CN104292070A - Multi-stage production method and device for trifluorotoluene - Google Patents
Multi-stage production method and device for trifluorotoluene Download PDFInfo
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- CN104292070A CN104292070A CN201410076315.4A CN201410076315A CN104292070A CN 104292070 A CN104292070 A CN 104292070A CN 201410076315 A CN201410076315 A CN 201410076315A CN 104292070 A CN104292070 A CN 104292070A
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Abstract
The invention discloses a multi-stage production method and device for trifluorotoluene. The method comprises the steps of (1) carrying out liquid phase fluoridation in a first reaction kettle; (2) adding trichlorotoluene in a second reaction kettle; (3) steaming excessive hydrogen fluoride from the first reaction kettle, condensing and introducing the hydrogen fluoride into the second reaction kettle, adding anhydrous hydrogen fluoride and a catalyst to carry out liquid phase fluoridation;(4) discharging residual materials from the first reaction kettle and adding trichlorotoluene; (5) operating the following reaction kettles according to step (2)-(4); (6) steaming excessive hydrogen fluoride from the last one reaction kettle, condensing and introducing the hydrogen fluoride into the first reaction kettle; and (7) discharging residual materials from the last one reaction kettle, adding trichlorotoluene, returning to step (2) to carry out cyclic operations, collecting the residual materials discharged by all the reaction kettles, filtering and distilling to obtain trifluorotoluene. The multi-stage production method provided by the invention greatly increases production efficiency and utilization rate of hydrogen fluoride; and the obtained product has high purity and high yield.
Description
Technical field
The invention belongs to phenylfluoroform technical field, be specifically related to a kind of multistage production method of phenylfluoroform, also relate to a kind of multistage production unit of phenylfluoroform simultaneously.
Background technology
Phenylfluoroform is intermediate important in fluorine chemistry, is widely used in the production of medicine, agricultural chemicals, dyestuff, and is used as the manufacture etc. of vulcanizing agent, sterilant and transformer oil, such as, can prepare the weedicides such as fluometuron, fluorochloridone, diflufenican.Phenylfluoroform can derive serial phenylfluoroform product, as m-nitryl benzotrifluoride, mamino-trifluoromethyl benzene, a bromo phenylfluoroform, 3,4-bis-chlorobenzotrifluoride, 3,5-dinitro-2-chlorobenzotrifluoride, 3,5-diamido-benzotrifluoride, a hydroxybenzotrifluoride, 3,5-dinitro-p-trifluorotoluenes etc.
Industrial, the production method of phenylfluoroform is mainly: in the presence of a catalyst, and trichlorotoluene zotrichloride and anhydrous hydrogen fluoride, by fluoridation, obtain phenylfluoroform after being separated.At present, flaorination process mainly contains gas phase fluorination and liquid-phase fluorination two kinds.Wherein, gas phase fluorination refers to many chlorine aromatic hydrocarbons and hydrogen fluoride in the presence of a catalyst, High Temperature Gas phase reaction, obtained polyfluoro aromatic hydrocarbons.The product yield of gas phase fluorination is good, but the temperature of reaction of this method is up to 300 ~ 500 DEG C, and existing equipment material is generally difficult to the requirement meeting high-temperature fluorination reaction.Liquid-phase fluorination refers to that trichlorotoluene zotrichloride is at catalyzer, pressurization (also can normal pressure), low temperature (less than 100 DEG C), the method for fluoridizing with anhydrous hydrogen fluoride.This method responds the features such as temperature is lower, equipment corrosion is little, prepare the most frequently used method of trifluoromethyl aromatic compound, but, the method batch production that existing production method often adopts " treating different things alike ", production efficiency is low, and product purity and yield are also lower; Meanwhile, fluoridation Raw utilization ratio is low, and excessive hydrogen fluoride reclaims difficulty, causes the serious wasting of resources and environmental pollution.
Summary of the invention
The object of this invention is to provide a kind of multistage production method of phenylfluoroform, solve that existing production method production efficiency is low, product purity and the also lower problem of yield.
Second object of the present invention is to provide a kind of multistage production unit of phenylfluoroform.
In order to realize above object, the technical solution adopted in the present invention is: a kind of multistage production method of phenylfluoroform, comprises the following steps:
1) in the first reactor, trichlorotoluene zotrichloride is added, the temperature controlling the first reactor is-20 ~ 10 DEG C, anhydrous hydrogen fluoride and catalyzer is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters the first condenser, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
2) in the second reactor, add trichlorotoluene zotrichloride, the temperature controlling the second reactor is-20 ~ 10 DEG C;
3) after the first reaction kettle for reaction terminates, first temperature of reaction kettle is risen to 20 ~ 60 DEG C, anhydrous hydrogen fluoride excessive in first reactor is distilled out of, enter in the second reactor after the second condenser condenses, in the second reactor, add anhydrous hydrogen fluoride and catalyzer simultaneously, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters the second condenser, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the second reactor, and hydrogen chloride gas is discharged from the second condenser-air outlet;
4) after the anhydrous hydrogen fluoride in the first reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride, the temperature controlling the first reactor is-20 ~ 10 DEG C;
5) according to the relation of front and back reactor with the corresponding principle of the relation of the first reactor, the second reactor, according to step 2), 3), 4), reactor is below operated, terminates to reaction kettle for reaction last;
6) after reaction kettle for reaction last terminates, temperature of reaction kettle last is risen to 20 ~ 60 DEG C, anhydrous hydrogen fluoride excessive in reactor last is distilled out of, enter in the first reactor after the first condenser condenses, anhydrous hydrogen fluoride and catalyzer is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters the first condenser, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
7) after the anhydrous hydrogen fluoride in reactor last steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride, the temperature controlling reactor last is-20 ~ 10 DEG C;
Return step 2) carry out cyclical operation; Collect the leftover materials that each reactor is released, filter and distill, obtaining phenylfluoroform.
In step 1), the anhydrous hydrogen fluoride added in the first reactor and the mass ratio of phenylfluoroform are 5 ~ 6:3.5 ~ 4; Step 2) in step 7), the anhydrous hydrogen fluoride added in each reactor and the mass ratio of phenylfluoroform are 1 ~ 1.3:3.5 ~ 4.
Described catalyzer is yellow precipitate.
The add-on of described catalyzer is: in each reactor, the mass ratio of catalyzer and phenylfluoroform is 0.18 ~ 0.25:3.5 ~ 4.
The temperature of described liquid phase fluorination reaction is-20 ~ 10 DEG C, and the reaction times is 3 ~ 6h.
The hydrogen chloride gas of discharging from condenser-air outlet enters tail gas absorbing system.
Total number of reactor is 3 ~ 5.
Also comprise the following steps:
When interval stops production, in still for subsequent use, add trichlorotoluene zotrichloride and catalyzer, the temperature controlling still for subsequent use is-20 ~ 10 DEG C; After wherein one or more reaction kettle for reaction terminate, temperature of reaction kettle is risen to 20 ~ 60 DEG C, anhydrous hydrogen fluoride excessive in reactor is distilled out of, enter after condenser condenses for subsequent use in still for subsequent use, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters condenser for subsequent use, and the hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to still for subsequent use, and hydrogen chloride gas is discharged from condenser-air outlet for subsequent use.
A multistage production unit for phenylfluoroform, comprises the single-stage production equipment that two or more is arranged in order, and each single-stage production equipment comprises reactor and condenser, is provided with discharge gate, top is provided with opening for feed and gas-liquid refluxing opening bottom described reactor; Be provided with gas-liquid mouth bottom described condenser, top is provided with pneumatic outlet for being connected with device for absorbing tail gas, the gas-liquid mouth of condenser is connected by pilot piping with the gas-liquid refluxing opening of reactor; The gas-liquid refluxing opening of the reactor of each single-stage production equipment or the pneumatic outlet of condenser are also connected by pilot piping with the gas-liquid refluxing opening of the reactor of a rear single-stage production equipment, and the gas-liquid refluxing opening of the reactor of last single-stage production equipment or the pneumatic outlet of condenser are connected by pilot piping with the gas-liquid refluxing opening of the reactor of first single-stage production equipment.
Also comprise production equipment for subsequent use, described production equipment for subsequent use comprises still for subsequent use and condenser for subsequent use, is provided with discharge gate, top is provided with opening for feed and gas-liquid refluxing opening bottom described still for subsequent use; Be provided with gas-liquid mouth bottom described condenser for subsequent use, top is provided with pneumatic outlet for being connected with device for absorbing tail gas, the gas-liquid mouth of condenser for subsequent use is connected by pilot piping with the gas-liquid refluxing opening of still for subsequent use; The gas-liquid refluxing opening of the reactor of each single-stage production equipment or the pneumatic outlet of condenser are also connected by pilot piping with the gas-liquid refluxing opening of still for subsequent use.
Described pilot piping refers to the pipeline being provided with by-pass valve control.
In the multistage production method of phenylfluoroform of the present invention, condensing reflux mode is all adopted in liquid phase fluorination reaction process, now in condenser, temperature of cooling water controls to: the hydrogen fluoride gas in mixed gas can condensing reflux in reactor, but the hydrogenchloride generated in reaction process removes tail gas absorbing system in gaseous form; Preferably-25 ~ 0 DEG C.When steaming excessive anhydrous hydrogen fluoride, in condenser, the temperature of water coolant controls to: the hydrogen fluoride gas steamed can be condensed in liquid anhydrous hydrogen fluoride to a rear reactor, but the hydrogenchloride steamed removes tail gas absorbing system in gaseous form; Preferably-25 ~ 0 DEG C.Wherein, the boiling point under hydrogen fluoride normal pressure is 19.5 DEG C, and the boiling point under hydrogenchloride normal pressure is-85 DEG C.
The multistage production method of phenylfluoroform of the present invention, when carrying out liquid phase fluorination reaction in each reactor, the hydrogen fluoride gas in the mixed gas of generation continues to participate in reaction through condensing reflux to reactor, improves the utilization ratio of raw material; Hydrogen chloride gas is discharged from condenser-air outlet, in time reaction product is discharged reactive system, improves speed of reaction, promotes the carrying out of liquid phase fluorination reaction, effectively reduces the generation of by product, improves purity and the yield of product; After liquid phase fluorination reaction in reactor terminates, excessive hydrogen fluoride is steamed, enters a rear reactor after condensation and continue to participate in reaction, excessive hydrogen fluoride obtains sufficient recycle, drastically increases hydrofluoric utilization ratio, solves the problem that excessive hydrogen fluoride reclaims difficulty; The multistage production method of the application, multiple reactor is produced successively, cyclical operation, and production effect is high; Reaction conditions is gentle, and security is high, is easy to operate and control, and is applicable to industrialization scale operation.
The multistage production unit of phenylfluoroform of the present invention, the pneumatic outlet of the condenser of each single-stage production equipment is also connected by pilot piping with the gas-liquid refluxing opening of the reactor of a rear single-stage production equipment, the pneumatic outlet of the condenser of last single-stage production equipment is connected by pilot piping with the gas-liquid refluxing opening of the reactor of first single-stage production equipment, make the condensing reflux of the anhydrous hydrogen fluoride in liquid phase fluorination reaction process, and reaction terminates the technique that rear excessive anhydrous hydrogen fluoride steamed, was condensed to a rear reactor and effectively carries out; Each single-stage reaction unit is connected mutually, excessive hydrogen fluoride obtains sufficient recycle, drastically increase hydrofluoric utilization ratio, make the utilization ratio of anhydrous hydrogen fluoride bring up to 95% ~ 98% by 70% ~ 80%, solve the problem that excessive hydrogen fluoride reclaims difficulty; Decrease hydrofluoric waste, reduce production cost; Effectively avoid leaking, reduce operational danger, environmental friendliness, security is high, has greatly ensured the personnel safety of employee; Achieve the continuous seepage of phenylfluoroform, production efficiency is high, and products obtained therefrom purity is high, productive rate is high; Reasonable in design, be easy to operate and control, be applicable to applying.
Accompanying drawing explanation
Fig. 1 is the structural representation of the multistage production unit of the phenylfluoroform of embodiment 1;
Fig. 2 is the structural representation of the single-stage production unit of phenylfluoroform;
Fig. 3 is the structural representation of the multistage production unit of the phenylfluoroform of embodiment 2;
Fig. 4 is the structural representation of the multistage production unit of the phenylfluoroform of embodiment 3.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The multistage production method of the phenylfluoroform of the present embodiment, comprises the following steps:
1) in the first reactor, trichlorotoluene zotrichloride 391kg is added, the temperature controlling the first reactor is-20 DEG C, anhydrous hydrogen fluoride 600kg, catalyzer yellow precipitate 20kg is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-20 DEG C, reaction times is 6h, the mixed gas that reaction produces enters the first condenser (0 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
2) in the second reactor, add trichlorotoluene zotrichloride 391kg, the temperature controlling the second reactor is-20 DEG C;
3) after the first reaction kettle for reaction terminates, first temperature of reaction kettle is risen to 20 DEG C, anhydrous hydrogen fluoride excessive in first reactor is distilled out of, enter in the second reactor after the second condenser (0 DEG C) condensation, in the second reactor, add anhydrous hydrogen fluoride 130kg simultaneously, catalyzer yellow precipitate 20kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-20 DEG C, reaction times is 6h, the mixed gas that reaction produces enters the second condenser (0 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the second reactor, hydrogen chloride gas is discharged from the second condenser-air outlet,
4) after the anhydrous hydrogen fluoride in the first reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 391kg, the temperature controlling the first reactor is-20 DEG C;
5) in the 3rd reactor, add trichlorotoluene zotrichloride 391kg, the temperature controlling the 3rd reactor is-20 DEG C;
6) after the second reaction kettle for reaction terminates, second temperature of reaction kettle is risen to 20 DEG C, anhydrous hydrogen fluoride excessive in second reactor is distilled out of, enter after the 3rd condenser (0 DEG C) condensation in the 3rd reactor, in the 3rd reactor, add anhydrous hydrogen fluoride 130kg simultaneously, catalyzer yellow precipitate 20kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-20 DEG C, reaction times is 6h, the mixed gas that reaction produces enters the 3rd condenser (0 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the 3rd reactor, hydrogen chloride gas is discharged from the 3rd condenser-air outlet,
7) after the anhydrous hydrogen fluoride in the second reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 391kg, the temperature controlling the second reactor is-20 DEG C;
8) after the 3rd reaction kettle for reaction terminates, 3rd temperature of reaction kettle is risen to 20 DEG C, in 3rd reactor, excessive anhydrous hydrogen fluoride is distilled out of, enter in the first reactor after the first condenser (0 DEG C) condensation, anhydrous hydrogen fluoride 130kg is added in the first reactor, catalyzer yellow precipitate 20kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-20 DEG C, reaction times is 6h, the mixed gas that reaction produces enters the first condenser (0 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, hydrogen chloride gas is discharged from the first condenser-air outlet,
9) after the anhydrous hydrogen fluoride in the 3rd reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 391kg, the temperature controlling the 3rd reactor is-20 DEG C;
Return step 2) carry out cyclical operation; Collect the leftover materials that each reactor is released, filter and distill, obtaining phenylfluoroform.
The purity of the present embodiment gained phenylfluoroform is 99.6%, and yield is 95.5%.
The multistage production unit of the phenylfluoroform of the present embodiment, as shown in Figure 1, 2, comprise three single-stage production equipments be arranged in order, each single-stage production equipment internal structure identical (as shown in Figure 2), comprise reactor 1 and condenser 2, be provided with discharge gate 3 bottom reactor 1, the pipeline be connected with discharge gate 3 is provided with blow-off valve F2, the top of reactor 1 is provided with opening for feed 4 and gas-liquid refluxing opening 5, and the pipeline be connected with opening for feed 4 is provided with feed valve F1, be provided with gas-liquid mouth 6 bottom condenser 2, top is provided with pneumatic outlet 7, pneumatic outlet 7 is connected with device for absorbing tail gas by tail gas pipeline 11, and tail gas pipeline is provided with vent valve F4, the gas-liquid mouth 6 of condenser 2 is connected by return line 10 with the gas-liquid refluxing opening 5 of reactor 1, and return line 10 is provided with reverse flow valve F3, be provided with whipping appts 8 in reactor 1 inner chamber, shell is provided with jacket heat-preservation device 9, and jacket heat-preservation device 9 is provided with refrigerant Heating medium, the outlet of refrigerant heating agent, three single-stage production equipments of the present embodiment are followed successively by one-level production equipment, secondary production equipment, three grades of production equipments, and wherein, the reactor of one-level production equipment is the first reactor 101, and condenser is the first condenser 102, the reactor of secondary production equipment is the second reactor 201, and condenser is the second condenser 202, the reactor of three grades of production equipments is the 3rd reactor 301, and condenser is the 3rd condenser 302, the pneumatic outlet of the first condenser 102 is also connected by the first pilot piping 103 with the gas-liquid refluxing opening of the second reactor 201, first pilot piping 103 is provided with the first control valve F5, the pneumatic outlet of the second condenser 202 is also connected by the second pilot piping 203 with the gas-liquid refluxing opening of the 3rd reactor 301, second pilot piping 203 is provided with the second control valve F7, the pneumatic outlet of the 3rd condenser 302 is connected by three grades of cycle control pipelines 305 with the gas-liquid refluxing opening of the first reactor 101, three grades of cycle control pipelines 305 are provided with the first circulation control valve F6 and the 3rd control valve F8.
During use, close the blow-off valve F2 of first order reaction device, first control valve F5 and the first circulation control valve F6, open reverse flow valve F3 and the vent valve F4 of first order reaction device, trichlorotoluene zotrichloride is added in the first reactor 101, anhydrous hydrogen fluoride and catalyzer react, the mixed gas that reaction produces enters the first condenser 102 through return line, be back to the first reactor 101 through return line after hydrogen fluoride gas condensation in mixed gas to continue to participate in reaction, hydrogen chloride gas is discharged from the pneumatic outlet of the first condenser 102, device for absorbing tail gas is entered through tail gas pipeline 11.Close blow-off valve F2, the second control valve F7 of second order reaction device, open reverse flow valve F3 and the vent valve F4 of second order reaction device, in the second reactor 201, add trichlorotoluene zotrichloride; After reaction in the first reactor 101 terminates, close the vent valve F4 of first order reaction device, open the first control valve F5, make the anhydrous hydrogen fluoride steamed in the first reactor 101 enter second order reaction device through the first pilot piping 103, simultaneously in the second reactor 201, add anhydrous hydrogen fluoride and catalyzer reacts.After the anhydrous hydrogen fluoride in the first reactor 101 steams completely, close the first control valve F5, after the blow-off valve F2 opening first order reaction device carries out blowing, close blow-off valve, then add trichlorotoluene zotrichloride raw material.Close blow-off valve F2, the second circulation control valve F8 of third order reaction device, open reverse flow valve F3 and the vent valve F4 of third order reaction device, in the 3rd reactor 301, add trichlorotoluene zotrichloride; After reaction in the second reactor 201 terminates, close the vent valve F4 of second order reaction device, open the second control valve F7, make the anhydrous hydrogen fluoride steamed in the second reactor 201 enter third order reaction device through the second pilot piping 203, simultaneously in the 3rd reactor 301, add anhydrous hydrogen fluoride and catalyzer reacts.After the anhydrous hydrogen fluoride in the second reactor 201 steams completely, close the second control valve F7, after the blow-off valve F2 opening second order reaction device carries out blowing, close blow-off valve, then add trichlorotoluene zotrichloride raw material.After reaction in the 3rd reactor 301 terminates, close the vent valve F4 of third order reaction device, open the first circulation control valve F6 and the 3rd control valve F8, make the anhydrous hydrogen fluoride steamed in the 3rd reactor 301 enter first order reaction device through three grades of cycle control pipelines 305, simultaneously in the first reactor 101, add anhydrous hydrogen fluoride and catalyzer reacts.Circulation continuous operation successively, realizes the multistage production method of the phenylfluoroform of the present embodiment.
Embodiment 2
The multistage production method of the phenylfluoroform of the present embodiment, comprises the following steps:
1) in the first reactor, trichlorotoluene zotrichloride 400kg is added, the temperature controlling the first reactor is 10 DEG C, anhydrous hydrogen fluoride 570kg, catalyzer yellow precipitate 25kg is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is 10 DEG C, reaction times is 3h, the mixed gas that reaction produces enters the first condenser (-10 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
2) in the second reactor, add trichlorotoluene zotrichloride 400kg, the temperature controlling the second reactor is 10 DEG C;
3) after the first reaction kettle for reaction terminates, first temperature of reaction kettle is risen to 60 DEG C, anhydrous hydrogen fluoride excessive in first reactor is distilled out of, enter after the second condenser (-10 DEG C) condensation in the second reactor, in the second reactor, add anhydrous hydrogen fluoride 100kg simultaneously, catalyzer yellow precipitate 25kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is 10 DEG C, reaction times is 3h, the mixed gas that reaction produces enters the second condenser (-10 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the second reactor, hydrogen chloride gas is discharged from the second condenser-air outlet,
4) after the anhydrous hydrogen fluoride in the first reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 400kg, the temperature controlling the first reactor is 10 DEG C;
5) in the 3rd reactor, add trichlorotoluene zotrichloride 400kg, the temperature controlling the 3rd reactor is 10 DEG C;
6) after the second reaction kettle for reaction terminates, second temperature of reaction kettle is risen to 60 DEG C, anhydrous hydrogen fluoride excessive in second reactor is distilled out of, enter after the 3rd condenser (-10 DEG C) condensation in the 3rd reactor, in the 3rd reactor, add anhydrous hydrogen fluoride 100kg simultaneously, catalyzer yellow precipitate 25kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is 10 DEG C, reaction times is 3h, the mixed gas that reaction produces enters the 3rd condenser (-10 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the 3rd reactor, hydrogen chloride gas is discharged from the 3rd condenser-air outlet,
7) after the anhydrous hydrogen fluoride in the second reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 400kg, the temperature controlling the second reactor is 10 DEG C;
8) after the 3rd reaction kettle for reaction terminates, 3rd temperature of reaction kettle is risen to 60 DEG C, in 3rd reactor, excessive anhydrous hydrogen fluoride is distilled out of, enter after the first condenser (-10 DEG C) condensation in the first reactor, anhydrous hydrogen fluoride 100kg is added in the first reactor, catalyzer yellow precipitate 25kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is 10 DEG C, reaction times is 3h, the mixed gas that reaction produces enters the first condenser (-10 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, hydrogen chloride gas is discharged from the first condenser-air outlet,
9) after the anhydrous hydrogen fluoride in the 3rd reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 400kg, the temperature controlling the 3rd reactor is 10 DEG C;
Return step 2) carry out cyclical operation; Collect the leftover materials that each reactor is released, filter and distill, obtaining phenylfluoroform.
When interval stops production, in still for subsequent use, add trichlorotoluene zotrichloride 400kg, catalyzer yellow precipitate 25kg, the temperature controlling still for subsequent use is 10 DEG C; After first, second, third reaction kettle for reaction terminates, three temperature of reaction kettle are risen to 60 DEG C, anhydrous hydrogen fluoride excessive in reactor is distilled out of, enter after condenser condenses for subsequent use in still for subsequent use, stir and carry out liquid phase fluorination reaction, temperature of reaction is 10 DEG C, reaction times is 3h, the mixed gas that reaction produces enters condenser for subsequent use, and the hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to still for subsequent use, and hydrogen chloride gas is discharged from condenser-air outlet for subsequent use.
The purity of the present embodiment gained phenylfluoroform is 99.2%, and yield is 91%.
The multistage production unit of the phenylfluoroform of the present embodiment, as shown in Figure 3, difference from Example 1 is: also comprise production equipment for subsequent use, described production equipment for subsequent use comprises still 111 for subsequent use and condenser for subsequent use 112, be provided with discharge gate bottom described still for subsequent use 111, the pipeline be connected with discharge gate is provided with blow-off valve F2; Still top for subsequent use is provided with opening for feed and gas-liquid refluxing opening, and the pipeline be connected with opening for feed is provided with feed valve F1; Be provided with gas-liquid mouth bottom described condenser for subsequent use 112, top is provided with pneumatic outlet, pneumatic outlet is connected with device for absorbing tail gas by tail gas pipeline 11, and tail gas pipeline is provided with vent valve F4; The gas-liquid mouth of condenser 112 for subsequent use is connected by pilot piping with the gas-liquid refluxing opening of still 001 for subsequent use, this pilot piping is provided with the structure of reverse flow valve F3(production equipment for subsequent use with single-stage production equipment, specifically see Fig. 2, wherein still for subsequent use is equivalent to the reactor of single-stage production equipment, and condenser for subsequent use is equivalent to the condenser in single-stage production equipment); First condenser 102, second condenser 202, the pneumatic outlet of the 3rd condenser 302 are connected respectively by the first spare duct 104, second spare duct 204, the 3rd spare duct 304 with the gas-liquid refluxing opening of still 111 for subsequent use, described first spare duct 104 is provided with the first make-up valve F9, second spare duct 204 is provided with the second make-up valve F10, and the 3rd spare duct 304 is provided with the 3rd make-up valve F11.
When interval stops production, open reverse flow valve F3 and the vent valve F4 of reaction unit for subsequent use, in still for subsequent use, add trichlorotoluene zotrichloride, catalyzer, when first, second, after 3rd reaction kettle for reaction terminates, close one-level, secondary, the vent valve of third order reaction device and the first control valve F5, second control valve F7, 3rd control valve F8, open the first make-up valve F9, second make-up valve F10 and the 3rd make-up valve F11, make first, second and the 3rd excessive anhydrous hydrogen fluoride in reactor steams, respectively through the first spare duct 104, second spare duct 204, 3rd spare duct 304 enters reaction unit for subsequent use and reacts, the mixed gas that reaction produces enters condenser 112 for subsequent use, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to still 111 for subsequent use, hydrogen chloride gas is discharged from the pneumatic outlet of condenser 112 for subsequent use, device for absorbing tail gas is entered through tail gas pipeline 11.
The multistage production unit of the phenylfluoroform of the present embodiment also comprises production equipment for subsequent use, solve existing installation interval when stopping production, excessive anhydrous hydrogen fluoride overflows the wasting of resources and problem of environmental pollution that cause, further increases the utilization ratio of anhydrous hydrogen fluoride, has saved resource; Meanwhile, improve the security of whole plant.
Embodiment 3
The multistage production method of the phenylfluoroform of the present embodiment, comprises the following steps:
1) in the first reactor, trichlorotoluene zotrichloride 350kg is added, the temperature controlling the first reactor is-10 DEG C, anhydrous hydrogen fluoride 500kg, catalyzer yellow precipitate 18kg is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the first condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
2) in the second reactor, add trichlorotoluene zotrichloride 350kg, the temperature controlling the second reactor is-10 DEG C;
3) after the first reaction kettle for reaction terminates, first temperature of reaction kettle is risen to 30 DEG C, anhydrous hydrogen fluoride excessive in first reactor is distilled out of, enter after the second condenser (-5 DEG C) condensation in the second reactor, in the second reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the second condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the second reactor, hydrogen chloride gas is discharged from the second condenser-air outlet,
4) after the anhydrous hydrogen fluoride in the first reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 350kg, the temperature controlling the first reactor is-10 DEG C;
5) in the 3rd reactor, add trichlorotoluene zotrichloride 350kg, the temperature controlling the 3rd reactor is-10 DEG C;
6) after the second reaction kettle for reaction terminates, second temperature of reaction kettle is risen to 30 DEG C, anhydrous hydrogen fluoride excessive in second reactor is distilled out of, enter after the 3rd condenser (-5 DEG C) condensation in the 3rd reactor, in the 3rd reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the 3rd condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the 3rd reactor, hydrogen chloride gas is discharged from the 3rd condenser-air outlet,
7) after the anhydrous hydrogen fluoride in the second reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 350kg, the temperature controlling the second reactor is-10 DEG C;
8) after the 3rd reaction kettle for reaction terminates, 3rd temperature of reaction kettle is risen to 30 DEG C, in 3rd reactor, excessive anhydrous hydrogen fluoride is distilled out of, enter after the first condenser (-5 DEG C) condensation in the first reactor, anhydrous hydrogen fluoride 110kg is added in the first reactor, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the first condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, hydrogen chloride gas is discharged from the first condenser-air outlet,
9) after the anhydrous hydrogen fluoride in the 3rd reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 350kg, the temperature controlling the 3rd reactor is-10 DEG C;
Return step 2) carry out cyclical operation; Collect the leftover materials that each reactor is released, filter and distill, obtaining phenylfluoroform.
When interval stops production, in still for subsequent use, add trichlorotoluene zotrichloride 350kg, catalyzer yellow precipitate 18kg, the temperature controlling still for subsequent use is-10 DEG C; After first, second, third reaction kettle for reaction terminates, three temperature of reaction kettle are risen to 30 DEG C, anhydrous hydrogen fluoride excessive in reactor is distilled out of, enter after condenser condenses for subsequent use in still for subsequent use, stir and carry out liquid phase fluorination reaction, temperature of reaction is-10 DEG C, reaction times is 4h, the mixed gas that reaction produces enters condenser for subsequent use, and the hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to still for subsequent use, and hydrogen chloride gas is discharged from condenser-air outlet for subsequent use.
The purity of the present embodiment gained phenylfluoroform is 99.4%, and yield is 93.0%.
The multistage production unit of the phenylfluoroform of the present embodiment is with embodiment 2.
Embodiment 4
The multistage production method of the phenylfluoroform of the present embodiment, comprises the following steps:
1) in the first reactor, trichlorotoluene zotrichloride 350kg is added, the temperature controlling the first reactor is-10 DEG C, anhydrous hydrogen fluoride 500kg, catalyzer yellow precipitate 18kg is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the first condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
2) in the second reactor, add trichlorotoluene zotrichloride 350kg, the temperature controlling the second reactor is-10 DEG C;
3) after the first reaction kettle for reaction terminates, first temperature of reaction kettle is risen to 30 DEG C, anhydrous hydrogen fluoride excessive in first reactor is distilled out of, enter after the second condenser (-5 DEG C) condensation in the second reactor, in the second reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the second condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the second reactor, hydrogen chloride gas is discharged from the second condenser-air outlet,
4) after the anhydrous hydrogen fluoride in the first reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 350kg, the temperature controlling the first reactor is-10 DEG C;
5) in the 3rd reactor, add trichlorotoluene zotrichloride 350kg, the temperature controlling the 3rd reactor is-10 DEG C;
6) after the second reaction kettle for reaction terminates, second temperature of reaction kettle is risen to 30 DEG C, anhydrous hydrogen fluoride excessive in second reactor is distilled out of, enter after the 3rd condenser (-5 DEG C) condensation in the 3rd reactor, in the 3rd reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the 3rd condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the 3rd reactor, hydrogen chloride gas is discharged from the 3rd condenser-air outlet,
7) after the anhydrous hydrogen fluoride in the second reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 391kg, the temperature controlling the second reactor is-10 DEG C;
8) in the 4th reactor, add trichlorotoluene zotrichloride 350kg, the temperature controlling the 4th reactor is-10 DEG C;
9) after the 3rd reaction kettle for reaction terminates, 3rd temperature of reaction kettle is risen to 30 DEG C, in 3rd reactor, excessive anhydrous hydrogen fluoride is distilled out of, enter after the 4th condenser (-5 DEG C) condensation in the 4th reactor, in the 4th reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the 4th condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the 4th reactor, hydrogen chloride gas is discharged from the 4th condenser-air outlet,
10) after the anhydrous hydrogen fluoride in the 3rd reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 391kg, the temperature controlling the 3rd reactor is-10 DEG C;
11) after the 4th reaction kettle for reaction terminates, 4th temperature of reaction kettle is risen to 30 DEG C, in 4th reactor, excessive anhydrous hydrogen fluoride is distilled out of, enter after the first condenser (-5 DEG C) condensation in the first reactor, anhydrous hydrogen fluoride 110kg is added in the first reactor, catalyzer yellow precipitate 18kg, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 5h, the mixed gas that reaction produces enters the first condenser (-5 DEG C), hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, hydrogen chloride gas is discharged from the first condenser-air outlet,
12) after the anhydrous hydrogen fluoride in the 4th reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride 350kg, the temperature controlling the 4th reactor is-10 DEG C;
Return step 2) carry out cyclical operation; Collect the leftover materials that each reactor is released, filter and distill, obtaining phenylfluoroform.
When interval stops production, in still for subsequent use, add trichlorotoluene zotrichloride 350kg, catalyzer yellow precipitate 18kg, the temperature controlling still for subsequent use is-10 DEG C; After first, second, third, fourth reaction kettle for reaction terminates, four temperature of reaction kettle are risen to 30 DEG C, anhydrous hydrogen fluoride excessive in reactor is distilled out of, enter after condenser condenses for subsequent use in still for subsequent use, liquid phase fluorination reaction is carried out in stirring, temperature of reaction is-10 DEG C, reaction times is 4h, the mixed gas that reaction produces enters condenser for subsequent use, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to still for subsequent use, and hydrogen chloride gas is discharged from condenser-air outlet for subsequent use.
The purity of the present embodiment gained phenylfluoroform is 99.4%, and yield is 93.0%.
The multistage production unit of the phenylfluoroform of the present embodiment, as shown in Figure 4, difference from Example 2 is: comprise four single-stage production equipments be arranged in order and a production equipment for subsequent use, and four single-stage production equipments are followed successively by one-level production equipment, secondary production equipment, three grades of production equipments, level Four production equipments; The reactor of level Four production equipment is the 4th reactor 401, and condenser is the 4th condenser 402; The pneumatic outlet of the first condenser 102 is connected by the first pilot piping 103 with the gas-liquid refluxing opening of the second reactor 201, and the first pilot piping 103 is provided with the first control valve F5; The pneumatic outlet of the second condenser 202 is connected by the second pilot piping 203 with the gas-liquid refluxing opening of the 3rd reactor 301, and the second pilot piping 203 is provided with the second control valve F7; The pneumatic outlet of the 3rd condenser 302 is connected by the 3rd control tube 303 tunnel with the gas-liquid refluxing opening of the 4th reactor 401, and the 3rd pilot piping 303 is provided with the 3rd control valve F8; The pneumatic outlet of the 4th condenser 402 is connected by level Four cycle control pipeline 405 with the gas-liquid refluxing opening of the first reactor 101, and level Four circulation line 405 is provided with the first circulation control valve F6 and the 4th control valve F12; First condenser 102, second condenser 202, the 3rd condenser 302, the pneumatic outlet of the 4th condenser 402 are connected respectively by the first spare duct 104, second spare duct 204, the 3rd spare duct 304 pilot piping, the 4th spare duct 404 with the gas-liquid refluxing opening of still 111 for subsequent use, described first spare duct 104 is provided with the first make-up valve F9, second spare duct 204 is provided with the second make-up valve F10,3rd spare duct 304 is provided with the 3rd make-up valve F11, and the 4th spare duct 404 is provided with the 4th make-up valve F13.
Claims (10)
1. a multistage production method for phenylfluoroform, is characterized in that: comprise the following steps:
1) in the first reactor, trichlorotoluene zotrichloride is added, the temperature controlling the first reactor is-20 ~ 10 DEG C, anhydrous hydrogen fluoride and catalyzer is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters the first condenser, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
2) in the second reactor, add trichlorotoluene zotrichloride, the temperature controlling the second reactor is-20 ~ 10 DEG C;
3) after the first reaction kettle for reaction terminates, first temperature of reaction kettle is risen to 20 ~ 60 DEG C, anhydrous hydrogen fluoride excessive in first reactor is distilled out of, enter in the second reactor after the second condenser condenses, in the second reactor, add anhydrous hydrogen fluoride and catalyzer simultaneously, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters the second condenser, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the second reactor, and hydrogen chloride gas is discharged from the second condenser-air outlet;
4) after the anhydrous hydrogen fluoride in the first reactor steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride, the temperature controlling the first reactor is-20 ~ 10 DEG C;
5) according to the relation of front and back reactor with the corresponding principle of the relation of the first reactor, the second reactor, according to step 2), 3), 4), reactor is below operated, terminates to reaction kettle for reaction last;
6) after reaction kettle for reaction last terminates, temperature of reaction kettle last is risen to 20 ~ 60 DEG C, anhydrous hydrogen fluoride excessive in reactor last is distilled out of, enter in the first reactor after the first condenser condenses, anhydrous hydrogen fluoride and catalyzer is added in the first reactor, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters the first condenser, hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to the first reactor, and hydrogen chloride gas is discharged from the first condenser-air outlet;
7) after the anhydrous hydrogen fluoride in reactor last steams completely, after releasing leftover materials, then add trichlorotoluene zotrichloride, the temperature controlling reactor last is-20 ~ 10 DEG C;
Return step 2) carry out cyclical operation; Collect the leftover materials that each reactor is released, filter and distill, obtaining phenylfluoroform.
2. the multistage production method of phenylfluoroform according to claim 1, is characterized in that: in step 1), and the anhydrous hydrogen fluoride added in the first reactor and the mass ratio of phenylfluoroform are 5 ~ 6:3.5 ~ 4; Step 2) in step 7), the anhydrous hydrogen fluoride added in each reactor and the mass ratio of phenylfluoroform are 1 ~ 1.3:3.5 ~ 4.
3. the multistage production method of phenylfluoroform according to claim 1, is characterized in that: described catalyzer is yellow precipitate.
4. the multistage production method of the phenylfluoroform according to claim 1 or 3, is characterized in that: the add-on of described catalyzer is: in each reactor, the mass ratio of catalyzer and phenylfluoroform is 0.18 ~ 0.25:3.5 ~ 4.
5. the multistage production method of phenylfluoroform according to claim 1, is characterized in that: the temperature of described liquid phase fluorination reaction is-20 ~ 10 DEG C, and the reaction times is 3 ~ 6h.
6. the multistage production method of phenylfluoroform according to claim 1, is characterized in that: the hydrogen chloride gas of discharging from condenser-air outlet enters tail gas absorbing system.
7. the multistage production method of phenylfluoroform according to claim 1, is characterized in that: total number of reactor is 3 ~ 5.
8. the multistage production method of phenylfluoroform according to claim 1, is characterized in that: also comprise the following steps:
When interval stops production, in still for subsequent use, add trichlorotoluene zotrichloride and catalyzer, the temperature controlling still for subsequent use is-20 ~ 10 DEG C; After wherein one or more reaction kettle for reaction terminate, temperature of reaction kettle is risen to 20 ~ 60 DEG C, anhydrous hydrogen fluoride excessive in reactor is distilled out of, enter after condenser condenses for subsequent use in still for subsequent use, liquid phase fluorination reaction is carried out in stirring, the mixed gas that reaction produces enters condenser for subsequent use, and the hydrogen fluoride gas in mixed gas continues to participate in reaction through condensing reflux to still for subsequent use, and hydrogen chloride gas is discharged from condenser-air outlet for subsequent use.
9. the multistage production unit of a phenylfluoroform, it is characterized in that: comprise the single-stage production equipment that two or more is arranged in order, each single-stage production equipment comprises reactor and condenser, is provided with discharge gate, top is provided with opening for feed and gas-liquid refluxing opening bottom described reactor; Be provided with gas-liquid mouth bottom described condenser, top is provided with pneumatic outlet for being connected with device for absorbing tail gas, the gas-liquid mouth of condenser is connected by pilot piping with the gas-liquid refluxing opening of reactor; The gas-liquid refluxing opening of the reactor of each single-stage production equipment or the pneumatic outlet of condenser are also connected by pilot piping with the gas-liquid refluxing opening of the reactor of a rear single-stage production equipment, and the gas-liquid refluxing opening of the reactor of last single-stage production equipment or the pneumatic outlet of condenser are connected by pilot piping with the gas-liquid refluxing opening of the reactor of first single-stage production equipment.
10. the multistage production unit of phenylfluoroform according to claim 9, it is characterized in that: also comprise production equipment for subsequent use, described production equipment for subsequent use comprises still for subsequent use and condenser for subsequent use, is provided with discharge gate, top is provided with opening for feed and gas-liquid refluxing opening bottom described still for subsequent use; Be provided with gas-liquid mouth bottom described condenser for subsequent use, top is provided with pneumatic outlet for being connected with device for absorbing tail gas, the gas-liquid mouth of condenser for subsequent use is connected by pilot piping with the gas-liquid refluxing opening of still for subsequent use; The gas-liquid refluxing opening of the reactor of each single-stage production equipment or the pneumatic outlet of condenser are also connected by pilot piping with the gas-liquid refluxing opening of still for subsequent use.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399618A (en) * | 2015-12-21 | 2016-03-16 | 浙江华亿工程设计有限公司 | Continuous production apparatus for synthesis of isobutyryl chloride |
| CN115041106A (en) * | 2022-06-21 | 2022-09-13 | 湖北新轩宏新材料有限公司 | Reactor for preparing trichlorobenzene and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1087509A2 (en) * | 1982-02-17 | 1984-04-23 | Предприятие П/Я В-8469 | Process for preparing benztrifluoride |
| CN1294568A (en) * | 1999-02-15 | 2001-05-09 | 三井化学株式会 | Fluorinating agent, process for producing same, and use thereof |
| CN102924226A (en) * | 2012-10-29 | 2013-02-13 | 浙江巍华化工有限公司 | Industrial method for continuous fluorination synthesis of benzotrifluoride product |
-
2014
- 2014-03-04 CN CN201410076315.4A patent/CN104292070B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1087509A2 (en) * | 1982-02-17 | 1984-04-23 | Предприятие П/Я В-8469 | Process for preparing benztrifluoride |
| CN1294568A (en) * | 1999-02-15 | 2001-05-09 | 三井化学株式会 | Fluorinating agent, process for producing same, and use thereof |
| CN102924226A (en) * | 2012-10-29 | 2013-02-13 | 浙江巍华化工有限公司 | Industrial method for continuous fluorination synthesis of benzotrifluoride product |
Non-Patent Citations (1)
| Title |
|---|
| 雷宏等: "《三氟甲基苯的合成》", 《精细化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399618A (en) * | 2015-12-21 | 2016-03-16 | 浙江华亿工程设计有限公司 | Continuous production apparatus for synthesis of isobutyryl chloride |
| CN115041106A (en) * | 2022-06-21 | 2022-09-13 | 湖北新轩宏新材料有限公司 | Reactor for preparing trichlorobenzene and preparation method |
| CN115041106B (en) * | 2022-06-21 | 2023-11-07 | 湖北新轩宏新材料有限公司 | Reactor for preparing trichlorotoluene and preparation method |
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