CN102093197A - Method for preparing aromatic dimethyl chloride - Google Patents
Method for preparing aromatic dimethyl chloride Download PDFInfo
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- CN102093197A CN102093197A CN2009102506924A CN200910250692A CN102093197A CN 102093197 A CN102093197 A CN 102093197A CN 2009102506924 A CN2009102506924 A CN 2009102506924A CN 200910250692 A CN200910250692 A CN 200910250692A CN 102093197 A CN102093197 A CN 102093197A
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Abstract
The invention discloses a method for preparing aromatic dimethyl chloride, which relates to the technical field of preparation methods of aromatic chloride compounds. The method comprises the following steps of: reacting aromatic dioctyl phthalate with a chlorinating agent to generate the aromatic dimethyl chloride; evaporating the chlorinating agent; exhausting tail gas; recycling the tail gas; and evaporating and recycling the aromatic dimethyl chloride. The tail gas is recycled by the following specific steps of: introducing the tail gas into a primary cooling tower for cooling, wherein the temperature of the primary cooling tower is between 0 DEG C and 10 DEG C; introducing the primarily cooled tail gas into a first cooling tower for collecting liquid, wherein the temperature of the first cooling tower is between 25 DEG C below zero and 15 DEG C below zero; introducing the liquid into a rectification tower for rectifying, wherein the temperature of the rectification tower is between 10 DEG C below zero and 50 DEG C below zero; introducing the tail gas passing through the first cooling tower into a falling film absorber for absorbing; and introducing the tail gas passing through the falling film absorber into alkali liquor for absorbing. By using the method, high-purity byproducts, namely hydrochloric acid and liquid sulfur dioxide are obtained while a main product, namely the aromatic dimethyl chloride, is prepared.
Description
Technical field
The present invention relates to preparation method's technical field of aromatic series chloride compounds, particularly a kind of preparation method of aromatic series dimethyl chloride.
Background technology
The aromatic series dimethyl chloride is mainly used in the production of high-tech products such as polymeric amide, polyester, polyarylester, polyaramide, liquid crystal polymer, meta-aramid and p-aramid fiber, and its increase of production is rapid.Chlorination process is the common method of preparation aromatic series dimethyl chloride.Chlorination process is to adopt chlorizating agent and the reaction of aromatic series dioctyl phthalate, at 80 ℃ of backflow 10-12 hours, revaporization goes out sulfur oxychloride, can produce a large amount of sulfurous gas and hydrogen chloride gas simultaneously, and chlorizating agent commonly used has chlorine, phosphorus trichloride, phosphorus pentachloride and sulfur oxychloride.Usually the method for carrying out the alkali lye absorption after the employing falling film absorption is handled this gas, but the purity of by product-hydrochloric acid that can obtain like this and sulfurous gas is low.
Summary of the invention
The preparation method who the purpose of this invention is to provide the high aromatic series chloride compounds of a kind of by product-hydrochloric acid that obtains and sulfurous gas purity.
The preparation method of aromatic series dimethyl chloride compound provided by the present invention comprises that aromatic series dioctyl phthalate and chlorination reaction generate the step of aromatic series dimethyl chloride; Evaporate the step of described chlorizating agent; Discharge the step of tail gas; The step that described tail gas recycle is handled; The step of described aromatic series dimethyl chloride is reclaimed in evaporation; Wherein, the step that described tail gas recycle is handled comprises that described tail gas enters refrigerative step in the first grade cooling tower, and the described temperature of grade cooling tower just is 0～10 ℃; Enter the step of collecting liquid in first cooling tower through elementary refrigerative tail gas, the temperature of described first cooling tower is-25 ℃～-15 ℃; Described liquid enters purified step in the rectifying tower, and described rectifying tower temperature is-10 ℃～-50 ℃; Tail gas through described first cooling tower enters the step that falling-film absorber absorbs; Tail gas through falling-film absorber enters the step that alkali lye absorbs.
The preparation method of aromatic series dimethyl chloride of the present invention, wherein, described rectifying tower column bottom temperature is-10～-15 ℃, and temperature is-20～-25 ℃ in the tower, and tower top temperature is-35～-40 ℃.
Described chlorizating agent be in chlorine, phosphorus trichloride, phosphorus pentachloride and the sulfur oxychloride any or appoint several.
Method for preparing obtains aromatic series dimethyl chloride and by-product hydrochloric acid and sulfur dioxide liquid.Material, sulfurous gas and the hydrogenchloride etc. that contain high boiling point such as unreacted gaseous state chlorizating agent in the tail gas that aromatic series dioctyl phthalate and chlorination reaction produce.High boiling point materials such as unreacted gaseous state chlorizating agent form liquid by elementary cooling and are removed, sulfurous gas in the tail gas enters and becomes sulfur dioxide liquid in the cooling tower and be separated, sulfur dioxide liquid enters the highly purified sulfur dioxide liquid of the refining acquisition of fractionate, and the hydrogenchloride in the tail gas is produced hydrochloric acid by falling-film absorber.
The preparation method of aromatic series dimethyl chloride of the present invention is introduced into the step of collecting liquid in second cooling tower before comprising that also the tail gas through described first cooling tower enters falling-film absorber and absorbs, and the temperature of described second cooling tower is-25 ℃～-15 ℃; Tail gas through described second cooling tower enters the step that described falling-film absorber absorbs.
Enter second cooling tower again through the tail gas of first cooling tower and carry out the secondary cooling, can improve the organic efficiency of sulfurous gas.
The preparation method of aromatic series dimethyl chloride of the present invention, wherein, described aromatic series dioctyl phthalate is meant that phenyl ring common in this area replaces the dioctyl phthalate of class, comprises m-phthalic acid, ditolyl dioctyl phthalate, terephthalic acid and phthalic acid etc.
The preparation method of aromatic series dimethyl chloride compound of the present invention compared with prior art has following advantage: obtain by-product hydrochloric acid and sulfur dioxide liquid, the purity height of hydrochloric acid and sulfur dioxide liquid when preparing principal product aromatic series dimethyl chloride.
Description of drawings
Fig. 1 is the process flow sheet of vent gas treatment among the preparation method of aromatic series dimethyl chloride.
Embodiment
Following embodiment is an example with preparation p-phthaloyl chloride and m-phthaloyl chloride, the preparation method and the effect of sets forth in detail aromatic series dimethyl chloride of the present invention.
Embodiment 1, preparation p-phthaloyl chloride
In retort, add the 100kg terephthalic acid, the 250L sulfur oxychloride, stir, beginning progressively is warmed up to 60 ℃, opens the reflux condensation mode water on the reactor, open reverse flow valve, control tail gas amount is 80～100L/h, treats that temperature is raised to 75 ℃, after tail gas does not have substantially, be considered as reaction end, 12 hours reaction times.After reaction finishes, reclaim sulfur oxychloride at 75～80 ℃.Open vacuum system and tail gas absorption system, vacuum tightness is behind-0.095MPa, and temperature in the kettle is collected p-phthaloyl chlorides at 170～180 ℃.
The technical process of vent gas treatment in the first grade cooling tower of tail gas importing, is opened falling film absorption system and alkali lye absorption unit as shown in Figure 1.Just the grade cooling tower temperature is controlled at 0～5 ℃, adopts the reverse type of cooling that gas is lowered the temperature, and isolates high boiling point materials such as unreacted gaseous state sulfur oxychloride; Residual exhaust enters first cooling tower, and controlling the first cooling tower temperature is-20 ℃～-15 ℃, and recovering liquid sulfurous gas, liquid enter in the rectifying tower; Enter second cooling tower through the residual exhaust behind first cooling tower, the temperature of second cooling tower is-20 ℃～-15 ℃, recovering liquid sulfurous gas, and liquid enters rectifying tower; Sulfur dioxide liquid is refining in rectifying tower, removes the hydrogenchloride in the sulfurous gas, and the rectifying tower temperature is-10 ℃～-50 ℃, wherein column bottom temperature is-10～-15 ℃, temperature is-20～-25 ℃ in the tower, and tower top temperature is-35～-40 ℃, and the sulfur dioxide liquid after making with extra care goes out from tower bottom flow; Feed in the falling-film absorber through the residual exhaust behind second cooling tower, circularly absorbing hydrogen chloride is to hydrochloric acid; The tail gas of process falling film absorption feeds in 10% aqueous sodium hydroxide solution and absorbs at last.
Detect the purity of the sulfur dioxide liquid after making with extra care and the concentration of hydrochloric acid.
After testing, the purity of the sulfur dioxide liquid of refining back acquisition is 99.6%; The concentration of the hydrochloric acid that obtains behind the circularly absorbing hydrogen chloride is 35%.
Embodiment 2, preparation m-phthaloyl chloride
In retort, add the 100kg m-phthalic acid, the 250L sulfur oxychloride, stir, beginning progressively is warmed up to 60 ℃, opens the reflux condensation mode water on the reactor, open reverse flow valve, control tail gas amount is 80～100L/h, treats that temperature is raised to 75 ℃, after tail gas does not have substantially, be considered as reaction end, 12 hours reaction times.After reaction finishes, reclaim sulfur oxychloride at 75～80 ℃.Open vacuum system and tail gas absorption system, vacuum tightness is behind-0.095MPa, and temperature in the kettle is collected m-phthaloyl chlorides at 170～180 ℃.
The technical process of vent gas treatment in the first grade cooling tower of tail gas importing, is opened falling film absorption system and alkali lye absorption unit as shown in Figure 1.Just the grade cooling tower temperature is controlled at 6～10 ℃, adopts the reverse type of cooling that gas is lowered the temperature, and isolates high boiling point materials such as unreacted gaseous state sulfur oxychloride; Residual exhaust enters first cooling tower, and controlling the first cooling tower temperature is-25 ℃～-20 ℃, and recovering liquid sulfurous gas, liquid enter in the rectifying tower; Enter second cooling tower through the residual exhaust behind first cooling tower, the temperature of second cooling tower is-25 ℃～-20 ℃, recovering liquid sulfurous gas, and liquid enters rectifying tower; Sulfur dioxide liquid is refining in rectifying tower, removes the hydrogenchloride in the sulfurous gas, and the rectifying tower temperature is-10 ℃～-50 ℃, wherein column bottom temperature is-10～-15 ℃, temperature is-20～-25 ℃ in the tower, and tower top temperature is-35～-40 ℃, and the sulfur dioxide liquid after making with extra care goes out from tower bottom flow; Feed in the falling-film absorber through the residual exhaust behind second cooling tower, circularly absorbing hydrogen chloride is to hydrochloric acid; The tail gas of process falling film absorption feeds in 10% aqueous sodium hydroxide solution and absorbs at last.
Detect the purity of the sulfur dioxide liquid after making with extra care and the concentration of hydrochloric acid.
After testing, the purity of the sulfur dioxide liquid of refining back acquisition is 99.5%; The concentration of the hydrochloric acid that obtains behind the circularly absorbing hydrogen chloride is 30%.
Above-described embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (4)
1. the preparation method of an aromatic series dimethyl chloride comprises that aromatic series dioctyl phthalate and chlorination reaction generate the step of aromatic series dimethyl chloride; Evaporate the step of described chlorizating agent; Discharge the step of tail gas; The step that described tail gas recycle is handled; The step of described aromatic series dimethyl chloride is reclaimed in evaporation; It is characterized in that: the step that described tail gas recycle is handled comprises that described tail gas enters refrigerative step in the first grade cooling tower, and the described temperature of grade cooling tower just is 0～10 ℃; Enter the step of collecting liquid in first cooling tower through elementary refrigerative tail gas, the temperature of described first cooling tower is-25 ℃～-15 ℃; Described liquid enters purified step in the rectifying tower, and described rectifying tower temperature is-10 ℃～-50 ℃; Tail gas through described first cooling tower enters the step that falling-film absorber absorbs; Tail gas through falling-film absorber enters the step that alkali lye absorbs.
2. preparation method according to claim 1 is characterized in that: described rectifying tower column bottom temperature is-10～-15 ℃, and temperature is-20～-25 ℃ in the tower, and tower top temperature is-35～-40 ℃.
3. preparation method according to claim 1 is characterized in that: described chlorizating agent be in chlorine, phosphorus trichloride, phosphorus pentachloride and the sulfur oxychloride any or appoint several.
4. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: before comprising that also tail gas through described first cooling tower enters falling-film absorber and absorbs, be introduced into the step of collecting liquid in second cooling tower, the temperature of described second cooling tower is-25 ℃～-15 ℃; Tail gas through described second cooling tower enters the step that described falling-film absorber absorbs.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466550A (en) * | 2013-08-28 | 2013-12-25 | 张吉瑞 | Recovery system of D-acid esterification tail gas in amoxicillin production technology |
| CN104138703A (en) * | 2014-08-06 | 2014-11-12 | 山东凯盛新材料有限公司 | Waste gas treatment process and device in isophthaloyl dichloride/paraphthaloyl chloride production |
| CN106431897A (en) * | 2016-09-27 | 2017-02-22 | 宿迁科思化学有限公司 | New compounding technology for 2,4,6-trimethyl phenylacetyl chloride |
| CN109705086A (en) * | 2018-12-26 | 2019-05-03 | 湖南科技大学 | One kind is based on the folding of ring polymers and the frame molecule assembled and preparation method thereof |
| CN112933880A (en) * | 2021-02-04 | 2021-06-11 | 济源市恒通高新材料有限公司 | Sulfur dioxide recovery process and device for terephthaloyl chloride production tail gas |
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| US4539190A (en) * | 1984-09-11 | 1985-09-03 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for the treatment of exhaust gases |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466550A (en) * | 2013-08-28 | 2013-12-25 | 张吉瑞 | Recovery system of D-acid esterification tail gas in amoxicillin production technology |
| CN103466550B (en) * | 2013-08-28 | 2015-07-15 | 张吉瑞 | Recovery system of D-acid esterification tail gas in amoxicillin production technology |
| CN104138703A (en) * | 2014-08-06 | 2014-11-12 | 山东凯盛新材料有限公司 | Waste gas treatment process and device in isophthaloyl dichloride/paraphthaloyl chloride production |
| CN104138703B (en) * | 2014-08-06 | 2016-01-20 | 山东凯盛新材料有限公司 | Between/paraphthaloyl chloride produce in waste gas treatment process and device |
| CN106431897A (en) * | 2016-09-27 | 2017-02-22 | 宿迁科思化学有限公司 | New compounding technology for 2,4,6-trimethyl phenylacetyl chloride |
| CN106431897B (en) * | 2016-09-27 | 2019-06-04 | 宿迁科思化学有限公司 | A kind of new synthesis process of 2,4,6- trimethylbenzene chloroacetic chloride |
| CN109705086A (en) * | 2018-12-26 | 2019-05-03 | 湖南科技大学 | One kind is based on the folding of ring polymers and the frame molecule assembled and preparation method thereof |
| CN109705086B (en) * | 2018-12-26 | 2021-12-03 | 湖南科技大学 | Framework molecule based on cyclopolymer folding and assembling and preparation method thereof |
| CN112933880A (en) * | 2021-02-04 | 2021-06-11 | 济源市恒通高新材料有限公司 | Sulfur dioxide recovery process and device for terephthaloyl chloride production tail gas |
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Owner name: YANTAI TAYHO ADVANCED MATERIALS CO., LTD. Free format text: FORMER OWNER: YANTAI SPANDEX CO., LTD. Effective date: 20120220 |
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Application publication date: 20110615 |