CN102974280B - Method and equipment for improving F-C acyl chloride reaction yield - Google Patents
Method and equipment for improving F-C acyl chloride reaction yield Download PDFInfo
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- CN102974280B CN102974280B CN201210495265.4A CN201210495265A CN102974280B CN 102974280 B CN102974280 B CN 102974280B CN 201210495265 A CN201210495265 A CN 201210495265A CN 102974280 B CN102974280 B CN 102974280B
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Abstract
The invention provides a method for improving an F-C acyl chloride reaction yield, comprising the following steps of: controlling an acyl chloride dripping speed in a feeding process by monitoring real-time production of hydrogen chloride; and/or controlling a temperature rise speed of a reaction kettle by monitoring the real-time production of the hydrogen chloride; and finally, judging whether the reaction is finished or not by monitoring the real-time production of tail gas. A reaction device comprises a material acylating agent dripping device, an acylating reaction kettle, a water cooling device and a tail gas absorbing device; the discharging end of the material dripping device is connected with the feeding end of the acylating reaction kettle; a material valve for controlling an inlet amount of a put-in material is arranged between the discharging end of the material dripping device with the feeding end of the acylating reaction kettle; a vapor valve for controlling a heating speed of the reaction kettle is further arranged on one side on the acylating reaction kettle; and the gas inlet end of the water cooling device and the gas outlet end of the acylating reaction kettle are connected through a gas discharging pipeline, and the gas outlet end of the water cooling device is connected with the inlet end of the tail gas absorbing device through the gas discharging pipeline. The device further comprises a gas monitoring device arranged on the gas discharging pipeline.
Description
Technical field
The present invention relates to Fu Ke acyl chloride reaction, particularly relate to and a kind ofly can improve the method for Fu Ke acyl chloride reaction yield and the equipment for the method thereof.
Background technology
Fu Ke acyl chloride reaction is under strong lewis acid does catalysts conditions, allows acyl chlorides and phenyl ring carry out the reaction of acidylate.The condition that reaction condition is similar to alkylated reaction is removed.The first step is under lewis acidic condition, and dissociating of chlorine forms acyl group carbonium ion: second step is ensuing aromatic ring electrophilic reagent attack acyl cation: final step, and Charger transfer forms HCl to chlorine atom, and AlCl
3catalyst is formed again.Reversible reaction by reaction expression known generation acyl group carbonium ion.Generally be divided in conventional Fu Ke acyl chloride reaction technique: control to feed intake, heat up and be incubated three stages, therefore, therefore, in the production process of current reality, be generally the process that the time for adding by controlling acyl chlorides, reaction temperature and reaction duration control to react, this reaction controlling means are more extensive, due to the reason of vapor liquid equilibrium, when not carrying out Real-Time Monitoring for reaction speed, when reaction is carried out violent, raw material can be caused to escape along with tail gas.With the existing explained hereafter of 2,4-dichloroacetophenone for example: 2,4-dichloroacetophenone production process is made up of chloroacetic chloride complexing, m-dichlorobenzene acidylate, washing, distillation, crystallization, the large step of packaging six.In acidylate pot, add 305 kilograms of m-dichlorobenzenes, open manhole, trial throw alchlor, after without exception, add up to the aluminum trichloride (anhydrous) of input 375 kilograms, stir, be warming up to 40 ~ 45 DEG C, then start the chloroacetic chloride dripping 180 kilograms, time for adding is 2.5 ~ 3h; After, start to heat up stage by stage, 45 ~ 55 DEG C of heating-up times are 1h, and 65 ~ 75 DEG C of heating-up times are 2.5h, 110 ~ 120 DEG C of temperature retention time 1.5h; Reaction terminates, and in ice bath situation, adds frozen water, hydrochloric acid is hydrolyzed at <85 DEG C; Hydrolysis terminates, stratification, and water layer process is discharged, suction distillation still after oil reservoir washing; Thick steaming, reclaim 2,4-dichloroacetophenone, essence steams to obtain foreshot and 2,4-dichloroacetophenone; After crystallisation by cooling, centrifugal, methanol rinse, pulverizing, after the assay was approved, pack and obtain 305 kilograms of finished products.2, the 4-dichloroacetophenones reclaimed and foreshot, centrifugate recycle, and the comprehensive yield of product is throwing 930 kilograms of m-dichlorobenzenes, 1143 kilograms of aluminum trichloride (anhydrous)s, 549 kilograms of chloroacetic chlorides obtain 1 ton of 2,4-dichloroacetophenone finished product.
Summary of the invention
For the deficiencies in the prior art, the invention provides one can detect in real time in Fu Ke acyl chloride reaction process, greatly can improve the method for Fu Ke acyl chloride reaction yield simultaneously; Another object of the present invention is to provide the equipment for said method.
For achieving the above object, the present invention adopts following technical scheme to realize:
Improve a method for Fu Ke acyl chloride reaction yield, it is specially: by monitoring the in-time generatin amount of hydrogen chloride, control the rate of addition of the acyl chlorides in the process of feeding intake;
And/or, by monitoring the in-time generatin amount of hydrogen chloride, control the programming rate of reactor;
Finally, by monitoring the in-time generatin amount of tail gas, judge whether reaction terminates.
For the device of said method, comprise material acylating agent Dropping feeder, acylation reaction still, water cooling plant and device for absorbing tail gas, the discharge end of described material dropping device is connected with the feed end of acylation reaction still, the material valve for controlling to throw in material inlet is provided with between described material dropping device and acylation reaction still, side on described acylation reaction still is also provided with the steam valve for controlling reactor firing rate, the inlet end of described water cooling plant is connected by gas exhaustion line with the gas outlet end of acylation reaction still, the outlet side of described water cooling plant is connected by gas exhaustion line with the arrival end of device for absorbing tail gas, also comprise the gas controlling device for monitoring the generation gas flow in Fu Ke acyl chloride reaction in described Fu Ke acyl chloride reaction device, described gas controlling device, its device is on gas exhaustion line.
Described Fu Ke acyl chloride reaction device also comprises the flow measurement device for detecting acylating agent rate of feeding, described flow measurement device is arranged between the discharge end of material dropping device and the feed end of acylation reaction still.
Described gas controlling device is arranged on inlet end or the outlet side of the water cooling plant of water cooling plant, and described gas controlling device is preferably arranged on the outlet side of water cooling plant.
Described reaction unit also comprises cryogenic system and storage tank, the arrival end of described cryogenic system is connected with the port of export of gas controlling device by gas exhaustion line, the port of export of described cryogenic system is connected with storage tank, described cryogenic system, its branch road is also provided with device for absorbing tail gas.
Described flow measurement device is fluid flowmeter.
Described tail gas receiving system is provided with the falling-film absorber for absorbing hydrogen chloride gas.
Described gas controlling device is selected: for detecting the mass-flow gas meter of gas weight, or for detecting the one in the gas volume flow gauge of gas flow.
In technique scheme, by the at-once monitor to hydrogen chloride, control Friedel-Crafts reaction severity, reclaim the material taken away mutually of hydrogen chloride gas, by subzero treatment, hydrogen chloride pure in tail gas can technical hydrochloric acid processed, the gas controlling device for monitoring the generation gas flow in Fu Ke acyl chloride reaction is also provided with in the Fu Ke acyl chloride reaction device adopted, described gas controlling device, its device is on gas exhaustion line, described gas controlling device is preferably arranged on water cooling plant inlet end or condenser outlet side, preferably be arranged on condenser outlet side, adopt this technical scheme, hydrogen chloride gas in course of reaction is after water cooling plant, again after gas controlling device detects, be confirmed whether need the material valve of regulable control rate of feeding and control the steam valve of still temperature, that is, if under low-temperature condition, do not have hydrogen chloride gas to produce, then can pass through the form fed intake fast, therefore then without the need to the material valve of regulable control rate of feeding, if at high operating temperatures, then there is a large amount of hydrogen chloride gas to produce, then need the material valve of regulable control rate of feeding, in technical scheme of the present invention, its gas controlling device can need according to concrete technology the mass-flow gas meter selected targetedly for gas-monitoring weight, or for monitoring the gas volume flow gauge surveying gas flow.
In addition, in the inventive solutions, additionally use cryogenic system, this cryogenic system can collect the escape material cooled down, then is entered in storage tank by discharge of materials.
Beneficial effect of the present invention is: the process can finding out Fu Ke acyl chloride reaction intuitively, because Tail gas measuring device and temperature control association get up, make the automation of Fu Ke acyl chloride reaction process units, response error is little, and the yield of Fu Ke acyl chloride reaction improves 10% than original Processes and apparatus.
Accompanying drawing explanation
Fig. 1 is the reaction expression in background technology;
Fig. 2 is 2,4-dichloroacetophenone process charts in background technology;
Fig. 3 is the structural representation of present device.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
Improve a method for Fu Ke acyl chloride reaction yield, by monitoring the in-time generatin amount of hydrogen chloride, controlling the rate of addition of the acyl chlorides in the process of feeding intake and the in-time generatin amount by monitoring hydrogen chloride, controlling the programming rate of reactor;
Finally, by monitoring the in-time generatin amount of tail gas, judge whether reaction terminates.
For realizing the device of said method, comprise material acylating agent Dropping feeder 1, acylation reaction still 2, water cooling plant 3 and device for absorbing tail gas 4, the discharge end of described material dropping device 1 is connected with the feed end of acylation reaction still 2, the side be provided with between described material dropping device 1 and acylation reaction still 2 on the acylation reaction still 2 described in material valve 11 for controlling to throw in material inlet is also provided with the steam valve 21 for controlling reactor firing rate, the inlet end of described water cooling plant 3 is connected by gas exhaustion line with the gas outlet end of acylation reaction still 2, the outlet side of described water cooling plant 3 is connected by gas exhaustion line with the arrival end of device for absorbing tail gas 4, described tail gas receiving system 4 is provided with tail gas absorption film, the gas controlling device 5 for detecting the generation gas flow in Fu Ke acyl chloride reaction is also comprised in described Fu Ke acyl chloride reaction device, described gas controlling device 5, its device is in the outlet side of water cooling plant 3, described gas controlling device 5 selects the mass-flow gas meter for detecting gas weight, described Fu Ke acyl chloride reaction device also comprises fluid flowmeter 6, and described fluid flowmeter 6 is arranged between the discharge end of material dropping device 1 and the feed end of acylation reaction still 2, described reaction unit also comprises cryogenic system 7 and storage tank 8, the arrival end of described cryogenic system 7 is connected by the port of export of gas exhaustion line with gas controlling device 5, the port of export of described cryogenic system 7 is connected with storage tank 8, and its branch road is also provided with device for absorbing tail gas 4.
Embodiment 2
Produce as example with 2,4-dichloroacetophenone below, embodiment be described in detail:
In acidylate pot, add 305 kilograms of m-dichlorobenzenes, open manhole, trial throw alchlor, after without exception, add up to the aluminum trichloride (anhydrous) of input 375 kilograms, stir, in temperature≤30 DEG C, drop into 180 kilograms of chloroacetic chlorides fast; After feeding intake, whole-process control exhaust flow is no more than 9m
3/ h, in still, held stationary heats up, and still temperature 45 ~ 55 DEG C is this reaction Main Stage, now can produce a large amount of tail gas, does not measure tail gas and generates, then be incubated 1h to 120 DEG C of inspections, and at the end of reaction, tail gas is accumulative generates 46m
3.Reaction terminates, and in ice bath situation, adds frozen water, hydrochloric acid is hydrolyzed at <85 DEG C; Hydrolysis terminates, stratification, and water layer process is discharged, suction distillation still after oil reservoir washing; Thick steaming, reclaim 2,4-dichloroacetophenone, essence steams to obtain foreshot and 2,4-dichloroacetophenone; After crystallisation by cooling, centrifugal, methanol rinse, pulverizing, after the assay was approved, pack and obtain 340 kilograms of finished products.2, the 4-dichloroacetophenones reclaimed and foreshot, centrifugate recycle, and the comprehensive yield of product is throwing 850 kilograms of m-dichlorobenzenes, 1045 kilograms of aluminum trichloride (anhydrous)s, 502 kilograms of chloroacetic chlorides obtain 1 ton of 2,4-dichloroacetophenone finished product.Tail gas absorbs through falling-film absorber and is processed into hydrochloric acid, only detects acetate in minute, illustrate that raw material chloroacetic chloride escapes less in hydrochloric acid.
Embodiment 3
In acidylate pot, add 305 kilograms of m-dichlorobenzenes, open manhole, trial throw alchlor, after without exception, add up to the aluminum trichloride (anhydrous) of input 375 kilograms, stir, whole-process control exhaust flow is no more than 9m
3/ h, is warming up to 40 ~ 45 DEG C, then starts the chloroacetic chloride at the uniform velocity dripping 180 kilograms, and time for adding is 1.5h, hydrogen chloride gas 8.7m
3; After feeding intake, start to heat up stage by stage, 45 ~ 55 DEG C of heating-up times are 4h, hydrogen chloride gas 32.3m
3, 55 ~ 75 DEG C of heating-up times are 0.5h, hydrogen chloride gas 1.3m
3; 75 ~ 120 DEG C of heating-up times are 1h, hydrogen chloride gas 2.3m
3, 120 DEG C of temperature retention time 1h, hydrogen chloride gas adds up 44.6m
3; Reaction terminates, and in ice bath situation, adds frozen water, hydrochloric acid is hydrolyzed at <85 DEG C; Hydrolysis terminates, stratification, and water layer process is discharged, suction distillation still after oil reservoir washing; Thick steaming, reclaim 2,4-dichloroacetophenone, essence steams to obtain foreshot and 2,4-dichloroacetophenone; After crystallisation by cooling, centrifugal, methanol rinse, pulverizing, after the assay was approved, pack and obtain 335 kilograms of finished products.2, the 4-dichloroacetophenones reclaimed and foreshot, centrifugate recycle.The comprehensive yield of product is throwing 870 kilograms of m-dichlorobenzenes, 1069 kilograms of aluminum trichloride (anhydrous)s, 513 kilograms of chloroacetic chlorides obtain 1 ton of 2,4-dichloroacetophenone finished product.Tail gas absorbs through falling-film absorber and is processed into hydrochloric acid, only detects acetate in minute, illustrate that raw material chloroacetic chloride escapes less in hydrochloric acid.
Claims (8)
1. one kind is improved the Fu Ke acyl chloride reaction device of Fu Ke acyl chloride reaction yield, it is characterized in that: comprise material acylating agent Dropping feeder, acylation reaction still, water cooling plant and device for absorbing tail gas, the discharge end of described material acylating agent Dropping feeder is connected with the feed end of acylation reaction still, the material valve for controlling to throw in material inlet is provided with between described material acylating agent Dropping feeder and acylation reaction still, side on described acylation reaction still is also provided with the steam valve for controlling reactor firing rate, the inlet end of described water cooling plant is connected by gas exhaustion line with the gas outlet end of acylation reaction still, the outlet side of described water cooling plant is connected by gas exhaustion line with the arrival end of device for absorbing tail gas, improve in the Fu Ke acyl chloride reaction device of Fu Ke acyl chloride reaction yield the gas controlling device also comprised for monitoring the generation gas flow in Fu Ke acyl chloride reaction, described gas controlling device, its device is on gas exhaustion line.
2. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to claim 1; it is characterized in that: described Fu Ke acyl chloride reaction device also comprises the flow measurement device for detecting acylating agent rate of feeding, described flow measurement device is arranged between the discharge end of material dropping device and the feed end of acylation reaction still.
3. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to claim 1, is characterized in that: described gas controlling device is arranged on water cooling plant inlet end or the outlet side of water cooling plant.
4. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to claim 1, it is characterized in that: described reaction unit also comprises cryogenic system and storage tank, the arrival end of described cryogenic system is connected with the port of export of gas controlling device by gas exhaustion line, the port of export of described cryogenic system is connected with storage tank, described cryogenic system, its branch road is also provided with device for absorbing tail gas.
5. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to claim 2, is characterized in that: described flow measurement device is fluid flowmeter.
6. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to claim 3, is characterized in that: described gas controlling device is arranged on the outlet side of water cooling plant.
7. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to any one of claim 1 or 4, is characterized in that: described device for absorbing tail gas is provided with the falling-film absorber for absorbing hydrogen chloride gas.
8. a kind of Fu Ke acyl chloride reaction device improving Fu Ke acyl chloride reaction yield according to any one of claim 1 or 3 or 4, it is characterized in that: described gas controlling device is selected: for detecting the mass-flow gas meter of gas weight, or for detecting the one in the gas volume flow gauge of gas flow.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210495265.4A CN102974280B (en) | 2012-11-28 | 2012-11-28 | Method and equipment for improving F-C acyl chloride reaction yield |
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| CN201210495265.4A CN102974280B (en) | 2012-11-28 | 2012-11-28 | Method and equipment for improving F-C acyl chloride reaction yield |
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| CN102974280B true CN102974280B (en) | 2015-04-15 |
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| CN112500277A (en) * | 2021-01-04 | 2021-03-16 | 江西永通科技股份有限公司 | Synthetic method of 2, 4-dichloroacetophenone |
| CN112500274A (en) * | 2021-01-04 | 2021-03-16 | 江西永通科技股份有限公司 | Synthetic method of 2, 2, 2', 4' -tetrachloroacetophenone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359892A (en) * | 2001-12-13 | 2002-07-24 | 张建国 | Process for preparing 1-hydroxycyclohexyl phenylketone |
| US6548722B1 (en) * | 2000-10-10 | 2003-04-15 | Council Of Scientific And Industrial Research | Process for the preparation of substituted aromatic compound employing friedel-crafts reaction using a reusable basic anionic clay catalyst |
| CN102167662A (en) * | 2011-03-23 | 2011-08-31 | 南通泰禾化工有限公司 | Low-pressure synthesis method of benzophenone by composite catalyst |
| CN203030259U (en) * | 2012-11-28 | 2013-07-03 | 周烜 | Friedel-crafts acyl chloride reaction device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07223991A (en) * | 1993-12-17 | 1995-08-22 | Takeda Chem Ind Ltd | Production process for acyl-substituted aromatic compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6548722B1 (en) * | 2000-10-10 | 2003-04-15 | Council Of Scientific And Industrial Research | Process for the preparation of substituted aromatic compound employing friedel-crafts reaction using a reusable basic anionic clay catalyst |
| CN1359892A (en) * | 2001-12-13 | 2002-07-24 | 张建国 | Process for preparing 1-hydroxycyclohexyl phenylketone |
| CN102167662A (en) * | 2011-03-23 | 2011-08-31 | 南通泰禾化工有限公司 | Low-pressure synthesis method of benzophenone by composite catalyst |
| CN203030259U (en) * | 2012-11-28 | 2013-07-03 | 周烜 | Friedel-crafts acyl chloride reaction device |
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