Publication number
WO2018214642A1
WO2018214642A1 PCT/CN2018/080985 CN2018080985W WO2018214642A1 WO 2018214642 A1 WO2018214642 A1 WO 2018214642A1 CN 2018080985 W CN2018080985 W CN 2018080985W WO 2018214642 A1 WO2018214642 A1 WO 2018214642A1
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Prior art keywords
reaction
reactor
stage
chlorine
photochlorination
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PCT/CN2018/080985
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English (en)
French (fr)
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王农跃
闻国强
赵全忠
邵建明
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方圆化工有限公司
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Publication of WO2018214642A1 publication Critical patent/WO2018214642A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation

Definitions

  • the present application relates to a column-type continuous photochlorination process for the production of benzyl chloride, and more particularly to a method for photochemically reacting an aromatic hydrocarbon compound with chlorine gas at a membrane interface to chlorinate a methyl group on a benzene ring.
  • the main method of the present invention is gas phase photochlorination at the interface of the membrane, which can greatly reduce by-products such as benzene ring chlorination and increase the yield of the target product.
  • the application also relates to a membrane interface photochlorination reactor.
  • a derivative product obtained by photochemical chlorination of an aromatic hydrocarbon compound of the formula (X) a C 6 H 6-ab (CH 3 ) b is an important organic synthesis intermediate.
  • trichloromethyl-substituted benzene as an example, bis(trichloromethyl)benzene and tris(trichloromethyl)benzene are important intermediate products for preparing polymer materials, medicines, dyes, and pesticides.
  • the chlorination of benzyl chloride by photochlorination is usually carried out by photochlorination.
  • the photochlorination reaction mainly uses photons to initiate side chain radicals to carry out chlorination reaction, and part of the reaction uses a radical photoinitiator or a complex initiation system composed of a radical thermal initiator.
  • the defects in the photochlorination reaction in the prior art are mainly: (1)
  • the photochlorination reaction is a free radical chain reaction, and the chlorination site and the chlorination depth are relatively difficult to control due to the presence of side reactions.
  • DE3146868 In order to separate complex photochlorination products, DE3146868 has to carry out a large number of rectification operations, greatly increasing the production cost of such products.
  • CN104591958B discloses a method for continuously producing a trichloromethyl-substituted benzene compound, which can greatly improve the purity and yield of trichloromethyl-substituted benzene by controlling reaction conditions such as temperature, illuminance and chlorine amount.
  • a membrane interface photochlorination reaction to better prepare a benzyl chloride, that is, a product in which a hydrogen atom on a side chain methyl group of a benzene ring is substituted with a chlorine atom. Because in the initial stage of the photochlorination reaction, the reaction occurs through the membrane interface, mainly occurs in the gas phase photochlorination reaction, basically the product of the hydrogen atom on the side chain methyl group of the benzene ring is replaced by a chlorine atom, and the benzene ring is A side reaction in which a hydrogen atom is replaced by a chlorine atom hardly occurs.
  • the present application relates to a column-type continuous photochlorination process for the production of benzyl chloride, the specific technical scheme of which is to make an aromatic hydrocarbon compound of the formula (X) a C 6 H 6-ab (CH 3 ) b in flow.
  • the X is chlorine or a bromine or fluorine atom
  • a is an integer selected from 0, 1, 2, 3, 4 or 5
  • b is an integer selected from 1, 2 or 3, and a + b ⁇ 6.
  • the membrane interface photochlorination reaction described in the present application refers to a liquid reaction material (for example, an aromatic hydrocarbon compound of the formula (X) a C 6 H 6-ab (CH 3 ) b described in the present application) to form a liquid film, and a gas. Contact, reaction under light conditions.
  • a liquid reaction material for example, an aromatic hydrocarbon compound of the formula (X) a C 6 H 6-ab (CH 3 ) b described in the present application
  • the chlorine gas has a volume concentration of 1 to 40%.
  • the chlorine gas volume concentration may be any value in the range of 1 to 40% or a combination of any value within the range, for example, 5%, 10%, 15%, 20%. 25%, 30%, 35%, 40%, 1% to 20%, 15% to 30%, etc., preferably chlorine gas volume concentration is 5 to 30%, and further preferably chlorine gas volume concentration is 10 to 20%.
  • the reaction temperature is from 20 ° C to 150 ° C.
  • the reaction temperature may be any value in the range of 20 ° C to 150 ° C or a combination of any value within the range, for example, 20 ° C, 30 ° C, 40 ° C, 45 ° C. 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130 °C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, preferably a reaction temperature of 60 to 100 ° C.
  • the amount of chlorine gas introduced is 2 to 40% of the theoretical stoichiometric amount required for the side chain methyl perchlorination of the benzene ring.
  • the amount of chlorine gas introduced may be any value in the range of 2 to 40% of the theoretical stoichiometric amount required for the side chain methyl perchlorination of the benzene ring or any value within the range.
  • the range formed by the combination is, for example, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, preferably 3 to 30%.
  • a polychlorobenzyl product such as dichlorobenzyl, trichlorobenzyl, tetrachlorobenzyl, pentachlorobenzyl, hexachlorobenzyl or heptachlor can be obtained.
  • Benzyl, octabenzyl or nonabenzyl chloride, etc. preferably, in the course of further reaction with chlorine, the reaction temperature is raised accordingly, and the maximum reaction temperature does not exceed 180 °C.
  • Further reaction with chlorine can be carried out in one reactor in the reaction stage with monochlorobenzyl or in a plurality of subsequent reactors connected in series.
  • Those skilled in the art can stop the reaction in time by controlling the temperature and chlorine gas to obtain a desired target product such as monochlorobenzyl, dichlorobenzyl or the like.
  • a desired target product such as monochlorobenzyl, dichlorobenzyl or the like.
  • the reaction can be stopped when the obtained product is mainly the desired target product, and the monochloro compound can be separated from the raw material aromatic hydrocarbon compound to obtain a higher purity target product.
  • the inventors have found that in the photo-chlorination reaction at the membrane interface, the substitution of a chlorine atom occurs on the side chain methyl group of the benzene ring, and after the substitution of chlorine, it is difficult to form a by-product of the hydrogen atom on the benzene ring which is substituted by the chlorine atom, on the methyl group.
  • the intermediate obtained after the hydrogen atom is replaced by a chlorine atom is very stable, and in the subsequent photochlorination reaction with a sufficient amount of chlorine gas, a trichloromethyl substituted benzene is formed (the benzene ring side chain methyl group) a product in which a hydrogen atom is completely replaced by a chlorine atom).
  • the product intermediate obtained by photo-chlorination of the membrane interface can be further chlorinated to obtain trichloromethyl-substituted benzene.
  • the trichloromethyl-substituted benzene reaction mixture obtained directly according to the method of the present invention contains little impurities similar to the boiling point of the main product, and a high-purity trichloromethyl-substituted benzene product can be obtained by simple distillation or primary rectification.
  • the present application relates to a method for the continuous chlorination of benzyl chloride into a column, which is divided into two stages, the first stage: the chemical formula is (X) a C 6 H 6-ab (CH 3 )
  • the aromatic hydrocarbon compound of b forms a liquid film in the flow, and undergoes photochemical chlorination reaction with chlorine gas under light conditions to detect the mass percentage of residual aromatic compound (X) a C 6 H 6-ab (CH 3 ) b
  • the content when the content is 0-20%, the first stage reaction ends;
  • the second stage the reaction intermediate obtained in the first stage is further photochlorinated with chlorine gas until the reaction is completed, to obtain trichloromethyl substituted benzene;
  • the X is chlorine or a bromine or fluorine atom, a is an integer selected from 0, 1, 2, 3, 4 or 5, b is an integer selected from 1, 2 or 3, and a + b ⁇ 6.
  • the mass percentage of the residual aromatic compound may be detected, and may be any value in the range of 0-20% or a combination of any value within the range, for example, 0, 0.5%, 1 %, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 10.5%, 11.0%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5% 18%, 18.5%, 19%, 19.5%, 20%, etc., the first phase of the reaction is over.
  • the mass percentage of the residual aromatic compound is detected, preferably when the content is 0 to 12%, further preferably when the content is 0 to 2%, particularly preferably when the content is 0%.
  • the first phase of the reaction is over.
  • the first stage chlorine gas has a volume concentration of 1 to 40%, preferably a chlorine gas volume concentration of 5 to 30%, and further preferably a chlorine gas volume concentration of 10 to 20%.
  • the reaction temperature of the photocatalytic reaction of the first stage membrane interface described in the present application is 20 ° C ⁇ 180 ° C.
  • reaction temperature of the film interface photochlorination reaction may be any value in the range of 20 ° C to 180 ° C or a combination of any value within the range, for example, 20 ° C, 25 ° C, 30 ° C, 35 °C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, 155 ° C, 160 ° C, 165 ° C, 170 ° C, 175 ° C, 180 ° C and the like.
  • the reaction temperature of the photo-chlorination reaction at the membrane interface is preferably from 80 ° C to 120 ° C.
  • the reaction temperature is too low, the reaction rate is slow, and the reaction time is long, which is not conducive to industrial production, and is not conducive to evaporation of the liquid reaction material into a gas, thereby achieving a gas-gas phase reaction between the aromatic hydrocarbon and the chlorine gas; if the reaction temperature is too high, it is disadvantageous
  • the reaction heat is removed, a side reaction occurs, and the product yield is lowered.
  • the first stage described in the present application may be completed in one or more reactors, and the plurality of reactors may be connected in series or in parallel or in other manners, for example, 2 to 10 reactors connected in series in the first stage. Preferably, 2 to 3 reactors connected in series are used.
  • the present application also relates to a scheme of performing photo-chlorination reaction at the membrane interface in one reactor until the reaction is completed, that is, the first stage and the second stage are carried out in the same reactor to carry out photo-chlorination reaction at the membrane interface. Until the reaction is completed, trichloromethyl substituted benzene is obtained.
  • reaction temperature of each series reactor is gradually increased.
  • the reaction temperature of the first reactor is 20 ° C ⁇ 150 ° C
  • the reaction temperature of the second reactor is 60 ° C ⁇ 180 ° C, preferably, the first The reaction temperature of the reactor is 80 ° C ⁇ 105 ° C
  • the reaction temperature of the second reactor is 100 ° C ⁇ 120 ° C
  • the reaction temperature of the first reactor is 20 ° C ⁇ 150 °C
  • the reaction temperature of the second reactor is 60 ° C ⁇ 180 ° C
  • the reaction temperature of the third reactor is 60 ° C ⁇ 180 ° C
  • the reaction temperature of the first reactor is 80 ° C ⁇ 100 ° C
  • the first The reaction temperature of the two reactors is from 90 ° C to 120 ° C
  • the reaction temperature of the third reactor is from 95 ° C to 120 ° C.
  • the reaction conditions are substantially the same as those in the photo-chlorination reaction of the membrane interface in a plurality of reactors, for example, methyl group on the benzene ring.
  • the volume concentration of the chlorine gas to be introduced is preferably controlled to be 1 to 40%, preferably 2 to 30%, more preferably 5 to 20%.
  • the chlorination reaction temperature increases correspondingly with the increase of the chlorination depth in the range of 20 ° C to 180 ° C.
  • the reaction product obtained in the first stage of the present application is basically a compound in which at least one hydrogen atom of the side chain of the benzene ring is substituted by a chlorine atom, and the part of the reaction product continues to undergo photochlorination without benzene ring chlorination. by-product. Further, the inventors have further found that as long as the mass percentage of the residual aromatic compound after the reaction is 0 to 20%, no particular limitation is imposed on the chlorine gas volume concentration, and even if the volume concentration is 100% chlorine gas, no reaction is caused. Material carbonization.
  • the volume concentration of chlorine gas introduced into the reactor does not need special control, and can be varied within the range of 1% to 100%, in order to ensure the reaction efficiency.
  • the chlorine gas has a volume concentration of 75 to 100%.
  • the chlorine gas volume concentration in the present application is not 100%, it may be diluted by adding an inert gas, for example, nitrogen gas, argon gas, helium gas, carbon dioxide gas or the like to obtain chlorine gas having a suitable volume concentration.
  • an inert gas for example, nitrogen gas, argon gas, helium gas, carbon dioxide gas or the like to obtain chlorine gas having a suitable volume concentration.
  • the photo-chlorination reaction of the second stage, the type of the reactor to be used, and the specific reaction conditions are not particularly limited, and those skilled in the art can realize according to the prior art.
  • the photochlorination reaction in the second stage preferably has a reaction temperature of from 80 ° C to 280 ° C, more preferably from 120 ° C to 170 ° C.
  • the reaction temperature can be determined according to different reaction materials and requirements.
  • the second stage may employ a conventional photochlorination reactor of the prior art, generally a liquid chlorination reactor in which a liquid is a continuous phase and a gas is dispersed in a liquid form for gas-liquid reaction, for example, CN203916645U.
  • a conventional photochlorination reactor of the prior art, generally a liquid chlorination reactor in which a liquid is a continuous phase and a gas is dispersed in a liquid form for gas-liquid reaction, for example, CN203916645U.
  • the disclosed photochlorination reactor a plurality of, for example, 2 to 3 conventional photochlorination reactors connected in series may be used to complete the reaction; 2 to 6 membrane interface photochlorination described in the present application may also be used.
  • the reactor is used to continue the reaction, for example, using 2 to 6 falling film reactors in series; it is also possible to carry out the reaction using a conventional photochlorination reactor in combination with a falling film reactor.
  • Those skilled in the art can
  • the membrane interface photochlorination reaction described herein can be achieved by existing reactors, such as packed column reactors, falling film reactors, ascending membrane reactors or trickle bed reactions well known to those skilled in the art. And so on.
  • the light condition is increased, so that the photo-chlorination reaction of the membrane interface can occur, which is referred to as membrane interface photochlorine. Reactor.
  • a light-transmissive filler and/or baffle is added to the reactor, and the liquid material flows along the filler and/or baffle into a liquid film state.
  • the photochlorination reaction described in the present application has an illuminance of 1000 Lux to about 400,000.
  • Lux preferably 20,000 Lux ⁇ 100000 Lux.
  • the reaction intermediate obtained in the first stage of the present application includes, in addition to the target product intermediate, a compound having at least one hydrogen substituted by chlorine on the side chain methyl group of the benzene ring, and a part of the target product trichloromethyl substituted benzene and/or A small amount of unreacted raw materials and by-products.
  • the trichloromethyl-substituted benzene product obtained by the present invention has high purity, and after the reaction is completed, substantially the reactant of the target product having a purity of 95% or more can be directly obtained.
  • the reaction product may be further purified if necessary, and the product obtained in the present application can be obtained by a conventional purification method such as distillation, rectification or recrystallization to obtain a product having a purity of 99% or more.
  • the present application provides a membrane interface photochlorination reactor comprising a reactor housing provided with a liquid feed port, a gas feed port, a gas outlet and a product outlet, the liquid feed A liquid film is formed in the flow, the light source of the photochlorination reaction being uniformly irradiated from the periphery and/or the inside of the reactor to the reaction zone, the light source being separated from the reaction zone by the reactor casing.
  • the membrane interface photochlorination reactor housing is a single cylinder or a hollow cylinder composed of two concentric cylinders.
  • the liquid material flows along the inner wall of the cylinder to form a liquid film, and the light source is disposed at the periphery of the cylinder wall, and uniformly irradiates from the outer periphery of the cylinder to the reaction zone;
  • the device is a hollow cylinder composed of two concentric cylinders, the liquid material flows along the inner wall of the outer cylinder and/or the outer wall of the inner cylinder into a liquid film, and the light source is disposed at the periphery of the outer cylinder and/or the inner cylinder. Internally, it is uniformly irradiated to the reaction zone.
  • the membrane interface photochlorination reactor is a hollow cylinder composed of two concentric cylinders
  • the material of any one or two cylinders is a light transmissive material
  • the materials of the two cylinders are all translucent.
  • a light source is disposed on the periphery of the outer cylinder and/or inside the inner cylinder to uniformly illuminate the reaction zone;
  • the outer cylinder is a light transmissive material, a light source is disposed on the outer periphery of the outer cylinder, and the uniform direction is
  • the inner cylinder is a light transmissive material
  • a light source is disposed inside the inner cylinder to uniformly illuminate the reaction zone.
  • the material is a material having light transmissivity, such as a material having good light transmittance such as glass or quartz, and preferably a material having light transmissivity and corrosion resistance.
  • the light transmissive material may be glass, quartz or the like, and the opaque material may be enamel or corrosion resistant metal material, such as fluorine-lined metal material, Hastelloy or the like.
  • the membrane interface photochlorination reactor liquid feed port is further provided with a liquid distributor; the gas feed port is further provided with a gas distributor.
  • the membrane interface photochlorination reactor can be placed vertically or inclined at different angles, and the residence time of the liquid material of the reactor can be adjusted by the inclination angle.
  • the reactor is placed in an inclined manner, it is preferred that the reactor is a hollow four-sided column structure or a multi-faceted column structure, and the liquid material has a large liquid film area. It is also possible to install an inclined baffle inside the column.
  • the liquid feedstock and chlorine may be in cocurrent or countercurrent contact within the reactor.
  • the membrane interface photochlorination reactor reaction zone is filled with a light-transmissive filler and/or baffle, and the liquid material flows uniformly in a liquid film state along the column wall and the filler and/or the baffle.
  • the specific shape of the column in the membrane interface photochlorination reactor housing is not particularly limited, and may be a hollow cylinder, a hollow multi-faceted cylinder, such as a hollow tetrahedral cylinder or the like.
  • the aromatic hydrocarbon compound of the formula (X) a C 6 H 6 ⁇ a ⁇ b (CH 3 ) b is subjected to photo-chlorination reaction of chlorine at room temperature under light conditions, and the photo-chlorination reaction at the interface of the membrane is mainly through the reaction.
  • the material specific surface area is large, in the process of this application, after the chlorine gas enters, especially in the specific chlorine gas volume concentration and temperature range Internally, the vapor of the aromatic hydrocarbon compound formed by evaporation of the aromatic hydrocarbon compound in the liquid film is mainly caused by the gas phase reaction of the chlorine gas under the light condition, and the reaction does not produce the benzene ring chlorinated by-product; and the chlorine gas and the surface of the material film occur internally and internally.
  • the reaction is supplemented; and the heat generated by the reaction in the present application is mainly concentrated in the gas phase, and is carried away by the unreacted gas in the mixed gas and the hydrogen chloride generated by the reaction, which is advantageous for timely removal of the heat of reaction and can reduce the heat-sensitive type.
  • the main two side reactions which are difficult to control in the photochlorination reaction are effectively suppressed, thereby effectively increasing the yield of the reaction product; and different chlorine can be obtained by controlling the chlorine gas feed, the chlorine gas concentration, the reaction temperature, and the like.
  • the reaction can be divided into two stages.
  • a membrane interface photochlorination reaction is employed, and chlorination occurs on the side chain methyl group of the benzene ring, and the benzene ring
  • the intermediate obtained after methyl chloride is very stable, and in the subsequent photochlorination reaction with chlorine gas, a chloro compound of a methyl group on the benzene ring is formed, so that the reaction conditions of the subsequent second stage are easy to control, for example,
  • the photochlorination reaction can be carried out by a conventional photochlorination reactor until the reaction is completed; the prepared trichloromethyl substituted benzene has high purity, is easy to be further purified, has high reaction efficiency, and has a short production cycle, and is suitable for industrial production.
  • Embodiment 5 is a process flow diagram of Embodiment 5 of the present invention.
  • Figure 2 is a schematic view showing the structure of a single column membrane interface photochlorination reactor
  • Figure 3 is a schematic view showing the structure of a double cylinder membrane interface photochlorination reactor
  • 1-membrane interface photochlorination reactor 2-liquid feed port; 3-gas feed port; 4-gas outlet; 5-reaction product outlet; 6-conventional photochlorination reactor;
  • the effective conversion ratio as referred to herein means the mass ratio of the sum of the amount of the aromatic hydrocarbon raw material converted to the target product and the target product intermediate to the amount of the chlorination reaction of the aromatic hydrocarbon raw material.
  • the yield referred to in the present application refers to the mass ratio of trichloromethyl-substituted benzene which is theoretically obtainable by a chlorination reaction of a trichloromethyl-substituted benzene which is actually obtained by a reaction with a raw material aromatic hydrocarbon compound.
  • the chlorine gas introduction rate described in the examples of the present application refers to the mass flow rate after converting each volume concentration of chlorine gas into pure chlorine gas.
  • a glass tube having a length of 100 cm and an inner diameter of 1.5 cm is vertically placed, and a 6 mm glass spring filler is internally filled as a reactor; the structure of the membrane interface photochlorination reactor of this embodiment can be seen in Fig. 2, and the light source 9 is from the periphery of the reactor. Evenly irradiate the material reaction zone.
  • the reaction process is: 1,4-xylene is added from the liquid feed port 2 of the reactor 1, and is formed on the inner wall of the glass tube and the surface of the glass spring filler by a liquid distributor (not shown), along the inner wall and the glass spring.
  • the surface of the packing flows downward, and chlorine gas is introduced from the lower gas feed port 3; the external light intensity is 20000 Lux, the 1,4-xylene feed rate is 5.2 g/min, the chlorine gas feed rate is 2.09 g/min, and the chlorine gas volume concentration 15%, during the reaction process, the maximum temperature of the glass tube reaction zone is controlled to 100 ° C, the tail gas is discharged from the reactor gas stream outlet 4, and the product from the reaction product outlet 5 of the reactor 1 is collected for gas chromatography analysis to obtain each substance.
  • the mass percentage and composition are: 6.51% 1,4-xylene, 91.53% product intermediate, 0.74% 1,4-bis(trichloromethyl)benzene, 1.22% impurities, among which, product intermediates Monochlorobenzyl in the accounted for 81.67% of the reaction product.
  • the effective conversion of 1,4-xylene reached 99.06%.
  • the reaction product was subjected to rectification purification to obtain monochlorobenzyl having a purity of 97%.
  • a ring of 25 mm glass rings is filled between two annular cylinders of different diameters. See Figure 3 for a schematic diagram of the structure of the membrane interface photochlorination reactor.
  • the inner tube has a length of 180 cm, an outer diameter of 8 cm, and a wall thickness of 0.5 cm.
  • the outer tube has a length of 150 cm, an inner diameter of 20 cm, and a wall thickness of 0.5 cm.
  • the reaction process is as follows: the external illumination intensity is 25000 Lux, the internal illumination intensity is 20000 Lux, the p-chlorotoluene feed rate is 35 kg/h, and the film is formed along the inner wall of the filler and the outer cylinder and the outer wall of the inner cylinder and flows downward, and the chlorine gas is passed.
  • the speed is 20.62kg/h, the volume concentration of chlorine gas is 20%; the highest temperature in the glass tube is 60°C during the reaction; the liquid product at the lower end is collected for gas chromatography analysis, and the mass percentage and composition of each substance are: 5.83% p-chlorotoluene, 90.57% of product intermediates, 2.46% of p-chlorotrichloromethylbenzene, 1.14% of impurities; among them, monochlorobenzyl in the product intermediates accounted for 85.21% of the reaction product.
  • the effective conversion rate of p-chlorotoluene reached 98.55%.
  • the reaction product was subjected to rectification purification to obtain p-chlorobenzyl chloride having a purity of 96%.
  • a glass tube having a length of 100 cm and an inner diameter of 1.5 cm was vertically placed, and a 6 mm glass spring filler was internally filled as a reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • Mesitylene is added from the liquid inlet of the reactor, and is formed on the inner wall of the glass tube and the surface of the glass spring through the liquid distributor, and flows downward along the inner wall and the surface of the glass spring, and chlorine gas is introduced from the lower gas inlet; external illumination
  • the strength is 20000 Lux
  • the feed rate of the mesitylene is 4.8 g/min
  • the chlorine gas inlet speed is 1.28 g/min
  • the chlorine gas volume concentration is 15%
  • the maximum temperature in the glass tube reaction zone is 120 ° C during the reaction
  • the exhaust gas is from the reactor gas.
  • the outlet of the stream is discharged; the liquid product obtained from the reactor is subjected to liquid chromatography analysis, and the mass percentage and composition of each substance are: 25.2% of mesitylene, 74.08% of product intermediate, and 0.72% of impurities; The monochlorobenzyl in the product intermediates accounted for 71.1% of the reaction product. The effective conversion of mesitylene reached 98.55%. The reaction product was subjected to rectification purification to obtain monochlorobenzyl having a purity of 97%.
  • a hollow glass tube having a length of 150 cm and an inner diameter of 1.5 cm was vertically placed, and a 6 mm glass spring filler was internally filled as a reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • Methylbenzene is added from the liquid inlet of the reactor, and is formed on the inner wall of the glass tube and the surface of the glass spring through the liquid distributor, and flows downward along the inner wall and the surface of the glass spring, and chlorine gas is introduced from the lower gas inlet; external illumination
  • the strength is 20000Lux
  • the feeding speed of methylbenzene is 5.5g/min
  • the chlorine gas inlet speed is 3.18g/min
  • the chlorine gas volume concentration is 17%
  • the highest temperature in the glass tube reaction zone is 80°C during the reaction
  • the exhaust gas is from the reactor gas.
  • the outlet of the stream is discharged; the liquid product obtained from the reactor is analyzed by gas chromatography, and the mass percentage and composition of each substance are: 18.87% methylbenzene, 80.27% product intermediate, 0.02% trichlorobenzyl, 0.84% of impurities; wherein, monochlorobenzyl in the product intermediate accounts for 76.55% of the reaction product.
  • the effective conversion rate of methylbenzene reached 98.1%.
  • the reaction product was subjected to rectification purification to obtain monochlorobenzyl having a purity of 98.55%.
  • the process flow is shown in Figure 1.
  • the hollow glass tube with a length of 100cm and an inner diameter of 1.5cm is placed vertically, and a 6mm glass spring filler is filled inside as a membrane interface photochlorination reactor 1.
  • the photo-chlorination reaction of the membrane interface in this embodiment Referring to Figure 2, the source 9 is uniformly illuminated from the periphery of the reactor to the material reaction zone.
  • the first stage: 1,4-xylene is added from the liquid feed port 2 of the reactor 1, and is formed on the inner wall of the glass tube and the surface of the glass spring packing by a liquid distributor (not shown), along the inner wall and the glass spring.
  • the surface of the packing flows downward, and chlorine gas is introduced from the lower gas feed port 3; the external light intensity is 20000 Lux, the 1,4-xylene feed rate is 5.2 g/min, the chlorine gas feed rate is 5.4 g/min, and the chlorine gas volume concentration 17.6%, during the reaction, the maximum temperature in the reaction zone of the glass tube is 102 ° C, the tail gas is discharged from the outlet 4 of the reactor gas stream, and the volume ratio of chlorine in the exhaust gas is 1.0%; the product from the outlet of the reaction product of the reactor 1 is collected in the gas phase. Chromatographic analysis showed that the mass percentage and composition of each substance were: 8.52% 1,4-xylene, 89.85% product intermediate, 0.51% 1,4-bis(trichloromethyl)benzene, 1.12% Impurities.
  • the product continues to enter the reactor 1 and is connected to the internal packed packing membrane photochromic reactor in series.
  • the external light intensity is 19850 Lux
  • the chlorine gas passing rate is 8.1 g/min
  • the chlorine gas volume concentration is 18%.
  • the maximum temperature in the reaction zone of the glass tube is 115 ° C
  • the chlorine content in the reaction tail gas is 1.0%.
  • Part of the liquid product was collected for gas chromatography analysis.
  • the composition was: 92.56% of product intermediate, 6.04% of 1,4-bis(trichloromethyl)benzene, 1.40% of impurities; during the two-stage reaction, 1,4 The effective conversion of x-xylene reached 98.60%.
  • the first phase of the reaction is over.
  • the second stage taking 200g of the chlorination solution obtained in the first stage, entering the conventional photochlorination reactor 6, continuing the photochlorination reaction, the light intensity is 60,000 Lux, and the chlorine gas inlet speed is 20 to 120 g/h (in operation)
  • the rate of introduction of chlorine gas can be appropriately adjusted by those skilled in the art based on the results of the reaction monitoring.
  • the chlorine gas can be introduced at a slightly faster rate, the content of raw materials and intermediates is reduced, and when the target product content is increased (1,4-di(trichloromethyl)benzene content is ⁇ 60%).
  • the chlorine gas inlet speed can be slightly slowed down.
  • the second phase chlorine gas volume concentration is 100%.
  • the temperature in the chlorination column is controlled at 120 ⁇ 170 °C; the obtained product is analyzed by gas chromatography, and the composition is: 98.58%. , 4-di(trichloromethyl)benzene, 1.42% impurity; 1,4-bis(trichloromethyl)benzene yield 97.56%.
  • the purity of the obtained product after one-time purification was 1,4-bis(trichloromethyl)benzene having a purity of 99.95%.
  • the first stage a glass tube having a length of 100 cm and an inner diameter of 1.5 cm was placed vertically as a first-stage reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • the 1,3-xylene is added from the liquid inlet of the reactor, formed on the inner wall of the glass tube by the liquid distributor, and flows down the inner wall, and the chlorine gas is introduced from the lower gas inlet port 3; the external light intensity is 25000 Lux, 1,
  • the feed rate of 3-xylene was 5.0g/min, the chlorine gas feed rate was 5.7g/min, the chlorine gas volume concentration was 15%, and the highest temperature in the glass tube reaction zone was 83°C during the reaction.
  • the tail gas was discharged from the reactor gas stream outlet.
  • the volume ratio of chlorine in the exhaust gas is 1.8%; the liquid product obtained from the reactor is analyzed by gas chromatography, and the mass percentage and composition of each substance are: 35.58% of 1,3-xylene and 63.39% of the product intermediate Body, 1.03% impurities.
  • the product in the first stage reactor continues to enter the second stage reactor in series for photochlorination reaction, the external light intensity is 21030 Lux, the chlorine gas inlet speed is 5.7 g/min, the chlorine gas volume concentration is 16%, and the glass during the reaction.
  • the maximum temperature in the reaction zone is 95 ° C, and the chlorine content in the reaction tail gas is 3.5%.
  • the liquid product obtained from the second-stage reactor was subjected to gas chromatography analysis, and the composition was: 0.5% xylene, 96.34% of product intermediate, 1.83% of 1,3-bis(trichloromethyl)benzene, 1.33 % impurity; in the two-stage reaction, the effective conversion rate of 1,3-xylene reaches 99.12%.
  • the second stage of this example uses a membrane interface photochlorination reactor in the form of a conventional photochlorination reactor.
  • the liquid product obtained from the first stage enters the membrane-phase photochlorination reactor in the second stage for photochlorination reaction, the external illumination intensity is 32000 Lux, the chlorine gas inlet speed is 7.1 g/min, and the chlorine gas volume concentration is 90.6%.
  • the maximum temperature in the reaction zone of the glass tube is 98 ° C, and the chlorine content in the reaction tail gas is 5.3%.
  • the liquid product obtained from the reactor was subjected to gas chromatography analysis, and the composition was: 79.59% of product intermediate, 18.96% of 1,3-bis(trichloromethyl)benzene, 1.45% of impurities;
  • 200g of the product obtained in the second stage of the reactor is passed to a conventional photochlorination reactor with an illumination intensity of 65000 Lux, a chlorine gas feed rate of 2-10 g/h, a chlorine gas volume concentration of 100%, and a chloride column during the reaction.
  • the internal temperature was controlled at 120-170 ° C; the obtained product was analyzed by gas chromatography, and the composition was: 97.61% of 1,3-bis(trichloromethyl)benzene and 2.39% of impurities.
  • the yield of 1,3-bis(trichloromethyl)benzene was 96.80%.
  • the purity of the obtained product after one-time purification was 1,3-bis(trichloromethyl)benzene having a purity of 99.96%.
  • the first stage a glass tube with a length of 100 cm and an inner diameter of 1.5 cm is used as the first-stage reactor; the glass tube is placed vertically, the inside is filled with a glass spring filler of 6 mm, and 1,4-xylene is added from the liquid inlet of the reactor.
  • the liquid distributor is used to form a film on the inner wall of the glass tube and the surface of the glass spring filler, and flows down the inner wall and the surface of the glass spring packing, and the chlorine gas is introduced from the lower gas inlet; the external light intensity is 20000 Lux, and the 1,4-xylene feeding speed is At 4.5g/min, the chlorine gas feed rate is 4.3 g/min, the chlorine gas volume concentration is 18.5%, and the maximum temperature in the glass tube is 100 °C during the reaction.
  • the tail gas is discharged from the reactor gas stream outlet, and the chlorine gas volume ratio in the tail gas is 0.8%.
  • the liquid product obtained from the first-stage reactor was subjected to gas chromatography analysis, and the composition was 7.62% of 1,4-xylene, 90.53% of product intermediate, and 1.85% of impurities.
  • the liquid product obtained in the first stage reactor directly enters the second stage reactor filled with 6 mm glass spring packing.
  • the second stage reactor chlorination conditions are: external light intensity of 21030 Lux and chlorine gas inlet speed of 4.8 g/min.
  • the volume concentration of chlorine gas is 17.2%.
  • the maximum temperature in the glass tube is 102 ° C.
  • the tail gas is discharged from the outlet of the gas stream of the reactor, and the volume ratio of chlorine in the tail gas is 1.7%.
  • the liquid product obtained from the second-stage reactor is subjected to gas phase. Chromatographic analysis, the composition is: 95.69% of product intermediates, 2.26% of 1,4-bis(trichloromethyl)benzene, 2.05% impurities;
  • the second stage in the second stage of the present embodiment, the membrane interface photochlorination reactor is continuously used, specifically, four membrane interface photochlorination reactors are used in series, and the inside of the reactor is filled with 6 mm glass spring filler.
  • the liquid product obtained from the first stage is heated to 150 ° C and then enters the first stage reactor in the second stage.
  • the chlorination conditions are: external light intensity is 50000 Lux, chlorine gas inlet speed is 3.9 g/min, chlorine gas volume concentration 81.7%, the maximum temperature in the glass tube during the reaction is 150 ° C, the tail gas is discharged from the outlet of the reactor gas stream, and the volume ratio of chlorine in the exhaust gas is 1.3%; the liquid product obtained from the reactor is analyzed by gas chromatography, and the composition is: 75.64% of product intermediates, 21.86% of 1,4-bis(trichloromethyl)benzene, 2.50% impurities;
  • the liquid product obtained from the second-stage first-stage reactor is heated to 160 ° C and then enters the second-stage second-stage reactor under the conditions of an external illumination intensity of 100,000 Lux and a chlorine gas permeation rate of 3.48 g/min.
  • the volume concentration of chlorine gas is 95.2%
  • the maximum temperature in the glass tube is 160 °C during the reaction
  • the tail gas is discharged from the outlet of the reactor gas stream
  • the volume ratio of chlorine in the tail gas is 5.0%
  • the liquid product obtained from the second stage second stage reactor Gas chromatographic analysis, the composition is: 27.27% of product intermediates, 70.34% of 1,4-bis(trichloromethyl)benzene, 2.39% of impurities;
  • the liquid product obtained from the second-stage second-stage reactor is heated to 170 ° C and then enters the second-stage third-stage reactor;
  • the chlorination conditions are: the external light intensity is 150,000 Lux, and the chlorine gas feed rate is 1.92 g/min.
  • the volume concentration of chlorine gas is 96.2%, the maximum temperature in the glass tube is 177 ° C during the reaction, the tail gas is discharged from the outlet of the reactor gas stream, and the volume ratio of chlorine in the tail gas is 5.5%;
  • the liquid obtained from the second stage third stage reactor The product was analyzed by gas chromatography, and the composition was: 6.35% of product intermediate, 91.29% of 1,4-bis(trichloromethyl)benzene, and 2.36% of impurities;
  • the liquid product obtained from the second-stage third-stage reactor is heated to 170 ° C and then enters the second-stage fourth-stage reactor;
  • the chlorination conditions are: the external light intensity is 250,000 Lux, and the chlorine gas feed rate is 1.6 g/min.
  • the volume concentration of chlorine gas is 100%, the maximum temperature in the glass tube is 160 °C during the reaction, the tail gas is discharged from the outlet of the reactor gas stream, and the volume ratio of chlorine in the tail gas is 1.5%;
  • the liquid product obtained from the second stage reactor of the second stage Gas chromatographic analysis the composition is: 0.00% of product intermediates, 97.64% of 1,4-bis(trichloromethyl)benzene, 2.36% of impurities; 1,4-bis(trichloromethyl)benzene yield It is 96.30%.
  • a ring of 25 mm glass rings is filled between two annular cylinders of different diameters. See Figure 3 for a schematic diagram of the reactor structure for the photo-chlorination reaction at the membrane interface.
  • the inner tube has a length of 180 cm, an outer diameter of 8 cm, and a wall thickness of 0.5 cm.
  • the outer tube has a length of 150 cm, an inner diameter of 20 cm, and a wall thickness of 0.5 cm.
  • the first stage reactor reaction conditions are: external illumination intensity is 25000 Lux, internal illumination intensity is 20000 Lux, p-chlorotoluene feed rate is 35 kg/h, chlorine gas velocity is 23.2 kg/h, chlorine concentration is 18.6%;
  • the maximum temperature in the glass tube is 120 ° C; the volume ratio of chlorine in the exhaust gas is 2.3%; at this time, the liquid product at the lower end is collected for gas chromatography analysis; the composition is: 0.80% p-chlorotoluene, 88.70% product intermediate, 8.30% target product 2.20% of impurities;
  • the second stage reactor with ⁇ 25mm glass ring packing is packed in series.
  • the reaction conditions are: external illumination intensity is 25000 Lux, internal illumination intensity is 23000 Lux, chlorine gas velocity is 33.6 kg/h, chlorine concentration is 17.8%; in the glass tube during the reaction The maximum temperature is 130 ° C; the chlorine gas volume ratio in the exhaust gas is 2.5%; the lower chlorination liquid is collected for gas chromatography analysis; the composition is 29.54% of the product intermediate, 68.15% of the product, 2.31% of the impurities;
  • the membrane interface photochlorination reactor was continuously used, specifically, two membrane-connected photo-chlorination reactors with a glass ring packing of 25 mm inside were used in series.
  • the liquid product obtained from the first stage enters the first stage reactor in the second stage, and the chlorination conditions are: the external illumination intensity is 55000 Lux, the internal illumination intensity is 23000 Lux, the chlorine gas velocity is 10.6 kg/h, and the chlorine concentration is 95.5%;
  • the maximum temperature in the glass tube was 130 ° C; the volume ratio of chlorine in the exhaust gas was 5.7%; the chlorination solution at the lower end was collected for gas chromatography; the composition was 5.70% of the product intermediate, 91.10% of the target product, and 3.20% of the impurities;
  • the liquid product obtained in the first stage reactor in the second stage enters the second stage second stage reactor, and the chlorination conditions are: external light intensity of 85000 Lux, internal light intensity of 23000 Lux, chlorine gas speed of 3.6 kg/h, chlorine concentration 100%; the maximum temperature in the glass tube during the reaction is 130 ° C; the volume ratio of chlorine in the exhaust gas is 8.7%; the chlorination solution at the lower end is collected for gas chromatography; the composition is 96.90% of the product, 3.10% of the impurity; the yield of p-chlorotoluene It is 96.01%.
  • the first stage a glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was internally filled as a first-stage reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • Mesitylene is added from the liquid inlet of the reactor, and is formed on the inner wall of the glass tube and the surface of the glass spring through the liquid distributor, and flows down the inner wall and the surface of the glass spring, and chlorine gas is introduced from the lower gas inlet; the intensity of the external light is 20000Lux, the feeding rate of mesitylene is 4.8g/min, the chlorine gas inlet speed is 7.8g/min, the chlorine gas volume concentration is 18.1%, the highest temperature in the glass tube reaction zone is 110°C during the reaction, and the tail gas is exported from the reactor gas stream.
  • the chlorine gas volume ratio in the exhaust gas is 1.5%; liquid chromatography analysis of the liquid product obtained from the first-stage reactor, the mass percentage and composition of each substance are: 23.30% of mesitylene, 75.90% Product intermediates, 0.8% impurities.
  • the liquid product obtained in the first stage reactor continued to enter the second stage reactor filled with 6 mm glass spring packing for photochlorination, the external light intensity was 25000 Lux, the chlorine gas inlet speed was 8.1 g/min, and the chlorine gas volume was The concentration was 18.2%.
  • the maximum temperature in the reaction zone of the glass tube was 130 °C, and the chlorine content in the reaction tail gas was 2.4%.
  • Liquid chromatography analysis of the liquid product obtained from the second-stage reactor, the composition is: 98.95% of the product intermediate, 1.05% of the impurities;
  • the second stage taking 200g of the liquid product obtained in the first stage into a conventional photochlorination reactor to continue the reaction, the light intensity is 150,000 Lux, the chlorine gas feed rate is 20-200 g/h, and the chlorine gas volume concentration is 100%.
  • the temperature in the middle chlorination tower was controlled at 200-280 ° C; the obtained product was analyzed by liquid chromatography, and the composition was: 98.96% of tris(trichloromethyl)benzene and 1.04% of impurities. The yield of tris(trichloromethyl)benzene was 97.84%.
  • the first stage a glass tube with a length of 150 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was filled inside as a reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone. Methylbenzene is added from the liquid inlet of the reactor, and is formed on the inner wall of the glass tube and the surface of the glass spring through the liquid distributor, and flows down the inner wall and the surface of the glass spring.
  • the chlorine gas is introduced through the gas inlet of the lower end; the intensity of the external illumination is 20000Lux, the feeding rate of methylbenzene is 5.5g/min, the chlorine gas inlet speed is 4.1g/min, the chlorine gas volume concentration is 19.4%, the highest temperature in the glass tube reaction zone is 120°C during the reaction, and the tail gas is exported from the reactor gas stream.
  • the chlorine gas volume ratio in the exhaust gas is 2.8%; the liquid product obtained from the reactor is subjected to gas chromatography analysis, and the mass percentage and composition of each substance are: 71.04% of the product intermediate, 26.71% of the target product, 2.25. % of impurities; the effective conversion of methylbenzene reached 97.75%.
  • the second stage taking 200g of the liquid product obtained in the first stage into a conventional photochlorination reactor to continue the reaction, the light intensity is 75000 Lux, the chlorine gas passing rate is 10-24 g/h, the chlorine gas volume concentration is 100%, and the reaction process
  • the temperature in the middle chlorination column was controlled at 140 ° C; the obtained product was subjected to gas chromatography analysis, and the composition was: 97.80% of trichloromethylbenzene and 2.20% of impurities.
  • the yield of trichloromethylbenzene was 96.84%.
  • a ring of 25 mm glass rings is filled between two annular cylinders of different diameters. See Figure 3 for a schematic of the reactor structure.
  • the inner tube has a length of 180 cm, an outer diameter of 8 cm, and a wall thickness of 0.5 cm.
  • the outer tube has a length of 150 cm, an inner diameter of 20 cm, and a wall thickness of 0.5 cm.
  • the first stage reactor reaction conditions are: external illumination intensity of 18000 Lux, internal illumination intensity of 20000 Lux, 1,4-xylene feed rate of 40 kg / h, chlorine gas velocity of 18 kg / h, chlorine concentration of 15.4%; reaction During the process, the maximum temperature in the glass tube is 68 ° C; the volume ratio of chlorine in the exhaust gas is 0.4%; at this time, the liquid product at the lower end is collected for gas chromatography analysis; the composition is: 60.12% of 1,4-xylene, 39.50% of product intermediate, 0.38% of impurities;
  • the second stage reactor with 25mm glass ring packing is packed in series.
  • the reaction conditions are: external light intensity is 20000Lux, internal light intensity is 20000Lux, chlorine gas speed is 23.63kg/h, chlorine concentration is 10.3%; the highest in the glass tube during the reaction The temperature is 70 ° C; the volume ratio of chlorine in the exhaust gas is 0.3%; the chlorination liquid at the lower end is collected for gas chromatography analysis; the composition is: 15.53% of 1,4-xylene, 83.62% of product intermediate, 0.85% of impurities;
  • the second stage taking 200kg of the liquid product obtained in the first stage into a conventional photochlorination reactor to continue the reaction, the light intensity is 70,000 Lux, the chlorine gas inlet speed is 20-120 Kg/h, and the chlorine gas volume concentration is 100%.
  • the temperature in the middle chlorination column was controlled at 120-170 ° C; the obtained product was subjected to gas chromatography analysis, and the composition was: 96.01% of the target product and 3.99% of impurities.
  • the yield of 1,4-bis(trichloromethyl)benzene was 95.5%.
  • a glass tube having a length of 100 cm and an inner diameter of 1.5 cm is vertically placed, and a 6 mm glass spring filler is internally filled as a reactor.
  • the structure of the reactor of this embodiment can be seen in FIG. 2, and the light source 9 is uniformly irradiated from the periphery of the reactor to the reaction zone. .
  • the first stage 1,4-xylene is added from the liquid inlet of the first-stage reactor, and is formed on the inner wall of the glass tube and the surface of the glass spring packing through the liquid distributor, and flows down the inner wall and the surface of the glass spring packing, and the chlorine gas is
  • the lower end gas inlet is open; the external light intensity is 20000 Lux, the 1,4-xylene feed rate is 5.0 g/min, the chlorine gas feed rate is 1.8 g/min, the chlorine gas volume concentration is 17.0%, and the glass tube during the reaction
  • the maximum temperature in the reaction zone is 50 ° C, the exhaust gas is discharged from the outlet of the reactor gas stream, and the volume ratio of chlorine in the exhaust gas is 0.2%; the liquid product obtained by the reaction from the first-stage reactor is subjected to gas chromatography analysis to obtain various substances.
  • the mass percentage and composition are: 85.09% of 1,4-xylene, 14.60% of product intermediates, and 0.31% of impurities.
  • the product in the first stage reactor continues to enter the second stage reactor filled with ⁇ 6mm glass spring packing for photochlorination.
  • the external light intensity is 30,000 Lux
  • the chlorine gas inlet speed is 2.5 g/min
  • the chlorine gas volume concentration is 16.7%.
  • the maximum temperature in the reaction zone of the glass tube is 78 ° C
  • the chlorine content in the reaction tail gas is 1.5%.
  • the liquid product obtained by the reaction of the second-stage reactor is subjected to gas chromatography analysis, and the composition is: 63.6% of 1,4-xylene, 35.70% of product intermediate, and 0.70% of impurities;
  • the liquid product obtained in the second-stage reactor enters the third-stage reactor filled with ⁇ 6mm glass spring packing to continue the photochlorination reaction, the external light intensity is 20000 Lux, the chlorine gas inlet speed is 2.5 g/min, and the chlorine gas volume concentration is 16%, the highest temperature in the reaction zone of the glass tube was 98 °C during the reaction, and the chlorine content in the reaction tail gas was 1.1%.
  • the liquid product obtained from the third-stage reactor reaction was subjected to gas chromatography analysis, and the composition was: 8.60% xylene, 89.64% of product intermediate, and 1.76% of impurities;
  • the second stage taking 200g of the liquid product obtained in the first stage, performing ordinary photochlorination reaction, the light intensity is 100000 Lux, the chlorine gas passing rate is 20-120 g/h, the chlorine gas volume concentration is 100%, and the chloride tower during the reaction
  • the internal temperature was controlled at 120-170 ° C; the obtained product was analyzed by gas chromatography, and the composition was: 97.06% of 1,4-bis(trichloromethyl)benzene, 2.94% of impurities; 1,4-bis(trichloromethyl)
  • the benzene yield was 95.96%.
  • a glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was filled inside as a reactor; the first stage: 1,4-xylene was introduced from the first stage reactor liquid feed port through the liquid
  • the distributor forms a film on the inner wall of the glass tube and the surface of the glass spring filler, and flows down the inner wall and the surface of the glass spring packing.
  • the chlorine gas is introduced from the lower gas inlet; the external light intensity is 6000 Lux, and the feeding speed of 1,4-xylene is 7.0.
  • the chlorine gas volume ratio in the exhaust gas is 1.0. %; collected part of the liquid product obtained from the reaction in the first-stage reactor was analyzed by gas chromatography, and the mass percentage and composition of each substance were: 78.60% of 1,4-xylene, 21.04% of product intermediate, 0.36 % impurities.
  • the product in the first stage reactor continued to enter the second stage reactor filled with ⁇ 6mm glass spring packing for photochlorination.
  • the external light intensity was 12000 Lux
  • the chlorine gas passing rate was 2.5 g/min
  • the chlorine gas volume concentration was 17.7. %
  • the highest temperature in the reaction zone of the glass tube is 80 ° C during the reaction
  • the chlorine content in the reaction tail gas is 1.2%.
  • the liquid product obtained by the reaction from the second-stage reactor is subjected to gas chromatography analysis, and the composition is: 53.3% of 1,4-xylene, 45.91% of product intermediate, and 0.79% of impurities;
  • the product obtained in the second-stage reactor was further subjected to photochlorination in a third-stage reactor packed with ⁇ 6 mm glass spring packing.
  • the external light intensity was 23,000 Lux
  • the chlorine gas velocity was 5.1 g/min
  • the chlorine gas volume concentration was 17.3. %
  • the highest temperature in the reaction zone of the glass tube is 105 ° C during the reaction
  • the chlorine content in the reaction tail gas is 2.0%.
  • the liquid product obtained from the third-stage reactor reaction was subjected to gas chromatography analysis, and the composition was: 2.67% of 1,4-xylene, 95.10% of product intermediate, 0.56% of target product, and 1.67% of impurities;
  • the second stage taking 200g of the liquid product obtained in the first stage, performing ordinary photochlorination reaction, the light intensity is 310000 Lux, the chlorine gas passing rate is 20-120 g/h, and the chlorine gas volume concentration is 80%-100%.
  • the temperature in the chlorination tower was controlled at 120 ⁇ 170 °C; the obtained product was analyzed by gas chromatography, the composition was: 98.30% of the target product, 1.70% of impurities; the yield of 1,4-bis(trichloromethyl)benzene was 96.08. %.
  • a glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was filled inside as a reactor; the first stage: 1,4-xylene was introduced from the first stage reactor liquid feed port through the liquid
  • the distributor forms a film on the inner wall of the glass tube and the surface of the glass spring packing, and flows down the inner wall and the surface of the glass spring packing.
  • the chlorine gas is introduced from the lower gas inlet; the external light intensity is 10000 Lux, and the feeding speed of 1,4-xylene is 5.9.
  • the chlorine gas volume ratio in the tail gas is 4.5. %; collected part of the liquid product obtained from the reaction in the first-stage reactor was analyzed by gas chromatography, and the mass percentage and composition of each substance were: 8.66% of 1,4-xylene, 89.80% of product intermediate, 1.54 % impurities.
  • the liquid product in the first-stage reactor continues to be subjected to photochlorination in a second-stage reactor packed with ⁇ 6 mm glass spring packing.
  • the external light intensity is 15000 Lux
  • the chlorine gas feed rate is 4.6 g/min
  • the chlorine gas volume concentration is 20%
  • the highest temperature in the reaction zone of the glass tube is 128 °C during the reaction
  • the chlorine content in the reaction tail gas is 3.8%.
  • the liquid product obtained from the second-stage reactor was subjected to gas chromatography analysis, and the composition was: 0.11% of 1,4-xylene, 96.14% of product intermediate, 2.15% of target product, and 1.6% of impurities;
  • the liquid product obtained in the second-stage reactor was heated to 160 ° C, and the photorechlorination reaction was continued in a third reactor filled with ⁇ 6 mm glass spring packing.
  • the external light intensity was 15000 Lux and the chlorine gas penetration rate was 11.5 g/min.
  • the volume concentration of chlorine gas is 20%.
  • the maximum temperature in the glass tube reaction zone is 160 °C, and the chlorine content in the reaction tail gas is 3.8%.
  • the liquid product obtained from the third-stage reactor reaction was subjected to gas chromatography analysis, and the composition was: 37.38% of product intermediate, 60.82% of 1,4 bis(trichloromethyl)benzene, and 1.80% of impurities;
  • the second stage taking 200g of the liquid product obtained in the first stage, performing ordinary photochlorination reaction, the light intensity is 100000 Lux, the chlorine gas passing rate is 20-120 g/h, the chlorine gas volume concentration is 100%, and the chloride tower during the reaction
  • the internal temperature is controlled at 120 ⁇ 170 ° C; the obtained product is analyzed by gas chromatography, the composition is: 98.25% of 1,4 bis(trichloromethyl)benzene, 1.75% of impurities; 1,4-bis(trichloromethyl)
  • the yield of benzene product was 97.68%.
  • a glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was filled inside as a reactor; the first stage: 1,4-xylene was introduced from the first stage reactor liquid feed port through the liquid
  • the distributor forms a film on the inner wall of the glass tube and the surface of the glass spring filler, and flows down the inner wall and the surface of the glass spring packing.
  • the chlorine gas is introduced from the lower gas inlet; the external light intensity is 10000 Lux, and the 1,4-xylene feeding speed is 6.1.
  • the product in the first-stage reactor continues to be subjected to photochlorination in a second-stage reactor packed with ⁇ 6 mm glass spring packing in series, the external light intensity is 20000 Lux, the chlorine gas feed rate is 3.9 g/min, and the chlorine gas volume concentration At 12.9%, the highest temperature in the reaction zone of the glass tube was 75 °C during the reaction, and the chlorine content in the reaction tail gas was 1.3%.
  • the liquid product obtained by the reaction of the second-stage reactor was subjected to gas chromatography analysis, and the composition was 35.40% of 1,4-xylene, 63.50% of product intermediate, and 1.10% of impurities.
  • the liquid product in the second-stage reactor continues to be subjected to a photo-chlorination reaction in a third-stage reactor packed with ⁇ 6 mm glass spring packing in series, the external light intensity is 30,000 Lux, the chlorine gas velocity is 4.7 g/min, and the chlorine gas volume The concentration is 13.0%, the highest temperature in the reaction zone of the glass tube is 75 °C during the reaction, and the chlorine content in the reaction tail gas is 2.5%.
  • the liquid product obtained from the third-stage reactor reaction was subjected to gas chromatography analysis, and the composition was 16.90% of 1,4-xylene, 81.85% of product intermediate, and 1.25% of impurities.
  • Second stage In the second stage of this example, two membrane-interface photochlorination reactors filled with ⁇ 6 mm glass spring packing were used in the form of a conventional photochlorination reactor.
  • the liquid product obtained from the first stage enters the first-stage reactor in the second stage for photochlorination reaction, the external light intensity is 30,000 Lux, the chlorine gas feed rate is 4.1 g/min, and the chlorine gas volume concentration is 14.0%.
  • the maximum temperature in the reaction zone of the glass tube is 73 ° C, and the chlorine content in the reaction tail gas is 7.5%.
  • the liquid product obtained from the fourth-stage reactor reaction was subjected to gas chromatography analysis, and the composition was 0.13% of 1,4-xylene, 98.22% of product intermediate, and 1.65% of impurities.
  • the product in the second stage first stage reactor continues to enter the second stage reactor for photochlorination reaction, the external light intensity is 30,000 Lux, the chlorine gas inlet speed is 4.1 g/min, and the chlorine gas volume concentration is 100%.
  • the highest temperature in the reaction zone of the glass tube is 125 ° C, and the chlorine content in the reaction tail gas is 1.9%.
  • the liquid product obtained from the fifth-stage reactor reaction was subjected to gas chromatography analysis, and the composition was: 91.88% of the product intermediate, 6.53% of the target product, and 1.59% of the impurity.
  • the light intensity is 80000Lux
  • the chlorine gas inlet speed is 20 ⁇ 120g/h
  • the chlorine gas volume concentration is 100%.
  • the temperature in the chlorination column was controlled at 120-170 ° C; the obtained product was analyzed by gas chromatography, and the composition was: 98.37% of the target product, 1.63% of the impurity; 1,4-bis(trichloromethyl)benzene product was collected. The rate is 95.32%.
  • the first stage a glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was internally filled as a first-stage reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • the 1,3-xylene is added from the liquid inlet of the reactor, formed on the inner wall of the glass tube through the liquid distributor, and flows down the inner wall, and the chlorine gas is introduced from the lower gas inlet port 3; the external light intensity is 28000 Lux, 1,
  • the feed rate of 3-xylene was 5.3g/min, the chlorine gas inlet speed was 5.6g/min, the chlorine gas volume concentration was 18%, and the highest temperature in the glass tube reaction zone was 90°C during the reaction.
  • the tail gas was discharged from the reactor gas stream outlet.
  • Gas chromatography analysis of the liquid product obtained from the reactor showed that the mass percentage and composition of each substance were: 31.54% of 1,3-xylene, 67.44% of product intermediate, and 1.02% of impurities.
  • the product in the first stage reactor continues into the second stage reactor in which the internal packed ⁇ 6mm glass spring packing is connected for photochlorination.
  • the external light intensity is 33000 Lux
  • the chlorine gas inlet speed is 5.7 g/min
  • the chlorine gas volume concentration is 18.7%
  • the highest temperature in the reaction zone of the glass tube was 95 °C during the reaction
  • the chlorine content in the reaction tail gas was 3.8%.
  • the liquid product obtained from the second-stage reactor was subjected to gas chromatography analysis, and the composition was: 0.2% xylene, 89.67% product intermediate, 8.9% 1,3-bis(trichloromethyl)benzene, 1.23 % impurity; in the two-stage reaction, the effective conversion of 1,3-xylene reaches 98.95%.
  • the second stage 200g of the product obtained in the first stage is introduced into a conventional photochlorination reactor with an illumination intensity of 70,000 Lux, a chlorine gas feed rate of 20-120 g/h, a chlorine gas volume concentration of 52%, and chlorination during the reaction.
  • the temperature in the column was controlled at 120-170 ° C; the obtained product was analyzed by gas chromatography, and the composition was: 97.33% of 1,3-bis(trichloromethyl)benzene and 2.67% of impurities.
  • the yield of 1,3-bis(trichloromethyl)benzene was 96.58%.
  • the purity of 1,3-bis(trichloromethyl)benzene obtained by one-step purification of the obtained product was 99.94%.
  • the first stage a glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was internally filled as a first-stage reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • 1,4-xylene is added from the liquid inlet of the reactor, formed on the inner wall of the glass tube through the liquid distributor, and flows down the inner wall, and chlorine gas is introduced from the lower gas inlet port 3; the external light intensity is 33000 Lux, 1,
  • the feed rate of 4-xylene was 5.4g/min, the chlorine gas inlet speed was 5.6g/min, the chlorine gas volume concentration was 17%, and the highest temperature in the glass tube reaction zone was 95°C during the reaction.
  • the tail gas was discharged from the reactor gas stream outlet.
  • Gas chromatography analysis of the liquid product obtained from the reactor showed that the mass percentage and composition of each substance were: 21.54% of 1,4-xylene, 77.41% of product intermediate, and 1.05% of impurities.
  • the product in the first stage reactor continues into the second stage reactor in which the internal ⁇ 6mm glass spring packing is packed in series for photochlorination.
  • the external light intensity is 50000 Lux
  • the chlorine gas inlet speed is 7.2 g/min
  • the chlorine gas volume concentration is 19%
  • the highest temperature in the glass tube reaction zone during the reaction is 100 °C.
  • the liquid product obtained from the second-stage reactor was subjected to gas chromatography analysis, and the composition was: 0% xylene, 89.53% of product intermediate, 9.2% of 1,4-bis(trichloromethyl)benzene, 1.27 % impurity; in the two-stage reaction, the effective conversion of 1,4-xylene reached 98.82%.
  • the second stage 200g of the product obtained in the first stage is introduced into a conventional photochlorination reactor with an illumination intensity of 55000 Lux, a chlorine gas feed rate of 20-120 g/h, a chlorine gas volume concentration of 22%, and chlorination during the reaction.
  • the temperature in the column was controlled at 120-170 ° C; the obtained product was analyzed by gas chromatography, and the composition was: 98.01% of 1,4-bis(trichloromethyl)benzene and 1.99% of impurities.
  • the yield of 1,4-bis(trichloromethyl)benzene was 97.74%.
  • the purity of 1,4-bis(trichloromethyl)benzene obtained by one-step purification of the obtained product was 99.97%.
  • a hollow glass tube with a length of 100 cm and an inner diameter of 1.5 cm was placed vertically, and a 6 mm glass spring filler was filled inside as a reactor; 1,4-xylene was introduced from the reactor liquid feed port through the liquid distributor on the inner wall of the glass tube. And the surface of the glass spring filler is formed into a film, and flows along the inner wall and the surface of the glass spring packing, and chlorine gas is introduced from the lower gas inlet; the external light intensity is 20000 Lux, and the 1,4-xylene feeding speed is 5.2 g/min.
  • the chlorine gas feed rate was 5.4 g/min, and the chlorine gas volume concentration was 45%. After the chlorine gas was passed for 20 minutes, the reaction solution carbonized and blackened, and the reaction failed.
  • a hollow glass tube with a length of 100 cm and an inner diameter of 1.5 cm is placed vertically, and a 6 mm glass spring filler is filled inside as a reactor; 1,3-xylene is added from the reactor liquid feed port through the liquid distributor on the inner wall of the glass tube And the surface of the glass spring filler is formed into a film, and flows along the inner wall and the surface of the glass spring filler, and the chlorine gas is introduced from the lower gas inlet; the external light intensity is 50000 Lux, and the 1,3-xylene feed rate is 5.7 g/min.
  • the chlorine gas feed rate was 3.2 g/min, the chlorine gas volume concentration was 55%, and after the chlorine gas was passed for 16 minutes, the reaction solution carbonized and blackened, and the reaction failed.
  • a hollow glass tube with a length of 100 cm and an inner diameter of 1.5 cm is placed vertically, and a 6 mm glass spring filler is filled inside as a reactor; p-chlorotoluene is added from the reactor liquid feed port through the liquid distributor on the inner wall of the glass tube and the glass spring The surface of the filler is filmed and flows down the inner wall and the surface of the glass spring packing.
  • the chlorine gas is passed through the lower gas inlet; the external light intensity is 32000 Lux, the p-chlorotoluene feeding rate is 4.5 g/min, and the chlorine gas inlet speed is 3.2. g/min, the volume concentration of chlorine gas is 50%, and after the chlorine gas is passed for 24 minutes, the reaction solution carbonizes to black, and the reaction fails.
  • a glass tube having a length of 100 cm and an inner diameter of 1.5 cm was vertically placed, and a 6 mm glass spring filler was internally filled as a first-stage reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • the 1,3-xylene is added from the liquid inlet of the reactor, formed on the inner wall of the glass tube by the liquid distributor, and flows down the inner wall, and the chlorine gas is introduced from the lower gas inlet port 3; the external light intensity is 25000 Lux, 1,
  • the feed rate of 3-xylene was 5.0g/min, the chlorine gas feed rate was 5.7g/min, the chlorine gas volume concentration was 15%, and the highest temperature in the glass tube reaction zone was 83°C during the reaction.
  • the tail gas was discharged from the reactor gas stream outlet.
  • Gas chromatography analysis of the liquid product obtained from the reactor showed that the mass percentage and composition of each substance were: 35.58% of 1,3-xylene, 63.39% of product intermediate, and 1.03% of impurities.
  • the above reaction product enters the second-stage membrane interface photochlorination reactor filled with ⁇ 6mm glass spring packing, and continues to pass chlorine gas for reaction.
  • the external light intensity is 21030 Lux
  • the chlorine gas inlet speed is 5.7 g/min
  • the chlorine gas volume concentration is 42. %
  • the highest temperature in the glass tube reaction zone during the reaction is 125 ° C.
  • the liquid product obtained from the second-stage reactor is analyzed by gas chromatography.
  • the composition is: 0% xylene, 32.2% of product intermediate, 51.1% 1,3-bis(trichloromethyl)benzene, 16.7% impurities; in the two-stage reaction, the effective conversion rate of 1,3-xylene is 80.54%.
  • a glass tube having a length of 100 cm and an inner diameter of 1.5 cm was vertically placed, and a 6 mm glass spring filler was internally filled as a first-stage reactor; the light source was uniformly irradiated from the periphery of the reactor to the reaction zone.
  • 1,4-xylene is added from the liquid inlet of the reactor, formed on the inner wall of the glass tube through the liquid distributor, and flows down the inner wall, and chlorine gas is introduced from the lower gas inlet port 3; the external light intensity is 2000 Lux, 1,
  • the feed rate of 4-xylene was 4.5g/min, the chlorine gas inlet speed was 4.0g/min, the chlorine gas volume concentration was 10%, and the maximum temperature in the glass tube reaction zone was 95°C during the reaction.
  • the tail gas was discharged from the reactor gas stream outlet.
  • Gas chromatography analysis of the liquid product obtained from the reactor showed that the mass percentage and composition of each substance were: 22.78% of 1,4-xylene, 72.93% of product intermediate, 3.24% of target product, 1.05 % impurities.
  • the above reaction product enters the second-stage membrane interface photochlorination reactor filled with ⁇ 6mm glass spring packing, and continues to pass chlorine gas for reaction.
  • the external light intensity is 45000 Lux
  • the chlorine gas inlet speed is 5.8 g/min
  • the chlorine gas volume concentration is 45. %
  • the maximum temperature of the glass tube in the reaction zone during the reaction is 130 ° C.
  • the liquid product obtained from the second-stage reactor is analyzed by gas chromatography.
  • the composition is: 0% xylene, 25.24% of product intermediate, 66.41% 1,4-bis(trichloromethyl)benzene, 8.35% impurities; in the two-stage reaction, the effective conversion of 1,4-dimethylbenzene is 85.07%.

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Abstract

本发明涉及塔式连续光氯化法制氯苄，使化学式为(X)aC6H6-a-b(CH3)b的芳烃类化合物在流动中成液膜，与氯气在光照条件下进行膜界面光氯化反应，反应开始时侧链甲基上的一个氢被氯取代生成一氯苄。并可以继续通入氯气反应，苄基上的两个氢被氯取代生成二氯苄，以此类推，侧链甲基上的氢逐渐被氯取代，并最终可以得到侧链甲基上的氢全部被氯取代的产物。本申请的主要优点在于：副反应少，产品收率高，产品纯度高，且易于进一步纯化，反应效率高，生产时间短，适宜于工业化生产。

Description

塔式连续光氯化法制氯苄 技术领域
本申请涉及一种塔式连续光氯化法制氯苄，尤其涉及一种由芳烃类化合物与氯气在膜界面发生光化学反应，从而使苯环上甲基氯化的方法。本申请方法在膜界面上主要发生的是气相光氯化反应，能够大幅度降低苯环氯代等副产物，提高目标产物的收率。本申请还涉及一种膜界面光氯化反应器。
 背景技术
化学式为(X) aC 6H 6-a-b(CH 3) b的芳烃类化合物侧链光氯化所得到的衍生产物，是重要的有机合成中间体。以三氯甲基取代苯为例，二（三氯甲基）苯、均三（三氯甲基）苯等是制备高分子材料、医药、染料、农药等重要的中间产物。光氯化法制氯苄通常是采用光氯化反应。光氯化反应主要是以光子来引发侧链自由基进行氯化反应，部分反应使用自由基光引发剂或与自由基热引发剂组成复合引发体系使用。
现有技术中光氯化反应存在的缺陷主要是：（1）光氯化反应是自由基链式反应，因存在副反应，氯化位点和氯化深度相对较难控制。为了分离复杂的光氯化产物，DE3146868不得不进行大量的精馏操作，极大地提高了该类产品的生产成本。（2）为了防止苯环上的氯取代反应，需要引入多种辅助成分，这些辅助成分会“污染”目标产物三氯甲基取代苯，不适于高纯度产品的制备，例如：US 1345373添加硫磺和乙酰氯、US 1384909添加金属碳酸盐、US 1733268添加磷和硫磺等。（3）光氯化反应还需要加入自由基引发剂来启动反应，王鲁敏等人（通化师范学院学报，2005，26（4）：46~47）的研究表明光氯化1,3-二（甲基）苯反应中需要加入自由基引发剂来维持反应。（4）光氯化反应是高度放热反应，反应热难于控制，而伴随着高反应热，反应原料会产生过度氯化以及其他不良副反应，出现焦油状物质，这些物质一旦形成，只能当作废弃物处理，对于产品质量有相当大的不利影响。
 CN104591958B公开了一种连续化生产三氯甲基取代苯化合物的方法，通过控制温度、光照度和氯气量等反应条件，能够大幅提高三氯甲基取代苯的纯度和收率。
然而，发明人通过进一步研究发现，现有技术反应过程中，氯气基本上都是以气泡形式分散在液体中进行反应，反应产物存在大量返混，会影响反应的选择性，在达到高纯度和高收率的同时，光氯化反应的效率有待进一步提高。
 技术问题
发明人前期研究发现，在通过光氯化反应使苯环上甲基氯化得到所需产物后，副产物难于分离，而这些副产物主要是发生苯环氯代的副产物，例如苯环一氯代同时侧链甲基氯代的副产物。因为这些苯环氯代的副产物与目标产物的沸点较为接近，因而分离过程困难、分离成本高。
 技术解决方案
发明人进一步研究发现，可以利用膜界面光氯化反应更好的制备氯苄，也即苯环侧链甲基上的氢原子被氯原子取代的产物。因为在光氯化反应初期，通过膜界面反应，主要发生的是气相光氯化反应，基本上得到的是苯环侧链甲基上的氢原子被氯原子取代的产物，而苯环上的氢原子被氯原子取代的副反应几乎不会发生。
因此，本申请涉及一种塔式连续光氯化法制氯苄，其具体的技术方案为：使化学式为(X) aC 6H 6-a-b(CH 3) b的芳烃类化合物在流动中成液膜，与氯气在光照条件下进行膜界面光氯化反应，反应开始时侧链甲基上的一个氢原子被氯原子取代生成一氯苄；
所述X为氯或溴或氟原子，a为选自0、1、2、3、4或5的整数，b为选自1、2或3 的整数，且a+b≤6。
进一步地，可以继续通入氯气反应，苄基上的两个氢原子被氯原子取代生成二氯苄，以此类推，侧链甲基上的氢原子逐渐被氯原子取代，并最终可以得到芳烃类化合物侧链甲基上的氢原子全部被氯原子取代的产物。
本申请所述膜界面光氯化反应是指液体反应物料（例如本申请所述的化学式为(X) aC 6H 6-a-b(CH 3) b的芳烃类化合物）形成液膜，与气体接触，在光照条件下进行的反应。
优选地，所述产物为一氯苄时，氯气体积浓度为1~40%。
本申请所述产物为一氯苄时，氯气体积浓度可以是所述1~40%范围中任意值或所述范围内任意值组合形成的范围，例如5%、10%、15%、20%、25%、30%、35%、40%、1~20%、15~30%等，优选氯气体积浓度为5~30%，进一步优选氯气体积浓度为10~20%。
优选地，所述产物为一氯苄时，反应温度为20℃~150℃。
本申请所述产物为一氯苄时，反应温度可以是所述20℃~150℃范围中任意值或所述范围内任意值组合形成的范围，例如20℃、30℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃，优选反应温度为60~100℃。
优选地，所述产物为一氯苄时，通入的氯气量为苯环侧链甲基全氯代所需的理论化学计算量的2~40%。
本申请所述产物为一氯苄时，通入的氯气量可以是苯环侧链甲基全氯代所需的理论化学计算量的2~40%范围中任意值或所述范围内任意值组合形成的范围，例如2%、5%、10%、15%、20%、25%、30%、35%、40%，优选3~30%。
在经过所述产物为一氯苄的反应阶段后，进一步与氯气进行反应，可以得到多氯苄产物，例如二氯苄、三氯苄、四氯苄、五氯苄、六氯苄、七氯苄、八氯苄或者九氯苄等，优选地，在进一步与氯气进行反应的过程中，相应的提高反应温度，且最高反应温度不超过180℃。进一步的与氯气进行反应的过程可以与一氯苄的反应阶段在一个反应器内完成或者在多个后续串联连接的反应器内完成。
本领域技术人员，可以通过对温度和氯气的控制，及时停止反应以得到所需的目标产物，例如一氯苄、二氯苄等。特别地，可以在得到的产物主要为所需的目标产物时，停止反应，并将一氯代物与原料芳烃类化合物分离，以得到纯度更高的目标产物。
发明人发现，在膜界面光氯化反应中，氯原子取代发生在苯环的侧链甲基上，一氯取代之后难于生成苯环上的氢原子被氯原子取代的副产物，甲基上的氢原子被氯原子取代以后得到的中间体非常稳定，在后续继续与足量的氯气接触发生光氯化反应过程中，均会生成三氯甲基取代苯（苯环侧链甲基上的氢原子全部被氯原子取代的产物）。可以得出：通过膜界面光氯化反应得到的产物中间体只需进行进一步氯化即可得到三氯甲基取代苯。并且，根据本发明的方法直接获得的三氯甲基取代苯反应混合物中很少含有与主产物沸点相近的杂质，可以通过简单蒸馏或一次精馏获得高纯度的三氯甲基取代苯产品。
因此，另一方面，本申请涉及一种塔式连续光氯化制氯苄的方法，分为两个阶段，第一阶段：使化学式为(X) aC 6H 6-a-b(CH 3) b的芳烃类化合物在流动中成液膜，与氯气在光照条件下进行膜界面光氯化反应，检测残余芳烃类化合物(X) aC 6H 6-a-b(CH 3) b的质量百分含量，当含量为0~20%时，第一阶段反应结束；第二阶段：将第一阶段得到的反应中间产物进一步与氯气进行光氯化反应直到反应完成，得到三氯甲基取代苯；所述X为氯或溴或氟原子，a为选自0、1、2、3、4或5的整数，b为选自1、2或3的整数，且a+b≤6。
本申请所述第一阶段，检测残余芳烃类化合物的质量百分含量，可以是所述0~20%范围中任意值或所述范围内任意值组合形成的范围，例如0、0.5%、1%、1.5%、2.0%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%、5.5%、6.0%、6.5%、7.0%、7.5%、8.0%、8.5%、9.0%、9.5%、10.0%、10.5%、11.0%、11.5%、12%、12.5%、13%、13.5%、14%、14.5%、15%、15.5%、16%、16.5%、17%、17.5%、18%、18.5%、19%、19.5%、20%等等，第一阶段反应结束。
在本发明的各种实施方式中，检测残余芳烃类化合物的质量百分含量，优选当含量为0~12%时，进一步优选当含量为0~2%时，特别优选当含量为0%时，第一阶段反应结束。
发明人发现，在膜界面光氯化反应过程中，对于氯气浓度的控制特别重要，特别是反应开始时，氯气浓度过高，反应物料很快发生碳化。因此，优选地，第一阶段氯气体积浓度为1~40%，优选氯气体积浓度为5~30%，进一步优选氯气体积浓度为10~20%。
本申请所述第一阶段膜界面光氯化反应的反应温度为20℃~180℃。
进一步地，所述膜界面光氯化反应的反应温度可以是所述20℃~180℃范围中任意值或所述范围内任意值组合形成的范围，例如20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃等等。在本发明的各种实施方式中，膜界面光氯化反应的反应温度优选为80℃~120℃。反应温度过低，反应速度慢，耗时长，不利于工业化生产，且不利于液体反应物料蒸发为气体，从而实现芳烃与氯气间的气-气相之间的反应；反应温度过高，则不利于反应热的移除，副反应发生，产品收率降低。
本申请所述第一阶段，可以采用在一个或者多个反应器内完成，所述多个反应器可以采用串联或者并联或者其他的连接方式，例如第一阶段采用2~10个串联的反应器，优选采用2~3个串联的反应器。
本领域技术人员能够理解，当发生膜界面光氯化反应的反应器设计的足够长，那么在该单个反应器中，即可以完成苯环上甲基全部被氯化的反应。本领域技术人员可以根据需求具体设计出合适长度的膜界面光氯化反应器。
因此，本申请还涉及在一个反应器内进行膜界面光氯化反应直到反应完成的方案，即所述第一阶段和第二阶段发生在同一个反应器内，进行膜界面光氯化反应，直到反应完成，得到三氯甲基取代苯。
当所述第一阶段采用多个串联的反应器时，优选各串联反应器的反应温度逐渐提高。
当所述第一阶段采用两个串联的反应器时，第一个反应器的反应温度为20℃~150℃，第二个反应器的反应温度为60℃~180℃，优选，第一个反应器的反应温度为80℃~105℃，第二个反应器的反应温度为100℃~120℃；当采用三个串联的反应器时，第一个反应器的反应温度为20℃~150℃，第二个反应器的反应温度为60℃~180℃，第三个反应器的反应温度为60℃~180℃，优选，第一个反应器的反应温度为80℃~100℃，第二个反应器的反应温度为90℃~120℃，第三个反应器的反应温度为95℃~120℃。
在同一个反应器内完成第一阶段和第二阶段的膜界面光氯化反应时，反应条件与在多个反应器内完成膜界面光氯化反应时基本相同，例如在苯环上甲基发生一氯代的反应过程中，通入的氯气体积浓度最好控制在1~40%，优选为2~30%，进一步优选为5~20%。且氯化反应温度随着氯化深度的提高在20℃~180℃的范围内相应提高。
本申请经过第一阶段得到的反应产物，基本是苯环侧链甲基上至少有一个氢原子被氯原子取代的化合物，该部分反应产物继续进行光氯化反应不会出现苯环氯代的副产物。且发明人进一步发现，只要反应后残余芳烃类化合物的质量百分含量为0~20%，对于氯气体积浓度就不需要进行特别的限制，即使使用体积浓度为100%氯气，也不会造成反应物料碳化。因此，在经历过所述第一阶段后，也即在第二阶段，通入反应器的氯气体积浓度不需要特别的控制，可以在1%~100%的范围内变动，为了保证反应效率，优选氯气体积浓度为75~100%。
本申请中氯气体积浓度非100%时，可以通过加入惰性气体进行稀释，例如加入氮气、氩气、氦气、二氧化碳等，从而得到体积浓度合适的氯气。
所述第二阶段的光氯化反应，采用的反应器的类型，及具体的反应条件，均没有特别的限制，本领域技术人员可以根据现有技术即可实现。
在本发明的各种实施方式中，第二阶段中的光氯化反应，反应温度优选为80℃~280℃，更优选为120℃~170℃。具体地，反应温度可以根据不同的反应物料和需求来确定。
所述第二阶段可以采用一个现有技术中的常规的光氯化反应器，一般以液体为连续相，气体以气泡形式分散在液体中进行气液反应的光氯化反应器，例如CN203916645U中所公开的光氯化反应器；也可以采用多个，例如2~3个串联的常规的光氯化反应器来完成反应；也可以采用2~6个本申请所述的膜界面光氯化反应器来继续完成反应，例如采用2~6个串联的降膜式反应器；还可以采用常规的光氯化反应器与降膜式反应器结合的形式来完成反应。本领域技术人员可以根据实际情况来进行合理安排。
本申请所述膜界面光氯化反应可以通过现有的反应器来实现，例如本领域技术人员所熟知的填料塔式反应器、降膜式反应器、升膜式反应器或者滴流床反应器等。例如，在上述液体反应物料能够在反应器内成液膜的反应器的基础上，增加光照条件，从而可以发生膜界面光氯化反应的反应器，本申请将其称之为膜界面光氯化反应器。
特别优选地，所述膜界面光氯化反应过程中，在反应器内添加具有透光性的填料和/或挡板，液体物料沿着所述填料和/或挡板成液膜状态流动。
本申请所述光氯化反应，光照度为1000 Lux~约400000 Lux，优选为20000 Lux ~100000 Lux。
本申请所述第一阶段得到的反应中间产物除苯环侧链甲基上至少有一个氢被氯取代的化合物也即目标产物中间体外，还包括部分目标产物三氯甲基取代苯和/或少量未反应的原料及副产物。
本申请制得的三氯甲基取代苯产品纯度高，在反应完成后，基本上可以直接获得目标产物纯度为95%以上的反应物。如有需要，可对反应产物进行进一步纯化，本申请所得反应物通过常规的纯化方法，例如蒸馏、精馏或重结晶等，即可获得纯度为99%以上的产物。
进一步地，本申请提供一种膜界面光氯化反应器，包括反应器壳体，反应器壳体上设置有液体进料口、气体进料口、气体出口和产物出口，所述液体进料在流动中生成液膜，所述光氯化反应的光源从反应器的周围和/或内部向反应区均匀照射，所述光源与发生光氯化反应的反应区域被反应器壳体隔开。
所述膜界面光氯化反应器壳体为单个柱体或者两个同心柱体组成的空心柱体。
所述膜界面光氯化反应器为单个柱体时，液体物料沿着柱体内壁成液膜流动，光源设置在柱体壁的外围，从柱体的外周均匀向反应区照射；所述反应器为两个同心柱体组成的空心柱体时，液体物料沿着外柱体的内壁和/或内柱体的外壁成液膜流动，光源设置在外柱体的外围和/或内柱体的内部，均匀向反应区照射。
所述膜界面光氯化反应器为两个同心柱体组成的空心柱体时，任意一个或两个柱体的材质为透光性材料，所述两个柱体的材质均为透光性的材料时，外柱体的外围和/或内柱体的内部设置有光源，均匀向反应区照射；所述仅外柱体为透光性材料时，外柱体的外围设置光源，均匀向反应区照射；所述仅内柱体为透光性材料时，内柱体的内部设置光源，均匀向反应区照射。
所述膜界面光氯化反应器为单个柱体时，其材质为具有透光性的材料，例如玻璃、石英等透光性好的材料，优选具有透光性兼具耐腐蚀性能的材料。所述反应器为两个同心柱体时，其透光材质可以是玻璃、石英等，其不透光的材质可以是搪瓷、耐腐蚀的金属材料，例如衬氟金属材料、哈氏合金等。
所述膜界面光氯化反应器液体进料口进一步设置有液体分布器；气体进料口进一步设置有气体分布器。
所述膜界面光氯化反应器可以垂直放置或者按照不同角度倾斜放置，通过倾斜角度可以调整反应器液体物料的停留时间。当反应器采用倾斜放置的方式时，优选反应器为空心四面柱体结构或者多面柱体结构，液体物料成液膜的面积较大。也可以在柱体内安装斜置的挡板。
所述液体原料与氯气在反应器内可以是并流或者逆流接触。
优选地，所述膜界面光氯化反应器反应区添加具有透光性的填料和/或挡板，液体物料沿着柱体壁以及填料和/或挡板均匀成液膜态流动。
所述膜界面光氯化反应器壳体中柱体的具体形状没有特别的限制，可以是空心圆柱体、空心多面柱体，例如空心四面柱体等。
本领域技术人员能够理解本申请所述的反应温度逐渐提高、氯气浓度逐渐提高等句子中“逐渐”的含义。
 有益效果
（1）化学式为(X) aC 6H 6~a~b(CH 3) b的芳烃类化合物与氯气在光照条件下进行膜界面光氯化反应，膜界面光氯化反应主要是通过反应器和/或填料设计，增加反应界面与汽化面积达到迅速反应与快速移走热量的目的,物料比表面积较大，本申请工艺中，氯气进入后，特别是在特定的氯气体积浓度及温度范围内，以液膜中的芳烃类化合物蒸发形成的芳烃类化合物蒸汽与氯气在光照条件下发生气相反应为主，该种反应不产生苯环氯代副产物；而氯气与物料膜表面及内部发生反应为辅；并且，本申请中反应产生的热量主要集中在气相，由通入的混合气体中没有反应的气体及反应产生的氯化氢带走，有利于及时除去反应热，可以减少热敏型的氯代产物在高温下副反应的发生。在光氯化反应中不易控制的主要的两种副反应均得到了有效抑制，从而有效提高了反应产物收率；并且可以通过控制氯气进量、氯气浓度、反应温度等，得到不同的多氯苄产物；
（2）当目标产物为三氯甲基取代苯时，反应可以分为两个阶段，在第一阶段采用膜界面光氯化反应，氯代发生在苯环的侧链甲基上，苯环甲基氯代以后得到的中间体非常稳定，在后续继续与氯气接触发生光氯化反应过程中，均会生成苯环上甲基的氯代物，因此后续第二阶段的反应条件易于控制，例如可以用常规的光氯化反应器进行进一步的光氯化反应直到反应完成；制备的三氯甲基取代苯，纯度高，易于进一步纯化，且反应效率高，生产周期短，适合于工业化生产。
 附图说明
图1为本发明实施例5的工艺流程图；
图2单柱体膜界面光氯化反应器结构示意图；
图3双柱体膜界面光氯化反应器结构示意图；
附图标记含义：
1-膜界面光氯化反应器；2-液体进料口；3-气体进料口；4-气体出口；5-反应产物出口； 6-常规光氯化反应器；7-光源。
 本发明的实施方式
本申请所述的有效转化率是指芳烃类化合物原料转化为目标产品以及目标产品中间体的量的总和与芳烃类化合物原料发生氯代反应的量的质量比。
本申请所述的收率是指反应实际所得三氯甲基取代苯与原料芳烃类化合物通过氯化反应在理论上可以得到的三氯甲基取代苯的质量比。
本申请实施例中所述的氯气通入速度是指将各体积浓度的氯气换算为纯氯气后的质量流量。
实施例1
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；本实施例膜界面光氯化反应器结构图可以参见图2，光源9从反应器的外围均匀照射于物料反应区。反应过程为：1,4-二甲苯由反应器1液体进料口2加入，通过液体分布器（图中未示出）在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面向下流动，氯气由下端气体进料口3通入；外照光强度为20000Lux，1,4-二甲苯加料速度为5.2g/min，氯气通入速度为2.09g/min，氯气体积浓度为15%，反应过程中控制玻璃管反应区内最高温度100℃，尾气从反应器气体物流出口4排出，采集部分从反应器1的反应产物出口5的产物进行气相色谱分析，得出各物质的质量百分比和成份为：6.51%的1,4-二甲苯、91.53%的产品中间体、0.74%的1,4-二（三氯甲基）苯、1.22%的杂质，其中，产品中间体中的一氯苄占反应产物的81.67%。1,4-二甲苯的有效转化率达到99.06%。对反应产物进行精馏纯化，得到纯度为97%的一氯苄。
实施例2
反应器的形式：两根不同直径的玻璃管组成的环状柱体之间填充Ф25mm的玻璃环。膜界面光氯化反应器结构示意图参见图3。
内管长度180cm，外径8cm、壁厚0.5cm。
外管长度150cm，内径20cm、壁厚0.5cm。
反应过程为：外照光强度为25000Lux，内照光强度为20000Lux，对氯甲苯加料速度35kg/h，并沿着填料和外柱体的内壁以及内柱体的外壁成膜并向下流动，通氯气速度20.62kg/h，氯气体积浓度20%；反应过程中玻璃管内最高温度60℃；收集下端的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：5.83%的对氯甲苯、90.57%的产品中间体、2.46%的对氯三氯甲基苯、1.14%的杂质；其中，产品中间体中的一氯苄占反应产物的85.21%。对氯甲苯的有效转化率达到98.55%。对反应产物进行精馏纯化，得到纯度为96%的对氯一氯苄。
实施例3
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；光源从反应器的外围均匀照射于反应区。均三甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧表面成膜，并沿内壁及玻璃弹簧表面向下流动，氯气由下端气体进料口通入；外照光强度为20000Lux，均三甲苯加料速度为4.8g/min，氯气通入速度为1.28g/min，氯气体积浓度为15%，反应过程中玻璃管反应区内最高温度120℃，尾气从反应器气体物流出口排出；对从反应器中得到的液体产物进行液相色谱分析，得出各物质的质量百分比和成份为：25.2%的均三甲苯、74.08%的产品中间体、0.72%的杂质；其中，产品中间体中的一氯苄占反应产物的71.1%。均三甲苯的有效转化率达到98.55%。对反应产物进行精馏纯化，得到纯度为97%的一氯苄。
实施例4
采用长度为150cm，内径1.5cm的空心玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；光源从反应器的外围均匀照射于反应区。甲基苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧表面成膜，并沿内壁及玻璃弹簧表面向下流动，氯气由下端气体进料口通入；外照光强度为20000Lux，甲基苯加料速度为5.5g/min，氯气通入速度为3.18g/min，氯气体积浓度为17%，反应过程中玻璃管反应区内最高温度80℃，尾气从反应器气体物流出口排出；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：18.87%的甲基苯，80.27%的产品中间体、0.02%的三氯苄、0.84%的杂质；其中，产品中间体中的一氯苄占反应产物的76.55%。甲基苯的有效转化率达到98.1%。对反应产物进行精馏纯化，得到纯度为98.55%的一氯苄。
实施例5
工艺流程如图1所示，采用长度为100cm，内径1.5cm的空心玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为膜界面光氯化反应器1；本实施例膜界面光氯化反应器结构图可以参见图2，光源9从反应器的外围均匀照射于物料反应区。第一阶段：1,4-二甲苯由反应器1液体进料口2加入，通过液体分布器（图中未示出）在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面向下流动，氯气由下端气体进料口3通入；外照光强度为20000Lux，1,4-二甲苯加料速度为5.2g/min，氯气通入速度为5.4g/min，氯气体积浓度为17.6%，反应过程中玻璃管反应区内最高温度102℃，尾气从反应器气体物流出口4排出，尾气中氯气体积比为1.0%；采集部分从反应器1反应产物出口5的产物进行气相色谱分析，得出各物质的质量百分比和成份为：8.52%的1,4-二甲苯、89.85%的产品中间体、0.51%的1,4-二（三氯甲基）苯、1.12%的杂质。
产物继续进入反应器1后串联的内部装填填料的膜界面光氯化反应器中进行反应，外照光强度为19850Lux，氯气通入速度为8.1g/min，氯气体积浓度为18%，反应过程中玻璃管反应区内最高温度115℃，反应尾气中氯气含量1.0%。采集部分液体产物进行气相色谱分析，成份为：92.56%的产品中间体、6.04%的1,4-二（三氯甲基）苯、1.40%的杂质；在两级反应过程中，1,4-二甲苯的有效转化率达到98.60%。第一阶段反应结束。
第二阶段：取200g第一阶段得到的氯化液，进入常规的光氯化反应器6，继续进行光氯化反应，光照强度为60000Lux，氯气通入速度为20~120g/h（操作中，通入氯气的速度可由本领域技术人员根据反应监测结果适当调整。
一般而言，当原料和中间体含量高时，氯气通入速度可以稍快，原料和中间体含量减少，目标产物含量增多时（1,4-二（三氯甲基）苯含量≥60%），氯气通入速度可以稍微放慢，第二阶段氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：98.58%的1,4-二（三氯甲基）苯、1.42%的杂质；1,4-二（三氯甲基）苯收率为97.56%。所得产物经一次精馏纯化后得到的1,4-二（三氯甲基）苯纯度为99.95%。
实施例6
第一阶段：采用长度为100cm，内径1.5cm的玻璃管垂直放置，作为第一级反应器；光源从反应器的外围均匀照射于反应区。1,3-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁成膜，并沿内壁下流，氯气由下端气体进料口3通入；外照光强度为25000Lux，1,3-二甲苯加料速度为5.0g/min，氯气通入速度为5.7g/min，氯气体积浓度为15%，反应过程中玻璃管反应区内最高温度83℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为1.8%；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：35.58%的1,3-二甲苯、63.39%的产品中间体、1.03%的杂质。
第一级反应器中的产物继续进入串联的第二级反应器进行光氯化反应，外照光强度为21030Lux，氯气通入速度为5.7g/min，氯气体积浓度为16%，反应过程中玻璃管反应区内最高温度95℃，反应尾气中氯气含量3.5%。对从第二级反应器中得到的液体产物进行气相色谱分析，成份为：0.5%的二甲苯、96.34%的产品中间体、1.83%的1,3-二（三氯甲基）苯、1.33%的杂质；在两级反应过程中，1,3-二甲苯的有效转化率达到99.12%。
第二阶段：本实施例中第二阶段采用膜界面光氯化反应器串联常规的光氯化反应器的形式。从第一阶段得到的液体产物进入第二阶段中的膜界面光氯化反应器中进行光氯化反应，外照光强度为32000Lux，氯气通入速度为7.1g/min，氯气体积浓度为90.6%，反应过程中玻璃管反应区内最高温度98℃，反应尾气中氯气含量5.3%。对从该反应器中得到的液体产物进行气相色谱分析，成份为： 79.59%的产品中间体、18.96%的1,3-二（三氯甲基）苯、1.45%的杂质；
取200g第二阶段中的反应器得到的产物进入常规的光氯化反应器，光照强度为65000Lux，氯气通入速度为2-10g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：97.61%的1,3-二（三氯甲基）苯、2.39%的杂质。1,3-二（三氯甲基）苯收率为96.80%。所得产物经一次精馏纯化后得到的1,3-二（三氯甲基）苯纯度为99.96%。
实施例7
第一阶段：采用长度为100cm，内径1.5cm的玻璃管作为第一级反应器；玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，1,4-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面下流，氯气由下端气体进料口通入；外照光强度为20000Lux，1,4-二甲苯加料速度为4.5g/min，氯气通入速度为4.3 g/min，氯气体积浓度为18.5%，反应过程中玻璃管内最高温度100℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为0.8%；对从第一级反应器中得到的液体产物进行气相色谱分析，成份为：7.62%的1,4-二甲苯、90.53%的产品中间体、1.85%的杂质。
 第一级反应器得到的液体产物直接进入内部装填Ф6mm的玻璃弹簧填料的第二级反应器，第二级反应器氯化条件为：外照光强度为21030Lux，氯气通入速度为4.8 g/min，氯气体积浓度为17.2%，反应过程中玻璃管内最高温度102℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为1.7%；对从第二级反应器中得到的液体产物进行气相色谱分析，成份为：95.69%的产品中间体、2.26%的1,4-二（三氯甲基）苯、2.05%的杂质；
以上两级氯化过程中，1,4-二甲苯的有效转化率达到97.95%；
第二阶段：本实施例中第二阶段继续采用膜界面光氯化反应器，具体为采用四个串联的膜界面光氯化反应器，反应器内部均装填Ф6mm的玻璃弹簧填料。将从第一阶段得到的液体产物加热到150℃后进入第二阶段中的第一级反应器，氯化条件为：外照光强度为50000Lux，氯气通入速度为3.9g/min，氯气体积浓度为81.7%，反应过程中玻璃管内最高温度150℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为1.3%；对从该反应器中得到的液体产物进行气相色谱分析，成份为：75.64%的产品中间体、21.86%的1,4-二（三氯甲基）苯、2.50%的杂质；
将从第二阶段第一级反应器得到的液体产物加热到160℃后进入第二阶段第二级反应器，氯化条件为：外照光强度为100000Lux，氯气通入速度为3.48g/min，氯气体积浓度为95.2%，反应过程中玻璃管内最高温度160℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为5.0%；对从第二阶段第二级反应器中得到的液体产物进行气相色谱分析，成份为：27.27%的产品中间体、70.34%的1,4-二（三氯甲基）苯、2.39%的杂质；
将从第二阶段第二级反应器中得到的液体产物加热到170℃后进入第二阶段第三级反应器；氯化条件为：外照光强度为150000Lux，氯气通入速度为1.92 g/min，氯气体积浓度为96.2%，反应过程中玻璃管内最高温度177℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为5.5%；对从第二阶段第三级反应器中得到的液体产物进行气相色谱分析，成份为：6.35%的产品中间体、91.29%的1,4-二（三氯甲基）苯、2.36%的杂质；
将从第二阶段第三级反应器得到的液体产物加热到170℃后进入第二阶段第四级反应器；氯化条件为：外照光强度为250000Lux，氯气通入速度为1.6g/min，氯气体积浓度为100%，反应过程中玻璃管内最高温度160℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为1.5%；对从第二阶段第四级反应器中得到的液体产物进行气相色谱分析，成份为：0.00%的产品中间体、97.64%的1,4-二（三氯甲基）苯、2.36%的杂质；1,4-二（三氯甲基）苯收率为96.30%。
实施例8
反应器的形式：两根不同直径的玻璃管组成的环状柱体之间填充Ф25mm的玻璃环。实现膜界面光氯化反应的反应器结构示意图参见图3。
内管长度180cm，外径8cm、壁厚0.5cm。
外管长度150cm，内径20cm、壁厚0.5cm。
第一阶段：第一级反应器反应条件为：外照光强度为25000Lux，内照光强度为20000Lux，对氯甲苯加料速度35kg/h，通氯气速度23.2kg/h，氯气浓度18.6%；反应过程中玻璃管内最高温度120℃；尾气中氯气体积比为2.3%；此时收集下端的液体产物进行气相色谱分析；成份为：0.80%的对氯甲苯、88.70%的产品中间体、8.30%的目标产品、2.20%的杂质；
串联的内部装填Ф25mm的玻璃环填料的第二级反应器，反应条件为：外照光强度为25000Lux，内照光强度为23000Lux，通氯气速度33.6kg/h，氯气浓度17.8%；反应过程中玻璃管内最高温度130℃；尾气中氯气体积比为2.5%；收集下端的氯化液进行气相色谱分析；成份为29.54%的产品中间体、68.15%的产品、2.31%的杂质；
以上两级反应过程中，对氯甲苯的有效转化率为97.69%。
第二阶段：本实施例中第二阶段继续采用膜界面光氯化反应器，具体为采用两个串联的内部装填Ф25mm的玻璃环填料的膜界面光氯化反应器。从第一阶段得到的液体产物进入第二阶段中的第一级反应器，氯化条件为： 外照光强度为55000Lux，内照光强度为23000Lux，通氯气速度10.6kg/h，氯气浓度95.5%；反应过程中玻璃管内最高温度130℃；尾气中氯气体积比为5.7%；收集下端的氯化液进行气相色谱分析；成份为5.70%的产品中间体、91.10%的目标产品、3.20%的杂质；
第二阶段中的第一级反应器得到的液体产物进入第二阶段第二级反应器，氯化条件为： 外照光强度在85000Lux，内照光强度23000Lux，通氯气速度3.6kg/h，氯气浓度100%；反应过程中玻璃管内最高温度130℃；尾气中氯气体积比为8.7%；收集下端的氯化液进行气相色谱分析；成份为96.90%的产品、3.10%的杂质；对氯甲苯收率为96.01%。
实施例9
第一阶段：采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为第一级反应器；光源从反应器的外围均匀照射于反应区。均三甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧表面成膜，并沿内壁及玻璃弹簧表面下流，氯气由下端气体进料口通入；外照光强度为20000Lux，均三甲苯加料速度为4.8g/min，氯气通入速度为7.8g/min，氯气体积浓度为18.1%，反应过程中玻璃管反应区内最高温度110℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为1.5%；对从第一级反应器中得到的液体产物进行液相色谱分析，得出各物质的质量百分比和成份为：23.30%的均三甲苯、75.90%的产品中间体、0.8%的杂质。
第一级反应器中得到的液体产物继续进入内部装填Ф6mm的玻璃弹簧填料的第二级反应器中进行光氯化反应，外照光强度为25000Lux，氯气通入速度为8.1g/min，氯气体积浓度为18.2%，反应过程中玻璃管反应区内最高温度130℃，反应尾气中氯气含量2.4%。对从第二级反应器中得到的液体产物进行液相色谱分析，成份为：98.95%的产品中间体、1.05%的杂质；
在两级反应过程中，均三甲苯的有效转化率达到98.95%。
第二阶段：取200g第一阶段得到的液体产物进入常规的光氯化反应器继续进行反应，光照强度为150000Lux，氯气通入速度为20-200g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在200~280℃；所得产物进行液相色谱分析，成份为：98.96%的均三（三氯甲基）苯、1.04%的杂质。均三（三氯甲基）苯收率为97.84%。
实施例10
第一阶段：采用长度为150cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；光源从反应器的外围均匀照射于反应区。甲基苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧表面成膜，并沿内壁及玻璃弹簧表面下流，氯气由下端气体进料口通入；外照光强度为20000Lux，甲基苯加料速度为5.5g/min，氯气通入速度为4.1g/min，氯气体积浓度为19.4%，反应过程中玻璃管反应区内最高温度120℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为2.8%；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：71.04%的产品中间体、26.71%的目标产物、2.25%的杂质；甲基苯的有效转化率达到97.75%。
第二阶段：取200g第一阶段得到的液体产物进入常规的光氯化反应器继续进行反应，光照强度为75000Lux，氯气通入速度为10-24g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在140℃；所得产物进行气相色谱分析，成份为：97.80%的三氯甲基苯、2.20%的杂质。三氯甲基苯收率为96.84%。
实施例11
反应器的形式：两根不同直径的玻璃管组成的环状柱体之间填充Ф25mm的玻璃环。反应器结构示意图参见图3。
内管长度180cm，外径8cm、壁厚0.5cm。
外管长度150cm，内径20cm、壁厚0.5cm。
第一阶段：第一级反应器反应条件为：外照光强度为18000Lux，内照光强度为20000Lux，1,4-二甲苯加料速度40kg/h，通氯气速度18kg/h，氯气浓度15.4%；反应过程中玻璃管内最高温度68℃；尾气中氯气体积比为0.4%；此时收集下端的液体产物进行气相色谱分析；成份为：60.12%的1,4-二甲苯、39.50%的产品中间体、0.38%的杂质；
串联的内部装填Ф25mm玻璃环填料的第二级反应器，反应条件为：外照光强度为20000Lux，内照光强度为20000Lux，通氯气速度23.63kg/h，氯气浓度10.3%；反应过程中玻璃管内最高温度70℃；尾气中氯气体积比为0.3%；收集下端的氯化液进行气相色谱分析；成份为：15.53%的1,4-二甲苯、83.62%的产品中间体、0.85%的杂质；
以上两级反应过程中，1,4-二甲苯的有效转化率为98.99%。
第二阶段：取200kg第一阶段得到的液体产物进入常规的光氯化反应器继续进行反应，光照强度为70000Lux，氯气通入速度为20-120Kg/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120-170℃；所得产物进行气相色谱分析，成份为：96.01%的目标产物、3.99%的杂质。1,4-二（三氯甲基）苯收率为95.5%。
实施例12
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；本实施例反应器结构图可以参见图2，光源9从反应器的外围均匀照射于反应区。第一阶段：1,4-二甲苯由第一级反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面下流，氯气由下端气体进料口通入；外照光强度为20000Lux，1,4-二甲苯加料速度为5.0g/min，氯气通入速度为1.8g/min，氯气体积浓度为17.0%，反应过程中玻璃管反应区内最高温度50℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为0.2%；采集部分从第一级反应器中反应得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：85.09%的1,4-二甲苯、14.60%的产品中间体、0.31%的杂质。
第一级反应器中的产物继续进入内部装填Ф6mm玻璃弹簧填料的第二级反应器进行光氯化反应，外照光强度为30000Lux，氯气通入速度为2.5g/min，氯气体积浓度为16.7%，反应过程中玻璃管反应区内最高温度78℃，反应尾气中氯气含量1.5%。采集部分从第二级反应器反应得到的液体产物进行气相色谱分析，成份为：63.6%的1,4-二甲苯、35.70%的产品中间体、0.70%的杂质；
第二级反应器得到的液体产物进入内部装填Ф6mm玻璃弹簧填料的第三级反应器中继续进行光氯化反应，外照光强度为20000Lux，氯气通入速度为2.5g/min，氯气体积浓度为16%，反应过程中玻璃管反应区内最高温度98℃，反应尾气中氯气含量1.1%。采集部分从第三级反应器反应得到的液体产物进行气相色谱分析，成份为：8.60%的二甲苯、89.64%的产品中间体、1.76%的杂质；
在上述三级反应过程中，1,4-二甲苯的有效转化率达到98.07%。第一阶段反应结束。
第二阶段：取200g第一阶段得到的液体产物，进行普通光氯化反应，光照强度为100000Lux，氯气通入速度为20~120g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：97.06%的1,4-二（三氯甲基）苯、2.94%的杂质；1,4-二（三氯甲基）苯收率为95.96%。
实施例13
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；第一阶段：1,4-二甲苯由第一级反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面下流，氯气由下端气体进料口通入；外照光强度为6000Lux，1,4-二甲苯加料速度为7.0g/min，氯气通入速度为1.5g/min，氯气体积浓度为18.8%，反应过程中玻璃管反应区内最高温度60℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为1.0%；采集部分从第一级反应器中反应得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：78.60%的1,4-二甲苯、21.04%的产品中间体、0.36%的杂质。
第一级反应器中的产物继续进入内部装填Ф6mm玻璃弹簧填料的第二级反应器中进行光氯化反应，外照光强度为12000Lux，氯气通入速度为2.5g/min，氯气体积浓度为17.7%，反应过程中玻璃管反应区内最高温度80℃，反应尾气中氯气含量1.2%。采集部分从第二级反应器中反应得到的液体产物进行气相色谱分析，成份为：53.3%的1,4-二甲苯、45.91%的产品中间体、0.79%的杂质；
第二级反应器得到的产物继续进入内部装填Ф6mm玻璃弹簧填料的第三级反应器中进行光氯化反应，外照光强度为23000Lux，氯气通入速度为5.1g/min，氯气体积浓度为17.3%，反应过程中玻璃管反应区内最高温度105℃，反应尾气中氯气含量2.0%。采集部分从第三级反应器反应得到的液体产物进行气相色谱分析，成份为：2.67%的1,4-二甲苯、95.10%的产品中间体、0.56%的目标产物、1.67%的杂质；
在上述三级反应过程中，1,4-二甲苯的有效转化率达到98.28%，第一阶段反应结束。
第二阶段：取200g第一阶段得到的液体产物，进行普通光氯化反应，光照强度为310000Lux，氯气通入速度为20~120g/h，氯气体积浓度为80%~100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：98.30%的目标产物、1.70%的杂质；1,4-二（三氯甲基）苯产品收率为96.08%。
实施例14
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；第一阶段：1,4-二甲苯由第一级反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面下流，氯气由下端气体进料口通入；外照光强度为10000Lux，1,4-二甲苯加料速度为5.9g/min，氯气通入速度为4.3g/min，氯气体积浓度为20%，反应过程中玻璃管反应区内最高温度81℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为4.5%；采集部分从第一级反应器中反应得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：8.66%的1,4-二甲苯、89.80%的产品中间体、1.54%的杂质。
第一级反应器中的液体产物继续进入内部装填Ф6mm玻璃弹簧填料的第二级反应器中进行光氯化反应，外照光强度为15000Lux，氯气通入速度为4.6g/min，氯气体积浓度为20%，反应过程中玻璃管反应区内最高温度128℃，反应尾气中氯气含量3.8%。采集部分从第二级反应器得到的液体产物进行气相色谱分析，成份为：0.11%的1,4-二甲苯、96.14%的产品中间体、2.15%的目标产物、1.6%的杂质；
将第二级反应器得到的液体产物加热到160℃，进入内部装填Ф6mm玻璃弹簧填料的第三反应器中继续进行光氯化反应，外照光强度为15000Lux，氯气通入速度为11.5g/min，氯气体积浓度为20%，反应过程中玻璃管反应区内最高温度160℃，反应尾气中氯气含量3.8%。采集部分从第三级反应器反应得到的液体产物进行气相色谱分析，成份为：37.38%的产品中间体、60.82%的1,4二（三氯甲基）苯、1.80%的杂质；
在上述三级反应过程中，1,4-二甲苯的有效转化率达到98.4%。第一阶段反应结束。
第二阶段：取200g第一阶段得到的液体产物，进行普通光氯化反应，光照强度为100000Lux，氯气通入速度为20~120g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：98.25%的1,4二（三氯甲基）苯、1.75%的杂质；1,4-二（三氯甲基）苯产品收率为97.68%。
实施例15
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；第一阶段：1,4-二甲苯由第一级反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面下流，氯气由下端气体进料口通入；外照光强度为10000Lux，1,4-二甲苯加料速度为6.1g/min，氯气通入速度为4.2g/min，氯气体积浓度为12.2%，反应过程中玻璃管反应区内最高温度78℃，尾气从反应器气体物流出口排出，尾气中氯气体积比为2.5%；采集部分从第一级反应器中反应得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：57.30%的1,4-二甲苯、42.03%的产品中间体、0.67%的杂质。
第一级反应器中的产物继续进入串联的内部装填Ф6mm玻璃弹簧填料的第二级反应器中进行光氯化反应，外照光强度为20000Lux，氯气通入速度为3.9g/min，氯气体积浓度为12.9%，反应过程中玻璃管反应区内最高温度75℃，反应尾气中氯气含量1.3%。采集部分从第二级反应器反应得到的液体产物进行气相色谱分析，成份为：35.40%的1,4-二甲苯、63.50%的产品中间体、1.10%的杂质。
第二级反应器中的液体产物继续进入串联的内部装填Ф6mm玻璃弹簧填料的第三级反应器中进行光氯化反应，外照光强度为30000Lux，氯气通入速度为4.7g/min，氯气体积浓度为13.0%，反应过程中玻璃管反应区内最高温度75℃，反应尾气中氯气含量2.5%。采集部分从第三级反应器反应得到的液体产物进行气相色谱分析，成份为：16.90%的1,4-二甲苯、81.85%的产品中间体、1.25%的杂质。
在上述三级反应过程中，1,4-二甲苯的有效转化率达到98.41%。第一阶段反应结束。
第二阶段：本实施例中第二阶段采用两个内部装填Ф6mm玻璃弹簧填料的膜界面光氯化反应器串联常规的光氯化反应器的形式。从第一阶段得到的液体产物进入第二阶段中的第一级反应器中进行光氯化反应，外照光强度为30000Lux，氯气通入速度为4.1g/min，氯气体积浓度为14.0%，反应过程中玻璃管反应区内最高温度73℃，反应尾气中氯气含量7.5%。采集部分从第四级反应器反应得到的液体产物进行气相色谱分析，成份为：0.13%的1,4-二甲苯、98.22%的产品中间体、1.65%的杂质。
第二阶段第一级反应器中的产物继续进入第二级反应器中进行光氯化反应，外照光强度为30000Lux，氯气通入速度为4.1g/min，氯气体积浓度为100%，反应过程中玻璃管反应区内最高温度125℃，反应尾气中氯气含量1.9%。采集部分从第五级反应器反应得到的液体产物进行气相色谱分析，成份为：91.88%的产品中间体、6.53%的目标产物、1.59%的杂质。
取200g第二阶段第二级膜界面光氯化反应器中得到的液体产物，进行普通光氯化，光照强度为80000Lux，氯气通入速度为20~120g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：98.37%的目标产物、1.63%的杂质；1,4-二（三氯甲基）苯产品收率为95.32%。
实施例16
第一阶段：采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为第一级反应器；光源从反应器的外围均匀照射于反应区。1,3-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁成膜，并沿内壁下流，氯气由下端气体进料口3通入；外照光强度为28000Lux，1,3-二甲苯加料速度为5.3g/min，氯气通入速度为5.6g/min，氯气体积浓度为18%，反应过程中玻璃管反应区内最高温度90℃，尾气从反应器气体物流出口排出；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：31.54%的1,3-二甲苯、67.44%的产品中间体、1.02%的杂质。
第一级反应器中的产物继续进入串联的内部装填Ф6mm玻璃弹簧填料的第二级反应器进行光氯化反应，外照光强度为33000Lux，氯气通入速度为5.7g/min，氯气体积浓度为18.7%，反应过程中玻璃管反应区内最高温度95℃，反应尾气中氯气含量3.8%。对从第二级反应器中得到的液体产物进行气相色谱分析，成份为：0.2%的二甲苯、89.67%的产品中间体、8.9%的1,3-二（三氯甲基）苯、1.23%的杂质；在两级反应过程中，1,3-二甲苯的有效转化率达到98.95%。
第二阶段：取200g第一阶段中得到的产物进入常规的光氯化反应器，光照强度为70000Lux，氯气通入速度为20-120g/h，氯气体积浓度为52%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：97.33%的1,3-二（三氯甲基）苯、2.67%的杂质。1,3-二（三氯甲基）苯收率为96.58%。所得产物经一次精馏纯化后得到的1,3-二（三氯甲基）苯纯度为99.94%。
实施例17
第一阶段：采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为第一级反应器；光源从反应器的外围均匀照射于反应区。1,4-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁成膜，并沿内壁下流，氯气由下端气体进料口3通入；外照光强度为33000Lux，1,4-二甲苯加料速度为5.4g/min，氯气通入速度为5.6g/min，氯气体积浓度为17%，反应过程中玻璃管反应区内最高温度95℃，尾气从反应器气体物流出口排出；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：21.54%的1,4-二甲苯、77.41%的产品中间体、1.05%的杂质。
第一级反应器中的产物继续进入串联的内部装填Ф6mm玻璃弹簧填料的第二级反应器进行光氯化反应，外照光强度为50000Lux，氯气通入速度为7.2 g/min，氯气体积浓度为19%，反应过程中玻璃管反应区内最高温度100℃。对从第二级反应器中得到的液体产物进行气相色谱分析，成份为：0%的二甲苯、89.53%的产品中间体、9.2%的1,4-二（三氯甲基）苯、1.27%的杂质；在两级反应过程中，1,4-二甲苯的有效转化率达到98.82%。
第二阶段：取200g第一阶段中得到的产物进入常规的光氯化反应器，光照强度为55000Lux，氯气通入速度为20-120g/h，氯气体积浓度为22%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：98.01%的1,4-二（三氯甲基）苯、1.99%的杂质。1,4-二（三氯甲基）苯收率为97.74%。所得产物经一次精馏纯化后得到的1,4-二（三氯甲基）苯纯度为99.97%。
对比实施例1
采用长度为100cm，内径1.5cm的空心玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；1,4-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面向下流动，氯气由下端气体进料口通入；外照光强度为20000Lux，1,4-二甲苯加料速度为5.2g/min，氯气通入速度为5.4g/min，氯气体积浓度为45%，氯气通入20分钟后，反应液碳化变黑，反应失败。
对比实施例2
采用长度为100cm，内径1.5cm的空心玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；1,3-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面向下流动，氯气由下端气体进料口通入；外照光强度为50000Lux，1,3-二甲苯加料速度为5.7g/min，氯气通入速度为3.2g/min，氯气体积浓度为55%，氯气通入16分钟后，反应液碳化变黑，反应失败。
对比实施例3
采用长度为100cm，内径1.5cm的空心玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为反应器；对氯甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁及玻璃弹簧填料表面成膜，并沿内壁及玻璃弹簧填料表面向下流动，氯气由下端气体进料口通入；外照光强度为32000Lux，对氯甲苯加料速度为4.5g/min，氯气通入速度为3.2g/min，氯气体积浓度为50%，氯气通入24分钟后，反应液碳化变黑，反应失败。
对比实施例4
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为第一级反应器；光源从反应器的外围均匀照射于反应区。1,3-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁成膜，并沿内壁下流，氯气由下端气体进料口3通入；外照光强度为25000Lux，1,3-二甲苯加料速度为5.0g/min，氯气通入速度为5.7g/min，氯气体积浓度为15%，反应过程中玻璃管反应区内最高温度83℃，尾气从反应器气体物流出口排出；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：35.58%的1,3-二甲苯、63.39%的产品中间体、1.03%的杂质。
上述反应产物进入内部装填Ф6mm玻璃弹簧填料的第二级膜界面光氯化反应器，继续通入氯气进行反应，外照光强度为21030Lux，氯气通入速度为5.7g/min，氯气体积浓度为42%，反应过程中玻璃管反应区内最高温度125℃，对从第二级反应器中得到的液体产物进行气相色谱分析，成份为：0 %的二甲苯、32.2%的产品中间体、51.1%的1,3-二（三氯甲基）苯、16.7%的杂质；在两级反应过程中，1,3-二甲苯的有效转化率达为80.54%。
取200g第二级膜界面光氯化反应器得到的产物进入常规的光氯化反应器，光照强度为60000Lux，氯气通入速度为20-120g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：82.9%的1,3-二（三氯甲基）苯、17.1%的杂质。1,3-二（三氯甲基）苯收率为83.26%。
对比实施例5
采用长度为100cm，内径1.5cm的玻璃管垂直放置，内部装填Ф6mm的玻璃弹簧填料，作为第一级反应器；光源从反应器的外围均匀照射于反应区。1,4-二甲苯由反应器液体进料口加入，通过液体分布器在玻璃管内壁成膜，并沿内壁下流，氯气由下端气体进料口3通入；外照光强度为2000Lux，1,4-二甲苯加料速度为4.5g/min，氯气通入速度为4.0g/min，氯气体积浓度为10%，反应过程中玻璃管反应区内最高温度95℃，尾气从反应器气体物流出口排出；对从反应器中得到的液体产物进行气相色谱分析，得出各物质的质量百分比和成份为：22.78%的1,4-二甲苯、72.93%的产品中间体、3.24%的目标产物、1.05%的杂质。
上述反应产物进入内部装填Ф6mm玻璃弹簧填料的第二级膜界面光氯化反应器，继续通入氯气进行反应，外照光强度为45000Lux，氯气通入速度为5.8g/min，氯气体积浓度为45%，反应过程中玻璃管反应区内最高温度130℃，对从第二级反应器中得到的液体产物进行气相色谱分析，成份为：0 %的二甲苯、25.24%的产品中间体、66.41%的1,4-二（三氯甲基）苯、8.35%的杂质；在两级反应过程中，1,4-二甲苯的有效转化率达为85.07%。
取200g第二级膜界面光氯化反应器得到的产物进入常规的光氯化反应器，光照强度为54000Lux，氯气通入速度为20-120g/h，氯气体积浓度为100%，反应过程中氯化塔内温度控制在120~170℃；所得产物进行气相色谱分析，成份为：90.47%的1,4-二（三氯甲基）苯、9.53%的杂质。1,4-二（三氯甲基）苯收率为90.14%。
本发明提出的塔式连续光氯化法制氯苄已通过较佳实施例子进行了描述，相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的结构和设备进行改动或适当变更与组合，来实现本发明技术。特别需要指出的是，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容中。

Claims (1)

1、一种塔式连续光氯化法制氯苄，其特征在于，使化学式为(X) aC 6H 6-a-b(CH 3) b的芳烃类化合物在流动中成液膜，与氯气在光照条件下进行膜界面光氯化反应，反应开始时侧链甲基上的一个氢原子被氯原子取代生成一氯苄；
所述X为氯或溴或氟原子，a为选自0、1、2、3、4或5的整数，b为选自1、2或3 的整数，且a+b≤6。
2、根据权利要求1所述的塔式连续光氯化法制氯苄，其特征在于，继续与氯气反应，苄基上的两个氢原子被氯原子取代生成二氯苄，以此类推，侧链甲基上的氢原子逐渐被氯原子取代，并最终可以得到芳烃类化合物侧链甲基上的氢原子全部被氯原子取代的产物。
3、根据权利要求1所述的塔式连续光氯化法制氯苄，其特征在于，所述产物为一氯苄时，氯气体积浓度为1~40%，优选氯气体积浓度为5~30%，进一步优选氯气体积浓度为10~20%。
4、根据权利要求1所述的塔式连续光氯化法制氯苄，其特征在于，所述产物为一氯苄时，反应温度为20℃~150℃，优选反应温度为60~100℃。
5、根据权利要求1所述的塔式连续光氯化法制氯苄，其特征在于，所述产物为一氯苄时，通入的氯气量为苯环侧链甲基全氯代所需的理论化学计算量的2~40%，优选3~30%。
6、根据权利要求1所述的塔式连续光氯化法制氯苄，其特征在于，在经过所述产物为一氯苄的反应阶段后，进一步与氯气进行反应，得到多氯苄产物。
7、一种塔式连续光氯化制氯苄，其特征在于，分为两个阶段，第一阶段：使化学式为(X) aC 6H 6-a-b(CH 3) b的芳烃类化合物在流动中成液膜，与氯气在光照条件下进行膜界面光氯化反应，检测残余芳烃类化合物(X) aC 6H 6-a-b(CH 3) b的质量百分含量，当含量为0~20%时，第一阶段反应结束；第二阶段：将第一阶段得到的反应中间产物进一步与氯气进行光氯化反应直到反应完成，得到三氯甲基取代苯；所述X为氯或溴或氟原子，a为选自0、1、2、3、4或5的整数，b为选自1、2或3的整数，且a+b≤6。
8、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，所述第一阶段，检测残余芳烃类化合物的质量百分含量，当含量为0~12%时，优选当含量为0~2%时，特别优选当含量为0%时，第一阶段反应结束。
9、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，第一阶段氯气体积浓度为1~40%，优选氯气体积浓度为5~30%，进一步优选氯气体积浓度为10~20%。
10、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，所述第一阶段中膜界面光氯化反应的反应温度为20℃~180℃，优选80℃~120℃。
11、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，所述第一阶段，采用在一个反应器或者多个反应器内完成，所述多个反应器采用串联或者并联或者其他的连接方式，优选地，所述第一阶段采用2~10个串联的反应器，进一步优选采用2~3个串联的反应器。
12、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，所述第一阶段和第二阶段发生在同一个反应器内，进行膜界面光氯化反应，直到反应完成，得到三氯甲基取代苯。
13、根据权利要求11所述的塔式连续光氯化法制氯苄，其特征在于，当所述第一阶段采用多个串联的反应器时，各串联反应器的反应温度逐渐提高。
14、根据权利要求11所述的塔式连续光氯化法制氯苄，其特征在于，当采用两个串联的反应器时，第一个反应器的反应温度为20℃~150℃，第二个反应器的反应温度为60℃-180℃，优选，第一个反应器的反应温度为80℃~105℃，第二个反应器的反应温度为100℃~120℃；当采用三个串联的反应器时，第一个反应器的反应温度为20℃~150℃，第二个反应器的反应温度为60℃~180℃，第三个反应器的反应温度为60℃~180℃，优选，第一个反应器的反应温度为80℃~100℃，第二个反应器的反应温度为90℃~120℃，第三个反应器的反应温度为95℃~120℃。
15、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，所述第二阶段中光氯化反应，氯气浓度为1%~100%，优选为75%~100%。
16、根据权利要求1~15任一项所述的塔式连续光氯化法制氯苄，其特征在于，所述氯气体积浓度非100%时，通过加入惰性气体进行稀释，例如加入氮气、氩气、氦气、二氧化碳。
17、根据权利要求7所述的塔式连续光氯化法制氯苄，其特征在于，所述第二阶段中光氯化反应，反应温度为80℃~280℃，优选为120℃~170℃。
18、根据权利要7所述的塔式连续光氯化法制氯苄，其特征在于，所述第二阶段，可以采用1~3个串联的常规的光氯化反应器来完成反应；或采用2~6个串联的膜界面光氯化反应器来完成反应；或采用常规的光氯化反应器与膜界面光氯化反应器结合的形式来完成反应。
19、根据权利要求1~16任一项所述的塔式连续光氯化法制氯苄，其特征在于，所述膜界面光氯化反应可以通过填料塔式反应器、降膜式反应器、升膜式反应器或者滴流床反应器来实现。
20、据权利要求1~16任一项所述的塔式连续光氯化法制氯苄，其特征在于，所述膜界面光氯化反应过程中，在反应器内添加具有透光性的填料和/或挡板，液体物料沿着所述填料和/或挡板成液膜状态流动。
21、据权利要求1~16任一项所述的塔式连续光氯化法制氯苄，其特征在于，所述光氯化反应中光照度为1000 Lux~约400000 Lux，优选为20000 Lux ~100000 Lux。  
22、一种实现如权利要求1~21任一项所述方法的膜界面光氯化反应器，其特征在于，包括反应器壳体，反应器壳体上设置有液体进料口、气体进料口、气体出口和产物出口，所述液体进料在流动中成液膜，所述光氯化反应的光源从反应器的周围和/或内部向物料反应区均匀照射，所述光源与发生光氯化反应的反应区域被反应器壳体隔开。
 
 
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