CN102701904A - Method for comprehensively utilizing hydrogen fluoride in exhausted gas generated in fluoridation - Google Patents
Method for comprehensively utilizing hydrogen fluoride in exhausted gas generated in fluoridation Download PDFInfo
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- CN102701904A CN102701904A CN2012101871208A CN201210187120A CN102701904A CN 102701904 A CN102701904 A CN 102701904A CN 2012101871208 A CN2012101871208 A CN 2012101871208A CN 201210187120 A CN201210187120 A CN 201210187120A CN 102701904 A CN102701904 A CN 102701904A
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Abstract
The invention discloses a method for comprehensively utilizing hydrogen fluoride in exhausted gas generated in fluoridation. According to the method, a tower-type or kettle-type reaction absorption treatment step is added in benzyl trichloride or benzyl bromide liquid-phase fluoridation, and the content of hydrogen fluoride in the exhausted gas generated in the fluoridation is reduced to less than 100ppm; the method is environment-friendly, high in absorption and utilization rate of hydrogen fluoride and reaction yield, and easy to operate; and an absorption and reaction solution can immediately enter the fluoridation, so the feasibility of industrialization and engineering of the method is improved.
Description
Technical field
The invention belongs to the Organic Chemical Engineering applied technical field; Specifically be hydrofluoric method of comprehensive utilization during a kind of fluoridation speeds to exit, particularly a kind of benzenyl trichloride class or trisbromomethyl benzene class prepare the hydrofluoric method of comprehensive utilization in the trifluoromethyl benzene-like compounds process.
Background technology
The trifluoromethyl benzene-like compounds is one type of important fluorine-containing fine chemicals, and it is widely used in the building-up reactions of medicine, agricultural chemicals, dyestuff, and it also can be used to the solvent of electronics and some specialty products.Along with the continuous expansion of its purposes, manufacturer is more and more.But wherein fluoridation all adopts liquid-phase fluorination process; It is different that its temperature of reaction is looked different material, and general temperature of reaction is at 50-180 ℃, and reaction pressure is at 1.0-8.0Mpa; Liquid phase reaction needs the hydrogen fluoride of larger proportion to participate in reaction; This just causes the hydrofluoric content of when discharging hydrogenchloride by-product, taking out of very high, generally all more than 10%, for the raw material that has electron-withdrawing group on the phenyl ring even can reach more than 30%.The direct water of generally will above-mentioned speeding exitting absorbed and prepared hydrochloric acid present stage, and this not only causes hydrofluoric a large amount of waste, and the use of this fluorine-containing hydrochloric acid also will cause great environmental pollution.How to utilize and handle fluoridation to speed to exit be a key and the difficult problem that fluorine-containing fine chemicals is produced.
The researchist of institute of Juhua Group Co. finds: from principle of absorption, found a kind ofly to remove the hydrofluoric wet method defluorinating agent of hydrogen chloride gas by 2 kinds of compounds being used for of forming, confirmed wet method defluorination process flow process.This defluorination process defluorinate efficient is high, and fluorine content is reduced to below the 15mg/L in the hydrochloric acid for preparing after the defluorinate.The fluorinated product strainability that obtains is good, and utility value is big, realized hydrofluoric resource utilization in the hydrogen chloride gas, thereby defluorination technology has better economic property and practicality.
Have recently with the reaction of the continuous fluorination of fat hydrocarbon to be basis, carry out compression rectification that fluoridation speeds to exit purify hydrogenchloride and hydrogen fluoride, but this to relate to a topping-up pump and a cover band pressure rectifier unit be the complex appts of major equipment.And the industrial scale of trifluoromethyl benzene-type products is less, does not have the production equipment of serialization, so aforesaid method is only applicable in the production reaction process of large-scale fluorine Lyons class.
In sum, prior art and synthetic route are in the process of preparation trifluoromethyl benzene-like compounds, and following problems of ubiquity all: 1, continuous production technology adopts few; 2, hydrogen fluoride content was high during fluoridation speeded to exit, and caused hydrofluoric utilization ratio low; 3, the treatment technology of the hydrogen chloride gas of fluorinated hydrogen is low, causes the influence of fluorine-containing hydrochloric acid to environment.
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Summary of the invention
In order to solve the problems of the technologies described above, the invention provides simple, the device simple of a kind of technology, in fluorination reaction process, can effectively improve hydrofluoric utilization ratio, reduce a kind of Technology of the hydrogen fluoride content in the emission gases.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit, the reaction that in three benzyl chlorides or three bromobenzyl liquid phase fluorination reactions, increases tower or still formula absorbs treatment step, and the hydrogen fluoride content during fluoridation is speeded to exit is reduced to below the 100ppm.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit; A still formula of series connection or tower gas absorption reaction unit behind the reaction unit of three benzyl chlorides or three bromobenzyl liquid phase fluorination reactions; Preferred tower gas absorption reaction unit, said reaction absorb treatment step to carry out at said gas absorption reaction unit.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit, said liquid phase fluorination reaction adopt intermittently fluoridation or continuous fluorination reaction, and preferred continuous fluorination reacts.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit absorbs adding absorption reaction agent and fluorination catalyst in the treatment step, preferably identical with front fluoridation material, three promptly identical benzyl chlorides or three bromobenzyls in said reaction.
The temperature of reaction that a kind of fluoridation of the present invention hydrofluoric method of comprehensive utilization in the venting of speeding, said reaction absorb treatment step is between the room temperature to 100 ℃, preferred 40-80 ℃, and more preferably 50-70 ℃.
Tower reactor is in absorbing hydrofluoric reaction process in the invention, but reaction mass continuously feeding or intermittent feeding, and absorption reaction liquid is discharging or intermittent take-off continuously also, preferred continuously feeding and continuous discharging.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit, said tower reaction absorb the blistering reaction form of the full tower of employing in the treatment step or the reaction formation of recycle pump spray.
A kind of fluoridation of the present invention hydrofluoric method of comprehensive utilization in the venting of speeding is provided with gas distributor in said still formula or tower gas absorption reaction unit.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit; Said still formula or tower gas absorption reaction unit adopt carbon steel material or stainless steel or impregnating material such as lining PO, PE or PTF; Preferred stainless steel and lining impregnating material; Filler in the gas absorption reaction unit adopts the structured packing or the dumped packing of stainless steel, carbon steel or plastics, preferred structured packing.
Hydrofluoric weight percentage was 5-20% during hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit, fluoridation speeded to exit.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit; Said reaction absorbs treatment step with single tower or the operation of single still or adopt two towers or multitower, two stills or many stills serial operation, general visual response situation to adopt two towers to connect or three tower cascade connectedly just can reach processing requirements.
If select the material identical with fluoridation among the present invention in the tower reactor for use, then absorption reaction liquid can get in front intermittence or the successive fluoridation device at regular time and quantity.
Hydrofluoric method of comprehensive utilization during a kind of fluoridation of the present invention speeds to exit, environmentally friendly, hydrofluoric absorption rate is high; Reaction yield is high; Simple to operate, absorption reaction liquid can get in the fluoridation immediately, has increased the feasibility of industriallization of the present invention and through engineering approaches.
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Embodiment
Come the present invention is further specified with some embodiment below, but the present invention is in no way limited to these embodiment.
Embodiment 1
At diameter 4cm, highly be in the carbon steel pipes of 100cm, gas is installed is fed mouthful, liquid sampling mouth and temperature-measuring port, the copper pipe of heating usefulness is twined in the outside, and gas mist eliminator and condensing surface are equipped with in top, the Stainless Steel Helices of packing in the reaction tubes then.With the experimental installation oven dry, toward wherein adding to chlorine three benzyl chloride 700ml (liquid level is 50cm), controlled temperature is in 50 ℃ after installing.Open gas and feed mouth, wherein feed pure hydrogen fluoride gas when the feeding amount reaches 50g so that the speed of 20g/h is past, the content that sampling analysis obtains chlorine dichloro trifluoro benzyl is 35%, and through calculating, the hydrogen fluoride utilization ratio of this reaction process is 60%.
Embodiment 2
Operation is with embodiment 1;, feed after 3 hours toward wherein feeding the hydrogen chloride gas that hydrogen fluoride content is 10% (w/w) with 150g/h speed, sampling analysis must be 28% to chlorine dichloro trifluoro benzyl content; Through calculating, the hydrofluoric utilization ratio of this reaction process is 50.24%.
Embodiment 3
With embodiment 2, change filler into the PE filler, sampling analysis must be 15% to chlorine dichloro one fluorine benzyl content, through calculating, the hydrofluoric utilization ratio of this reaction process is 28.98%.
Embodiment 4
With embodiment 2, substitute chlorine three benzyl chlorides with trichlorotoluene zotrichloride.It is 32% that sampling analysis gets dichloro one fluorine benzyl content, and through calculating, the hydrofluoric utilization ratio of this reaction process is 73.93%.
Embodiment 5
In producing 10000 tons the tail gas of p-chloro benzo trifluoride-99 device per year, diameter 80cm being installed, highly is the spray absorption reaction tower of 12m, and this tower is that two towers are connected.Interior dress stainless steel or PE filler, 75 ℃ of the temperature of absorption reaction.Absorption reaction liquid adopts chlorine three benzyl chlorides, and employing outer circulation spray absorbs, and through detecting, fluorinion concentration is 95ppm in the hydrochloric acid of absorption preparation, and hydrofluoric absorption rate is 99.3%.
The present invention only lifts the foregoing description; All documents that the present invention mentions all in this application as a reference; Just quoted that kind as a reference separately, should be understood that in addition after having read above-mentioned teachings of the present invention as each piece document; Those skilled in the art can do various changes or modification to the present invention, and these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. hydrofluoric method of comprehensive utilization during a fluoridation speeds to exit; It is characterized in that the reaction that in three benzyl chlorides or three bromobenzyl liquid phase fluorination reactions, increases tower or still formula absorbs treatment step, the hydrogen fluoride content during fluoridation is speeded to exit is reduced to below the 100ppm.
2. hydrofluoric method of comprehensive utilization during a kind of fluoridation as claimed in claim 1 speeds to exit; It is characterized in that a still formula of series connection or tower gas absorption reaction unit behind the reaction unit of three benzyl chlorides or three bromobenzyl liquid phase fluorination reactions; Preferred tower gas absorption reaction unit, said reaction absorb treatment step to carry out at said gas absorption reaction unit.
3. hydrofluoric method of comprehensive utilization during a kind of fluoridation as claimed in claim 1 speeds to exit is characterized in that said liquid phase fluorination reaction adopts intermittently fluoridation or continuous fluorination reaction, and preferred continuous fluorination reacts.
4. hydrofluoric method of comprehensive utilization during a kind of fluoridation as claimed in claim 1 speeds to exit is characterized in that absorbing adding absorption reaction agent and fluorination catalyst in the treatment step, preferred three benzyl chlorides of said absorption reaction agent or three bromobenzyls in said reaction.
5. a kind of fluoridation as claimed in claim 1 hydrofluoric method of comprehensive utilization in the venting of speeding is characterized in that temperature of reaction that said reaction absorbs treatment step is between the room temperature to 100 ℃, preferred 40-80 ℃, and more preferably 50-70 ℃.
6. hydrofluoric method of comprehensive utilization during a kind of fluoridation as claimed in claim 1 speeds to exit is characterized in that said tower reaction absorbs the blistering reaction form of the full tower of employing in the treatment step or the reaction formation of recycle pump spray.
7. a kind of fluoridation as claimed in claim 2 hydrofluoric method of comprehensive utilization in the venting of speeding is characterized in that in said still formula or tower gas absorption reaction unit, gas distributor being set.
8. hydrofluoric method of comprehensive utilization during a kind of fluoridation as claimed in claim 2 speeds to exit; It is characterized in that said still formula or tower gas absorption reaction unit adopt carbon steel material or stainless steel or impregnating material such as lining PO, PE or PTF; Preferred stainless steel and lining impregnating material; Filler in the gas absorption reaction unit adopts the structured packing or the dumped packing of stainless steel, carbon steel or plastics, preferred structured packing.
9. a kind of fluoridation as claimed in claim 1 speed the venting in hydrofluoric method of comprehensive utilization, it is characterized in that fluoridation speed the venting in hydrofluoric weight percentage be 5-20%.
10. hydrofluoric method of comprehensive utilization during a kind of fluoridation as claimed in claim 1 speeds to exit is characterized in that said reaction absorbs treatment step and perhaps adopts two towers or multitower, two stills or many stills serial operation with single tower or the operation of single still.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101871208A CN102701904A (en) | 2012-06-08 | 2012-06-08 | Method for comprehensively utilizing hydrogen fluoride in exhausted gas generated in fluoridation |
| CN201510029545.XA CN104628515B (en) | 2012-06-08 | 2012-06-08 | Hydrofluoric method of comprehensive utilization in a kind of fluoridation periodic off-gases |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101871208A CN102701904A (en) | 2012-06-08 | 2012-06-08 | Method for comprehensively utilizing hydrogen fluoride in exhausted gas generated in fluoridation |
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| CN201510029545.XA Division CN104628515B (en) | 2012-06-08 | 2012-06-08 | Hydrofluoric method of comprehensive utilization in a kind of fluoridation periodic off-gases |
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| CN2012101871208A Pending CN102701904A (en) | 2012-06-08 | 2012-06-08 | Method for comprehensively utilizing hydrogen fluoride in exhausted gas generated in fluoridation |
| CN201510029545.XA Active CN104628515B (en) | 2012-06-08 | 2012-06-08 | Hydrofluoric method of comprehensive utilization in a kind of fluoridation periodic off-gases |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911009A (en) * | 2012-10-29 | 2013-02-06 | 浙江巍华化工有限公司 | Industrialization method for synthetizing (trichloromethyl) benzeneby products by continuous photo-initiation chlorination |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4976802A (en) * | 1972-12-06 | 1974-07-24 | ||
| US3859372A (en) * | 1969-12-03 | 1975-01-07 | Hooker Chemicals Plastics Corp | Process for the preparation of organic fluorine compounds |
| JPH0976802A (en) * | 1995-09-13 | 1997-03-25 | Aisin Seiki Co Ltd | Seat back turning device |
| CN1826304A (en) * | 2003-05-23 | 2006-08-30 | 霍尼韦尔国际公司 | Method of making hydrofluorocarbons |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100230B (en) * | 1987-02-16 | 1988-11-23 | 中国科学院上海有机化学研究所 | Fluoration catalyst and its applications |
-
2012
- 2012-06-08 CN CN2012101871208A patent/CN102701904A/en active Pending
- 2012-06-08 CN CN201510029545.XA patent/CN104628515B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859372A (en) * | 1969-12-03 | 1975-01-07 | Hooker Chemicals Plastics Corp | Process for the preparation of organic fluorine compounds |
| JPS4976802A (en) * | 1972-12-06 | 1974-07-24 | ||
| JPH0976802A (en) * | 1995-09-13 | 1997-03-25 | Aisin Seiki Co Ltd | Seat back turning device |
| CN1826304A (en) * | 2003-05-23 | 2006-08-30 | 霍尼韦尔国际公司 | Method of making hydrofluorocarbons |
Non-Patent Citations (1)
| Title |
|---|
| 马英高: "对氯三氟甲苯合成工艺的进展", 《辽宁化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911009A (en) * | 2012-10-29 | 2013-02-06 | 浙江巍华化工有限公司 | Industrialization method for synthetizing (trichloromethyl) benzeneby products by continuous photo-initiation chlorination |
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| CN104628515A (en) | 2015-05-20 |
| CN104628515B (en) | 2016-04-06 |
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Application publication date: 20121003 |