CN104292070B - The multistage production method of a kind of benzotrifluoride and equipment - Google Patents
The multistage production method of a kind of benzotrifluoride and equipment Download PDFInfo
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- CN104292070B CN104292070B CN201410076315.4A CN201410076315A CN104292070B CN 104292070 B CN104292070 B CN 104292070B CN 201410076315 A CN201410076315 A CN 201410076315A CN 104292070 B CN104292070 B CN 104292070B
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Abstract
The invention discloses the multistage production method of a kind of benzotrifluoride and equipment, the method includes: 1) carry out liquid phase fluorination reaction in the first reactor；2) in the second reactor, benzotrichloride is added；3) enter the second reactor after fluohydric acid gas excessive in the first reactor being steamed, condensed, add anhydrous hydrogen fluoride and catalyst carries out liquid phase fluorination reaction；4) leftover materials in the first reactor are released, add benzotrichloride；5) according to step 2)～4), reactor below is operated；6) the first reactor is entered after fluohydric acid gas excessive in reactor last being steamed, condensed；7) leftover materials in reactor last are released, add benzotrichloride；Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, to obtain final product.The multistage production method of the present invention, drastically increases production efficiency and hydrofluoric utilization rate, and products obtained therefrom purity is high, yield is high.
Description
Technical field
The invention belongs to benzotrifluoride technical field, be specifically related to the multistage production method of a kind of benzotrifluoride, also relate to the multistage production equipment of a kind of benzotrifluoride.
Background technology
Benzotrifluoride is intermediate important in fluorine chemistry, is widely used in the production of medicine, pesticide, dyestuff, and is used as the manufacture etc. of vulcanizing agent, insecticide and insulating oil, for instance can prepare the herbicides such as fluometuron, fluorochloridone, Diflufenican.Benzotrifluoride can derive series benzotrifluoride product, as m-nitryl benzotrifluoride, mamino-trifluoromethyl benzene, a bromo benzotrifluoride, 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 benzotrifluoride is mainly: in the presence of a catalyst, and benzotrichloride and anhydrous hydrogen fluoride, by fluorination reaction, obtain benzotrifluoride after separated.At present, flaorination process mainly has gas phase fluorination and liquid-phase fluorination two kinds.Wherein, gas phase fluorination refers to many chlorine aromatic hydrocarbons and fluohydric acid gas in the presence of a catalyst, High Temperature Gas phase reaction, prepares polyfluoro aromatic hydrocarbons.The product yield of gas phase fluorination is good, but the reaction temperature of this method is up to 300～500 DEG C, and existing equipment material is generally difficult to meet the requirement of high-temperature fluorination reaction.Liquid-phase fluorination refers to that benzotrichloride is at catalyst, pressurization (also can normal pressure), low temperature (less than 100 DEG C), by the method for anhydrous hydrogen fluoride fluoride.This method responds the features such as temperature is relatively low, equipment corrosion is little, is prepare trifluoromethyl aromatic most common method, but, existing production method often adopts the method batch production of " treating different things alike ", and production efficiency is low, and product purity and yield are relatively low；Meanwhile, fluorination reaction Raw utilization rate is low, and excessive fluohydric acid gas reclaims difficulty, causes the serious wasting of resources and environmental pollution.
Summary of the invention
It is an object of the invention to provide the multistage production method of a kind of benzotrifluoride, solve that existing production method production efficiency is low, problem that product purity and yield are relatively low.
Second purpose of the present invention is to provide the multistage production equipment of a kind of benzotrifluoride.
In order to realize object above, the technical solution adopted in the present invention is: the multistage production method of a kind of benzotrifluoride, comprises the following steps:
1) in the first reactor, benzotrichloride is added, the temperature controlling the first reactor is-20～10 DEG C, anhydrous hydrogen fluoride and catalyst is added in the first reactor, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters the first condenser, condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, and hydrogen chloride gas is discharged from the first condenser-air outlet；
2) adding benzotrichloride in the second reactor, 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 condensation, in the second reactor, add anhydrous hydrogen fluoride and catalyst simultaneously, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters the second condenser, condensed second reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride, the temperature controlling the first reactor is-20～10 DEG C；
5) according to the relation of the front and back reactor corresponding principle of relation with the first reactor, the second reactor, according to step 2), 3), 4), reactor below is 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 condensation, anhydrous hydrogen fluoride and catalyst is added in the first reactor, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters the first condenser, condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride, the temperature controlling reactor last is-20～10 DEG C；
Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, obtaining benzotrifluoride.
In step 1), the anhydrous hydrogen fluoride added in the first reactor and the mass ratio of benzotrifluoride are 5～6:3.5～4；Step 2) to step 7), the anhydrous hydrogen fluoride added in each reactor and the mass ratio of benzotrifluoride are 1～1.3:3.5～4.
Described catalyst is yellow mercury oxide.
The addition of described catalyst is: in each reactor, catalyst is 0.18～0.25:3.5～4 with the mass ratio of benzotrifluoride.
The temperature of described liquid phase fluorination reaction is-20～10 DEG C, and the response time is 3～6h.
The hydrogen chloride gas discharged 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, adding benzotrichloride and catalyst in standby still, the temperature controlling standby still 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 in standby still after standby condenser condenses, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters standby condenser, and hydrogen fluoride gas in mixing gas is condensed to be back to standby still and continue to participate in reaction, and hydrogen chloride gas is discharged from the outlet of standby condenser-air.
The multistage production equipment of a kind of benzotrifluoride, including the single-stage process units that two or more is arranged in order, each single-stage process units includes reactor and condenser, is provided with discharge gate, top is provided with charging aperture and gas-liquid refluxing opening bottom described reactor；Be provided with gas-liquid mouth bottom described condenser, top is provided with the gas outlet for being connected with device for absorbing tail gas, and the gas-liquid mouth of condenser is connected by control piper with the gas-liquid refluxing opening of reactor；The gas-liquid refluxing opening of the reactor of each single-stage process units or the gas outlet of condenser are also connected by control piper with the gas-liquid refluxing opening of the reactor of later single-stage process units, and the gas-liquid refluxing opening of the reactor of last single-stage process units or the gas outlet of condenser are connected by control piper with the gas-liquid refluxing opening of the reactor of first single-stage process units.
Also including standby process units, described standby process units includes standby still and standby condenser, and described standby bottom portion is provided with discharge gate, top is provided with charging aperture and gas-liquid refluxing opening；Be provided with gas-liquid mouth bottom described standby condenser, top is provided with the gas outlet for being connected with device for absorbing tail gas, and the gas-liquid mouth of standby condenser is connected by control piper with the gas-liquid refluxing opening of standby still；The gas-liquid refluxing opening of the reactor of each single-stage process units or the gas outlet of condenser are also connected by control piper with the gas-liquid refluxing opening of standby still.
Described control piper refers to be provided with the pipeline controlling valve.
In the multistage production method of the benzotrifluoride of the present invention, liquid phase fluorination reaction process all adopts condensing reflux mode, now in condenser, cooling water temperature controls to arrive: mixing gas in hydrogen fluoride gas can condensing reflux in reactor, but in course of reaction generate hydrogen chloride remove tail gas absorbing system in gaseous form；Preferably-25～0 DEG C.When steaming excessive anhydrous hydrogen fluoride, condenser cools down the temperature of water and controls to: the hydrogen fluoride gas steamed to be condensed into liquid anhydrous hydrogen fluoride in later reactor, but the hydrogen chloride steamed removes tail gas absorbing system in gaseous form；Preferably-25～0 DEG C.Wherein, the boiling point under fluohydric acid gas normal pressure is 19.5 DEG C, and the boiling point under hydrogen chloride normal pressure is-85 DEG C.
The multistage production method of the benzotrifluoride of the present invention, when carrying out liquid phase fluorination reaction in each reactor, the condensed reactor that is back to of hydrogen fluoride gas in the mixing gas of generation continues to participate in reaction, improves the utilization rate of raw material；Hydrogen chloride gas is discharged from condenser-air outlet, and product is discharged response system in time, improves reaction rate, 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, enter later reactor after excessive fluohydric acid gas is steamed, condensed and continue to participate in reaction, excessive fluohydric acid gas is recycled fully, drastically increases hydrofluoric utilization rate, solves the problem that excessive fluohydric acid gas reclaims difficulty；The multistage production method of the application, multiple reactors produce successively, and circulation operation, production effect is high；Reaction condition is gentle, and safety is high, it is easy to operation and control, is suitable for industrialization large-scale production.
The multistage production equipment of the benzotrifluoride of the present invention, the gas outlet of the condenser of each single-stage process units is also connected by control piper with the gas-liquid refluxing opening of the reactor of later single-stage process units, the gas outlet of the condenser of last single-stage process units is connected by control piper with the gas-liquid refluxing opening of the reactor of first single-stage process units, make the condensing reflux of anhydrous hydrogen fluoride in liquid phase fluorination reaction process, and reaction terminate after excessive anhydrous hydrogen fluoride steams, the technique that condenses to later reactor effectively carries out；Each single-stage reaction unit is mutually linked, excessive fluohydric acid gas is recycled fully, drastically increase hydrofluoric utilization rate, make the utilization rate of anhydrous hydrogen fluoride be brought up to 95%～98% by 70%～80%, solve the problem that excessive fluohydric acid gas reclaims difficulty；Decrease hydrofluoric waste, reduce production cost；Being prevented effectively from leakage, reduce operational danger, environmental friendliness, safety is high, has greatly ensured the personal safety of employee；Achieving the continuous production of benzotrifluoride, production efficiency is high, and products obtained therefrom purity is high, productivity is high；Reasonable in design, it is easy to operation and control, it is suitable for popularization and application.
Accompanying drawing explanation
Fig. 1 is the structural representation of the multistage production equipment of the benzotrifluoride of embodiment 1；
Fig. 2 is the structural representation of the single-stage production equipment of benzotrifluoride；
Fig. 3 is the structural representation of the multistage production equipment of the benzotrifluoride of embodiment 2；
Fig. 4 is the structural representation of the multistage production equipment of the benzotrifluoride of embodiment 3.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
Embodiment 1
The multistage production method of the benzotrifluoride of the present embodiment, comprises the following steps:
1) in the first reactor, benzotrichloride 391kg is added, the temperature controlling the first reactor is-20 DEG C, anhydrous hydrogen fluoride 600kg, catalyst yellow mercury oxide 20kg is added in the first reactor, stirring carries out liquid phase fluorination reaction, reaction temperature is-20 DEG C, response time is 6h, the mixing gas that reaction produces enters the first condenser (0 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, and hydrogen chloride gas is discharged from the first condenser-air outlet；
2) adding benzotrichloride 391kg in the second reactor, 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) condenses, in the second reactor, add anhydrous hydrogen fluoride 130kg simultaneously, catalyst yellow mercury oxide 20kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-20 DEG C, response time is 6h, the mixing gas that reaction produces enters the second condenser (0 DEG C), condensed second reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 391kg, the temperature controlling the first reactor is-20 DEG C；
5) adding benzotrichloride 391kg in the 3rd reactor, 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) condenses in the 3rd reactor, in the 3rd reactor, add anhydrous hydrogen fluoride 130kg simultaneously, catalyst yellow mercury oxide 20kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-20 DEG C, response time is 6h, the mixing gas that reaction produces enters the 3rd condenser (0 DEG C), condensed the 3rd reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 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) condenses, anhydrous hydrogen fluoride 130kg is added in the first reactor, catalyst yellow mercury oxide 20kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-20 DEG C, response time is 6h, the mixing gas that reaction produces enters the first condenser (0 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 391kg, the temperature controlling the 3rd reactor is-20 DEG C；
Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, obtaining benzotrifluoride.
The purity of the present embodiment gained benzotrifluoride is 99.6%, and yield is 95.5%.
The multistage production equipment of the benzotrifluoride of the present embodiment, as shown in Figure 1, 2, including three single-stage process units being arranged in order, each single-stage process units internal structure identical (as shown in Figure 2), including reactor 1 and condenser 2, being provided with discharge gate 3 bottom reactor 1, the pipeline being connected with discharge gate 3 is provided with blow-off valve F2；The top of reactor 1 is provided with charging aperture 4 and gas-liquid refluxing opening 5, and the pipeline being connected with charging aperture 4 is provided with inlet valve F1；Be provided with gas-liquid mouth 6 bottom condenser 2, top is provided with gas outlet 7, and gas outlet 7 is connected with device for absorbing tail gas by tail gas pipeline 11, and tail gas pipeline is provided with air bleeding valve F4；The gas-liquid mouth 6 of condenser 2 is connected by reflux pipe 10 with the gas-liquid refluxing opening 5 of reactor 1, and reflux pipe 10 is provided with reflux inlet F3；Being provided with agitating device 8 in reactor 1 inner chamber, shell is provided with jacket heat-preservation device 9, and jacket heat-preservation device 9 is provided with coolant Heating medium, the outlet of coolant heating agent；Three single-stage process units of the present embodiment are followed successively by one-level process units, two grades of process units, three grades of process units, and wherein, the reactor of one-level process units is the first reactor 101, and condenser is the first condenser 102；The reactor of two grades of process units is the second reactor 201, and condenser is the second condenser 202；The reactor of three grades of process units is the 3rd reactor 301, and condenser is the 3rd condenser 302；The gas outlet of the first condenser 102 is also connected by the first control piper 103 with the gas-liquid refluxing opening of the second reactor 201, first control piper 103 is provided with the first control valve F5, the gas outlet of the second condenser 202 is also connected by the second control piper 203 with the gas-liquid refluxing opening of the 3rd reactor 301, second control piper 203 is provided with the second control valve F7, the gas outlet of the 3rd condenser 302 is connected by three grades of loop control pipelines 305 with the gas-liquid refluxing opening of the first reactor 101, three grades of loop control pipelines 305 are provided with the first circulation control valve F6 and the three and control valve F8.
During use, close the blow-off valve F2 of first order reaction device, first controls valve F5 and the first circulation control valve F6, open the reflux inlet F3 and air bleeding valve F4 of first order reaction device, benzotrichloride is added in the first reactor 101, anhydrous hydrogen fluoride and catalyst react, the mixing gas that reaction produces enters the first condenser 102 through reflux pipe, it is back to the first reactor 101 through reflux pipe after hydrogen fluoride gas condensation in mixing gas and continues to participate in reaction, hydrogen chloride gas is discharged from the gas outlet of the first condenser 102, device for absorbing tail gas is entered through tail gas pipeline 11.Close the blow-off valve F2 of secondary response device, the second control valve F7, open the reflux inlet F3 and air bleeding valve F4 of secondary response device, in the second reactor 201, add benzotrichloride；After in the first reactor 101, reaction terminates, close the air bleeding 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 secondary response device through the first control piper 103, in the second reactor 201, add anhydrous hydrogen fluoride simultaneously and catalyst reacts.After the anhydrous hydrogen fluoride in the first reactor 101 steams completely, close the first control valve F5, open after the blow-off valve F2 of first order reaction device carries out blowing, close blow-off valve, add benzotrichloride raw material.Close the blow-off valve F2 of third-order reaction device, the second circulation control valve F8, open the reflux inlet F3 and air bleeding valve F4 of third-order reaction device, in the 3rd reactor 301, add benzotrichloride；After in the second reactor 201, reaction terminates, close the air bleeding valve F4 of secondary response 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 control piper 203, in the 3rd reactor 301, add anhydrous hydrogen fluoride simultaneously and catalyst reacts.After the anhydrous hydrogen fluoride in the second reactor 201 steams completely, close the second control valve F7, open after the blow-off valve F2 of secondary response device carries out blowing, close blow-off valve, add benzotrichloride raw material.After in the 3rd reactor 301, reaction terminates, close the air bleeding valve F4 of third-order reaction device, open the first circulation control valve F6 and the three and control valve F8, make the anhydrous hydrogen fluoride steamed in the 3rd reactor 301 enter first order reaction device through three grades of loop control pipelines 305, in the first reactor 101, add anhydrous hydrogen fluoride simultaneously and catalyst reacts.Circulation continuous operation successively, it is achieved the multistage production method of the benzotrifluoride of the present embodiment.
Embodiment 2
The multistage production method of the benzotrifluoride of the present embodiment, comprises the following steps:
1) in the first reactor, benzotrichloride 400kg is added, the temperature controlling the first reactor is 10 DEG C, anhydrous hydrogen fluoride 570kg, catalyst yellow mercury oxide 25kg is added in the first reactor, stirring carries out liquid phase fluorination reaction, reaction temperature is 10 DEG C, response time is 3h, the mixing gas that reaction produces enters the first condenser (-10 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, and hydrogen chloride gas is discharged from the first condenser-air outlet；
2) adding benzotrichloride 400kg in the second reactor, 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 in the second reactor after the second condenser (-10 DEG C) condenses, in the second reactor, add anhydrous hydrogen fluoride 100kg simultaneously, catalyst yellow mercury oxide 25kg, stirring carries out liquid phase fluorination reaction, reaction temperature is 10 DEG C, response time is 3h, the mixing gas that reaction produces enters the second condenser (-10 DEG C), condensed second reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 400kg, the temperature controlling the first reactor is 10 DEG C；
5) adding benzotrichloride 400kg in the 3rd reactor, 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 in the 3rd reactor after the 3rd condenser (-10 DEG C) condensation, in the 3rd reactor, add anhydrous hydrogen fluoride 100kg simultaneously, catalyst yellow mercury oxide 25kg, stirring carries out liquid phase fluorination reaction, reaction temperature is 10 DEG C, response time is 3h, the mixing gas that reaction produces enters the 3rd condenser (-10 DEG C), condensed the 3rd reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 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 in the first reactor after the first condenser (-10 DEG C) condenses, anhydrous hydrogen fluoride 100kg is added in the first reactor, catalyst yellow mercury oxide 25kg, stirring carries out liquid phase fluorination reaction, reaction temperature is 10 DEG C, response time is 3h, the mixing gas that reaction produces enters the first condenser (-10 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 400kg, the temperature controlling the 3rd reactor is 10 DEG C；
Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, obtaining benzotrifluoride.
When interval stops production, adding benzotrichloride 400kg, catalyst yellow mercury oxide 25kg in standby still, the temperature controlling standby still 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, entering in standby still after standby condenser condenses, stirring carries out liquid phase fluorination reaction, and reaction temperature is 10 DEG C, response time is 3h, the mixing gas that reaction produces enters standby condenser, and hydrogen fluoride gas in mixing gas is condensed to be back to standby still and continue to participate in reaction, and hydrogen chloride gas is discharged from the outlet of standby condenser-air.
The purity of the present embodiment gained benzotrifluoride is 99.2%, and yield is 91%.
The multistage production equipment of the benzotrifluoride of the present embodiment, as shown in Figure 3, difference from Example 1 is in that: also include standby process units, described standby process units includes standby still 111 and standby condenser 112, being provided with discharge gate bottom described standby still 111, the pipeline being connected with discharge gate is provided with blow-off valve F2；Standby still top is provided with charging aperture and gas-liquid refluxing opening, and the pipeline being connected with charging aperture is provided with inlet valve F1；Be provided with gas-liquid mouth bottom described standby condenser 112, top is provided with gas outlet, and gas outlet is connected with device for absorbing tail gas by tail gas pipeline 11, and tail gas pipeline is provided with air bleeding valve F4；The gas-liquid mouth of standby condenser 112 is connected by control piper with the gas-liquid refluxing opening of standby still 001, this control piper is provided with the structure of the standby process units of reflux inlet F3(with single-stage process units, it is specifically shown in Fig. 2, wherein standby still is equivalent to the reactor of single-stage process units, and standby condenser is equivalent to the condenser in single-stage process units)；The gas outlet of first condenser the 102, second condenser the 202, the 3rd condenser 302 is connected respectively through first spare duct the 104, second spare duct the 204, the 3rd spare duct 304 with the gas-liquid refluxing opening of standby still 111, described first spare duct 104 is provided with the first service valve F9, second spare duct 204 is provided with the second service valve F10, and the 3rd spare duct 304 is provided with the 3rd service valve F11.
When interval stops production, open the reflux inlet F3 and air bleeding valve F4 of standby reaction unit, in standby still, add benzotrichloride, catalyst；When first, second, after 3rd reaction kettle for reaction terminates, close one-level, two grades, the air bleeding valve of third-order reaction device and first controls valve F5, second controls valve F7, 3rd controls valve F8, open the first service valve F9, second service valve F10 and the three service 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 standby reaction unit and reacts, the mixing gas that reaction produces enters standby condenser 112, hydrogen fluoride gas in mixing gas is condensed to be back to standby still 111 and continues to participate in reaction, hydrogen chloride gas is discharged from the gas outlet of standby condenser 112, device for absorbing tail gas is entered through tail gas pipeline 11.
The multistage production equipment of the benzotrifluoride of the present embodiment also includes standby process units, solve existing equipment interval when stopping production, excessive anhydrous hydrogen fluoride overflows the wasting of resources and problem of environmental pollution that cause, further increases the utilization rate of anhydrous hydrogen fluoride, has saved resource；Meanwhile, improve the safety of complete equipment.
Embodiment 3
The multistage production method of the benzotrifluoride of the present embodiment, comprises the following steps:
1) in the first reactor, benzotrichloride 350kg is added, the temperature controlling the first reactor is-10 DEG C, anhydrous hydrogen fluoride 500kg, catalyst yellow mercury oxide 18kg is added in the first reactor, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the first condenser (-5 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, and hydrogen chloride gas is discharged from the first condenser-air outlet；
2) adding benzotrichloride 350kg in the second reactor, 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 in the second reactor after the second condenser (-5 DEG C) condenses, in the second reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the second condenser (-5 DEG C), condensed second reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 350kg, the temperature controlling the first reactor is-10 DEG C；
5) adding benzotrichloride 350kg in the 3rd reactor, 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 in the 3rd reactor after the 3rd condenser (-5 DEG C) condensation, in the 3rd reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the 3rd condenser (-5 DEG C), condensed the 3rd reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 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 in the first reactor after the first condenser (-5 DEG C) condenses, anhydrous hydrogen fluoride 110kg is added in the first reactor, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the first condenser (-5 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 350kg, the temperature controlling the 3rd reactor is-10 DEG C；
Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, obtaining benzotrifluoride.
When interval stops production, adding benzotrichloride 350kg, catalyst yellow mercury oxide 18kg in standby still, the temperature controlling standby still 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, entering in standby still after standby condenser condenses, stirring carries out liquid phase fluorination reaction, and reaction temperature is-10 DEG C, response time is 4h, the mixing gas that reaction produces enters standby condenser, and hydrogen fluoride gas in mixing gas is condensed to be back to standby still and continue to participate in reaction, and hydrogen chloride gas is discharged from the outlet of standby condenser-air.
The purity of the present embodiment gained benzotrifluoride is 99.4%, and yield is 93.0%.
The multistage production equipment of the benzotrifluoride of the present embodiment is with embodiment 2.
Embodiment 4
The multistage production method of the benzotrifluoride of the present embodiment, comprises the following steps:
1) in the first reactor, benzotrichloride 350kg is added, the temperature controlling the first reactor is-10 DEG C, anhydrous hydrogen fluoride 500kg, catalyst yellow mercury oxide 18kg is added in the first reactor, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the first condenser (-5 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, and hydrogen chloride gas is discharged from the first condenser-air outlet；
2) adding benzotrichloride 350kg in the second reactor, 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 in the second reactor after the second condenser (-5 DEG C) condenses, in the second reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the second condenser (-5 DEG C), condensed second reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 350kg, the temperature controlling the first reactor is-10 DEG C；
5) adding benzotrichloride 350kg in the 3rd reactor, 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 in the 3rd reactor after the 3rd condenser (-5 DEG C) condensation, in the 3rd reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the 3rd condenser (-5 DEG C), condensed the 3rd reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 391kg, the temperature controlling the second reactor is-10 DEG C；
8) adding benzotrichloride 350kg in the 4th reactor, 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 in the 4th reactor after the 4th condenser (-5 DEG C) condensation, in the 4th reactor, add anhydrous hydrogen fluoride 110kg simultaneously, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the 4th condenser (-5 DEG C), condensed the 4th reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 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 in the first reactor after the first condenser (-5 DEG C) condenses, anhydrous hydrogen fluoride 110kg is added in the first reactor, catalyst yellow mercury oxide 18kg, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 5h, the mixing gas that reaction produces enters the first condenser (-5 DEG C), condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride 350kg, the temperature controlling the 4th reactor is-10 DEG C；
Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, obtaining benzotrifluoride.
When interval stops production, adding benzotrichloride 350kg, catalyst yellow mercury oxide 18kg in standby still, the temperature controlling standby still 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 in standby still after standby condenser condenses, stirring carries out liquid phase fluorination reaction, reaction temperature is-10 DEG C, response time is 4h, the mixing gas that reaction produces enters standby condenser, hydrogen fluoride gas in mixing gas is condensed to be back to standby still and continues to participate in reaction, and hydrogen chloride gas is discharged from the outlet of standby condenser-air.
The purity of the present embodiment gained benzotrifluoride is 99.4%, and yield is 93.0%.
The multistage production equipment of the benzotrifluoride of the present embodiment, as shown in Figure 4, difference from Example 2 is in that: include four single-stage process units being arranged in order and a standby process units, and four single-stage process units are followed successively by one-level process units, two grades of process units, three grades of process units, level Four process units；The reactor of level Four process units is the 4th reactor 401, and condenser is the 4th condenser 402；The gas outlet of the first condenser 102 is connected by the first control piper 103 with the gas-liquid refluxing opening of the second reactor 201, and the first control piper 103 is provided with the first control valve F5；The gas outlet of the second condenser 202 is connected by the second control piper 203 with the gas-liquid refluxing opening of the 3rd reactor 301, and the second control piper 203 is provided with the second control valve F7；The gas outlet of the 3rd condenser 302 controls pipe 303 tunnel with the gas-liquid refluxing opening of the 4th reactor 401 by the 3rd and is connected, and the 3rd control piper 303 is provided with the 3rd control valve F8；The gas outlet of the 4th condenser 402 is connected by level Four loop 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 four and controls valve F12；The gas outlet of first condenser the 102, second condenser the 202, the 3rd condenser the 302, the 4th condenser 402 is connected respectively through first spare duct the 104, second spare duct the 204, the 3rd spare duct 304 control piper, the 4th spare duct 404 with the gas-liquid refluxing opening of standby still 111, described first spare duct 104 is provided with the first service valve F9, second spare duct 204 is provided with the second service valve F10,3rd spare duct 304 is provided with the 3rd service valve F11, and the 4th spare duct 404 is provided with the 4th service valve F13.
Claims (8)
1. the multistage production method of a benzotrifluoride, it is characterised in that: comprise the following steps:
1) in the first reactor, benzotrichloride is added, the temperature controlling the first reactor is-20～10 DEG C, anhydrous hydrogen fluoride and catalyst is added in the first reactor, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters the first condenser, condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, and hydrogen chloride gas is discharged from the first condenser-air outlet；
2) adding benzotrichloride in the second reactor, 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 condensation, in the second reactor, add anhydrous hydrogen fluoride and catalyst simultaneously, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters the second condenser, condensed second reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride, the temperature controlling the first reactor is-20～10 DEG C；
5) according to the relation of the front and back reactor corresponding principle of relation with the first reactor, the second reactor, according to step 2), 3), 4), reactor below is 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 condensation, anhydrous hydrogen fluoride and catalyst is added in the first reactor, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters the first condenser, condensed first reactor that is back to of hydrogen fluoride gas in mixing gas continues to participate in reaction, 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, adding benzotrichloride, the temperature controlling reactor last is-20～10 DEG C；
Return step 2) it is circulated operation；Collect the leftover materials that each reactor is released, filter and distill, obtaining benzotrifluoride；
In step 1), the anhydrous hydrogen fluoride added in the first reactor and the mass ratio of benzotrichloride are 5～6:3.5～4；Step 2) to step 7), the anhydrous hydrogen fluoride added in each reactor and the mass ratio of benzotrichloride are 1～1.3:3.5～4；
Total number of reactor is 3～5.
2. the multistage production method of benzotrifluoride according to claim 1, it is characterised in that: described catalyst is yellow mercury oxide.
3. the multistage production method of benzotrifluoride according to claim 1 and 2, it is characterised in that: the addition of described catalyst is: in each reactor, catalyst is 0.18～0.25:3.5～4 with the mass ratio of benzotrichloride.
4. the multistage production method of benzotrifluoride according to claim 1, it is characterised in that: the temperature of described liquid phase fluorination reaction is-20～10 DEG C, and the response time is 3～6h.
5. the multistage production method of benzotrifluoride according to claim 1, it is characterised in that: the hydrogen chloride gas discharged from condenser-air outlet enters tail gas absorbing system.
6. the multistage production method of benzotrifluoride according to claim 1, it is characterised in that: also comprise the following steps:
When interval stops production, adding benzotrichloride and catalyst in standby still, the temperature controlling standby still 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 in standby still after standby condenser condenses, stirring carries out liquid phase fluorination reaction, the mixing gas that reaction produces enters standby condenser, and hydrogen fluoride gas in mixing gas is condensed to be back to standby still and continue to participate in reaction, and hydrogen chloride gas is discharged from the outlet of standby condenser-air.
7. the multistage production equipment of a benzotrifluoride, it is characterized in that: include the single-stage process units that two or more is arranged in order, each single-stage process units includes reactor and condenser, is provided with discharge gate, top is provided with charging aperture and gas-liquid refluxing opening bottom described reactor；Be provided with gas-liquid mouth bottom described condenser, top is provided with the gas outlet for being connected with device for absorbing tail gas, and the gas-liquid mouth of condenser is connected by control piper with the gas-liquid refluxing opening of reactor；The gas-liquid refluxing opening of the reactor of each single-stage process units or the gas outlet of condenser are also connected by control piper with the gas-liquid refluxing opening of the reactor of later single-stage process units, and the gas-liquid refluxing opening of the reactor of last single-stage process units or the gas outlet of condenser are connected by control piper with the gas-liquid refluxing opening of the reactor of first single-stage process units.
8. the multistage production equipment of benzotrifluoride according to claim 7, it is characterized in that: also include standby process units, described standby process units includes standby still and standby condenser, and described standby bottom portion is provided with discharge gate, top is provided with charging aperture and gas-liquid refluxing opening；Be provided with gas-liquid mouth bottom described standby condenser, top is provided with the gas outlet for being connected with device for absorbing tail gas, and the gas-liquid mouth of standby condenser is connected by control piper with the gas-liquid refluxing opening of standby still；The gas-liquid refluxing opening of the reactor of each single-stage process units or the gas outlet of condenser are also connected by control piper with the gas-liquid refluxing opening of standby still.
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| 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 |
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| 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 |
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