CN100497164C - Multistage rectification process for high-purity thionyl chloride - Google Patents
Multistage rectification process for high-purity thionyl chloride Download PDFInfo
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- CN100497164C CN100497164C CNB2008100011956A CN200810001195A CN100497164C CN 100497164 C CN100497164 C CN 100497164C CN B2008100011956 A CNB2008100011956 A CN B2008100011956A CN 200810001195 A CN200810001195 A CN 200810001195A CN 100497164 C CN100497164 C CN 100497164C
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Abstract
The invention relates to a multistage distillation method for high purity thionyl chloride. A crude product of the thionyl chloride with the purity of about 70 percent can be purified to more than 99.6 percent by adopting the multistage purification method by steps.
Description
Technical field
What the present invention relates to is a kind of multistage rectification process for high-purity thionyl chloride, purifies by the method that adopts multistage substep, and the sulfur oxychloride crude product with about 70% is purified to more than 99.6%.
Background technology
Sulfur oxychloride is dissolved in benzene, chloroform and tetracol phenixin, in water, decompose and generate sulfurous acid and hydrogenchloride, be heated to 140 degree and decompose generation chlorine, sulfurous gas and sulfur monochloride, the chlorine atom substituted hydroxy of sulfur oxychloride and sulfydryl very capable, sometimes also can replace sulfurous gas, oxygen or hydrogen, can generate the corresponding chlorinated thing with organic compound reactions such as phenol that hydroxyl is arranged or alcohol, generate SULPHURYL CHLORIDE with the sulfonic acid reaction, the sharp refined reagent react of dative generates corresponding sulfoxide compound etc.Sulfur oxychloride is very important in organic synthesis, and it is agricultural chemicals, medicine, sensitive materials and superpolymer intermediate synthetic intermediate raw material, and prior art discloses the technical scheme of synthesizing, purifying of some sulfur oxychlorides, comprising:
ZL95110380 discloses a kind of manufacture method of sulfur oxychloride, this method is to utilize the monochloride of sulfurous gas with sulfur subchloride, dichloride with gac as making the sulfur oxychloride crude product with gas-phase reaction in the presence of the catalyzer, again crude product and SULPHUR POWDER are distilled together and make elaboration, concrete reactions steps has the synthetic of disulphur dichloride, synthesizing of sulfur dichloride, the purification of the synthetic and crude product of sulfur oxychloride, but, the described intermittent mode of production of this patent, because polystep reaction wherein is reversible reaction, therefore, in order to realize the complete of forward reaction, the part starting raw material that needs volume, the great difficulty that has caused the reaction back to be reclaimed, simultaneously, the utilization ratio of raw materials of the described technology of this patent only can improve more than 50 percent, and yield also improves 50 percent than prior art.
US2431823 discloses and has utilized disulphur dichloride (S
2Cl
2) and chlorine reaction, the sulfur dichloride (SCl of generation
2) and excessive chlorine and chlorine gas-phase reaction under activated carbon catalysis of sulfurous gas and importing, obtain sulfur oxychloride through distillation; The document also discloses that will reaction after the being mainly sulfur monochloride mixture that comprises sulphur after over cure bed and the distillation adds preheater A after through the chlorinator chlorination, begin new reaction.
US2,779,663 disclose acquisition SOCl
2Method, comprise the degassing (sulfurous gas and chlorine), condensation, mention S in the background technology
2Cl
2, SO
2And Cl
2Reaction generates SOCl
2, and the sulfur dichloride reaction that product will be wherein in vulcanizing apparatus is sulfur monochloride, turn back to the reactor of beginning; The reactor that sulfurous gas that reclaims and chlorine turn back to beginning.
But it all is single-stage rectifying that sulfur oxychloride that above method relates to is purified, and is difficult to obtain the high-purity thionyl chloride more than 99.6%.The present invention adopts the method for multistage substep to purify, and the sulfur oxychloride crude product with about 70% can be purified to (all sulfur oxychloride purity all are meant mass percent in the literary composition) more than 99.6%.
Summary of the invention
The object of the present invention is to provide a kind of multistage rectification process for high-purity thionyl chloride.
A kind of multistage rectification process for high-purity thionyl chloride provided by the invention, employing be the mode of continuous three grades of rectifying, comprise one-level rectifying, two-stage rectification and three grades of rectifying, corresponding employing one-level rectifying tower, two-stage rectification tower and three grades of rectifying tower; What wherein, one-level rectifying was adopted is " intermittent feeding " mode.
Comprise that in described one-level rectifying 50～75% sulfur oxychlorides are fed the one-level rectifying tower, and tower still temperature is at 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank.
Preferred one-level rectifying parameter comprises: 70% sulfur oxychloride is fed the one-level rectifying tower, and tower still temperature is at 110-130 ℃, and cat head obtains 92% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank.
Adopted the mode of continuously feeding at described secondary and three grades of rectifying with continuous discharging.
Comprise 80～95% sulfur oxychlorides feeding two-stage rectification tower in described two-stage rectification, processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reached 3/4 still liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to one-level rectifying tower still, obtains 98-99%SOCl from cat head
2
Preferably, preferably include 85～95% sulfur oxychlorides feeding two-stage rectification Tata still in described two-stage rectification, processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reaches 3/4 still liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 98-99%SOCl from cat head
2
Be that described three grades of rectifying comprise the SOCl with 98-99%
2Join three grades of rectifying Tata stills, control tower still temperature is at 78-89 ℃, cat head 72-80 ℃, tower top pressure is-0.01～-the decompressing and continuous rectifying condition of 0.06MPa under, can obtain purity 99.6-99.8% SOCl from cat head like this
2
Preferably, described three grades of rectifying comprise the SOC1 with 98-99%
2Join three grades of rectifying Tata stills, control tower still temperature is at 78-89 ℃, cat head 72-75 ℃, tower top pressure is-the decompressing and continuous rectifying condition of 0.03MPa under, can obtain purity 99.6%-99.8% SOCl from cat head like this
2
At least place sulphur at the top of one-level rectifying tower, described intermittent feeding can provide much more more time to make sulfur dichloride in the crude product sulfur oxychloride contact with sulphur to convert the bottom that sulfur monochloride has been back to the one-level rectifying tower again to, preferably, all place sulphur at the top of described one-level rectifying tower, two-stage rectification tower and three grades of rectifying tower.
The rectifier unit operational process of described three grades of rectifying is to carry out under the condition of-0.01MPa fully.
Below be detailed description of the present invention:
For technical scheme of the present invention is described, below as follows to the process prescription of synthesizing chlorinated sulfoxide common in the prior art:
1, synthetic sulfur monochloride (S
2Cl
2), reaction principle: the synthetic sulfur monochloride of the directly logical chlorine of powdery sulphur, reaction process is emitted heat, 70～80 ℃ of temperature of reaction.Equation is:
Cl
2+2S→S
2Cl
2
2, synthetic sulfur dichloride (SCl
2), chemical equation: S
2Cl
2+ Cl
2→ 2SCl
2Reaction principle: the further chlorination of the excessive logical chlorine of sulfur monochloride generates sulfur dichloride, 65～85 ℃ of temperature of reaction;
3, synthesizing chlorinated sulfoxide, building-up reactions is carried out in the sulfur oxychloride reactor, and temperature of reaction is 200～250 ℃.Reaction principle: SCl
2, Cl
2And SO
2Form mixed gas by a certain percentage.This gas mixture reacts on the activated-carbon catalyst surface, generates the crude product sulfur oxychloride.In the present invention, SOCl
2Building-up reactions adopt no fixed carbon compositing catalyst.This step equation is:
Then with gasiform crude product sulfur oxychloride through condenser, and the de-gassing vessel degassing is purified and is removed big portion and be dissolved in wherein Cl
2And SO
2, promptly obtain liquid crude product SOCl
2
4, sulfur oxychloride rectifying, liquid crude product SOCl
2In contain unreacted SCl
2, S
2Cl
2And be partly dissolved therein Cl
2And SO
2, rectifying is to utilize the different principle of each component relative volatility in the mixture, reaches the purpose of separating the purification sulfur oxychloride.After rectifying finishes, with bottom product S
2Cl
2Make synthetic SCl
2Raw material use, thereby finish circulation.
The present invention has improved feeding manner, in the crude product sulfur oxychloride, add excessive sulphur, with the crude product sulfur oxychloride is starting point, utilize the resistates in the crude product sulfur oxychloride, described resistates comprises sulfur monochloride, sulfur dichloride, a spot of chlorine and sulfurous gas, and reaction of Salmon-Saxl, generates the mixing high boiling material that is mainly the sulfur monochloride product, this is because in order to be separated completely, must be with low-boiling-point substance SCl wherein
2(59 ℃ of boiling points) changes into high boiling material S
2Cl
2(137 ℃ of boiling points), reaction equation is
S+SCl
2→S
2Cl
2；
Then with the S that generates
2Cl
2Loop back in the sulfur oxychloride synthesis reactor, cooperate chlorine, sulfurous gas and from sulfur oxychloride the condenser after synthetic and the gaseous product of crude product purification process, synthesizing chlorinated sulfoxide through condensation, the degassing, forms a totally-enclosed working cycle.
Then, adopt the method for multistage substep to purify again, the sulfur oxychloride crude product can be purified to more than 99.6%.
Though having provided instruction, prior art claims, the simple rectifying tower that increases, promptly carry out the purity that multistage rectification can improve sulfur oxychloride, even, claim that the purity that provides has surpassed purity of the present invention, still, these documents openly can not realized the concrete parameter of described purity, therefore, their described purity only is a kind of expectation or conjecture.
Researchist of the present invention finds that described sulfur oxychloride activity is very strong, meets water and can decompose easily, if do not adopt isolating step by step mode, because the content of the sulfur monochloride in the crude product sulfur oxychloride is higher, the azeotrope of its formation is very high to the manufacturing requirement of rectifying tower, therefore, in multistage rectification of the present invention, main purpose is the same, that is, and and the rectifying sulfur oxychloride, but the stressing of each grade distinguished to some extent.
Particularly, in the multistage rectification of the present invention, what one-level rectifying was adopted is " intermittent feeding ", be discontinuous feeding intake, with the still is unit, advance rectifying behind the full still material, treat behind the evaporate to dryness to be that sulfur monochloride enters the sulfur monochloride storage tank at the bottom of the still, and then charging rectifying, since the top of the rectifying tower that in the present invention continuous three grades of rectifying are used at least one or all be placed with sulphur, the more times that intermittent feeding can provide makes the sulfur dichloride in the crude product sulfur oxychloride contact the sulfur monochloride merging that converts at the bottom of sulfur monochloride has been back to the bottom of one-level rectifying tower again and had remained in tower originally with sulphur; Therefore, one-level rectifying mainly is existed and the sulfur monochloride that be transformed of separation as much as possible.
Two-stage rectification has adopted the mode of continuously feeding and continuous discharging, i.e. charging is uninterrupted, goes out the mode of product continuously.The researchist finds, adopts the mode of continuously feeding and continuous discharging in the two-stage rectification tower, can increase the stability of the processing parameter of rectifying tower.
Equally, three grades of rectifying tower also are the modes that has adopted continuously feeding and continuous discharging.
The specific implementation of multistage rectification process of the present invention is as follows:
1, one-level rectifying
50～75% sulfur oxychlorides are fed one-level rectifying Tata still, and tower still temperature is at 110-130 ℃, and cat head obtains the sulfur oxychloride of 80-95%, the high boiling material S of tower still
2Cl
2Be discharged to storage tank; Preferably 70% sulfur oxychloride is fed one-level rectifying Tata still, tower still temperature is at 110-130 ℃, and cat head obtains 92% sulfur oxychloride, below left S
2Cl
2Be discharged to storage tank.
2, two-stage rectification
The 80-95% sulfur oxychloride is fed the two-stage rectification tower, and processing parameter is: tower still temperature is controlled at 78-89 ℃, and when the tower still reached 3/4 still liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to one-level rectifying tower still, obtains 98-99%SOCl from cat head
2Preferably, 85～95% sulfur oxychlorides are fed the two-stage rectification tower, and processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reaches 3/4 still liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 98%-99%SOCl from cat head
2
3, three grades of rectifying
With 98-99% SOCl
2By being metered into three grades of rectifying Tata stills, control tower still temperature is at 78-89 ℃, cat head 72-80 ℃, tower top pressure is-0.01～-the decompressing and continuous rectifying condition of 0.06MPa under, can obtain purity 99.6-99.8% SOCl from cat head like this
2, preferred, with 98-99% SOCl
2Join three grades of rectifying tower stills, control tower still temperature is at 78-89 ℃, cat head 72-75 ℃, tower top pressure is-the decompressing and continuous rectifying condition of 0.03MPa under, can obtain purity from cat head like this is 99.6%-99.8% SOCl
2
At least placing sulphur at the top of one-level rectifying tower, described intermittent feeding can provide much more more time to make sulfur dichloride in the crude product sulfur oxychloride contact with sulphur to convert the bottom that sulfur monochloride has been back to the one-level rectifying tower again to, preferably, sulphur is all placed at top at described three grades of rectifying tower, to improve the purity of sulfur oxychloride.
The rectifier unit operational process of more preferably described continuous three grades of rectifying is to carry out under the condition of-0.01MPa fully.So both reduce steam consumption, also prevented environmental pollution
By the rectificating method of multistage substep of the present invention, can with the crude product synthesis reactor through condensation, outgas, add the sulfur oxychloride crude product of about 70% behind the reaction of Salmon-Saxl, be purified to more than 99.6%.
Description of drawings
Accompanying drawing 1 is a multitower series connection decompressing and continuous distillation process synoptic diagram of the present invention.
Embodiment
Embodiment 1
1, one-level rectifying
50% sulfur oxychloride is fed the one-level rectifying tower, and tower still temperature is at 110 ℃, and cat head obtains 80% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank;
2, two-stage rectification
80% sulfur oxychloride is fed the two-stage rectification tower, and processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reaches 3/4 still liquid level and temperature reaches 89 ℃, the time, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 98% left and right sides SOCl from cat head
2
3, three grades of rectifying
With 98% SOCl
2By being metered into three grades of rectifying tower stills, control tower still temperature is at 78-89 ℃, cat head 72-75 ℃, tower top pressure is-the decompressing and continuous rectifying condition of 0.01MPa under, can obtain purity 99.6%SOCl from cat head like this
2
Whole multistage rectification device operational process is to carry out under the vacuum of-0.03MPa fully.So both reduce steam consumption, also prevented environmental pollution.
Embodiment 2
Other are identical with embodiment 1, and different is to have selected following parameter in the present embodiment for use:
1, one-level rectifying
70% sulfur oxychloride is fed the one-level rectifying tower, and tower still temperature is at 130 ℃, and cat head obtains 92% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank;
2, two-stage rectification
92% sulfur oxychloride is fed the two-stage rectification tower, and processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reaches 3/4 still liquid level and temperature reaches 89 ℃, the time, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 98% left and right sides SOCl from cat head
2
3, three grades of rectifying
With 98%SOCl
2By being metered into three grades of rectifying tower stills, control tower still temperature is at 78-89 ℃, cat head 76-80 ℃, tower top pressure is-the decompressing and continuous rectifying condition of 0.06MPa under, can obtain purity 99.7% SOCl from cat head like this
2
Embodiment 3
Other are identical with embodiment 1, and different is to have selected following parameter in the present embodiment for use:
1, one-level rectifying
75% sulfur oxychloride is fed the one-level rectifying tower, and tower still temperature is at 120 ℃, and cat head obtains 95% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank;
2, two-stage rectification
95% sulfur oxychloride is fed the two-stage rectification tower, and processing parameter is: tower still temperature is controlled at 78-89 ℃, when tower still temperature reaches 3/4 still liquid level and temperature reaches 89 ℃, the time, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 99% left and right sides SOCl from cat head
2
3, three grades of rectifying
With 99% SOCl
2By being metered into three grades of rectifying tower stills, control tower still temperature is at 78-89 ℃, cat head 72-75 ℃, tower top pressure is-the decompressing and continuous rectifying condition of 0.03MPa under, can obtain purity 99.8% SOCl from cat head like this
2
Claims (9)
1, a kind of multistage rectification process for high-purity thionyl chloride is characterized in that, employing be the mode of continuous three grades of rectifying, comprise one-level rectifying, two-stage rectification and three grades of rectifying, corresponding employing one-level rectifying tower, two-stage rectification tower and three grades of rectifying tower; Wherein, what one-level rectifying was adopted is " intermittent feeding " mode, the mode of two-stage rectification and three grades of rectifying employing continuously feedings and continuous discharging, at least place sulphur at the top of described one-level rectifying tower, described intermittent feeding provides many more time to make sulfur dichloride in the crude product sulfur oxychloride contact with sulphur to convert the bottom that sulfur monochloride has been back to described one-level rectifying tower again to.
2, method according to claim 1 is characterized in that comprising in described one-level rectifying, and 50～75% sulfur oxychlorides are fed one-level rectifying Tata still, and tower still temperature is at 110-130 ℃, and cat head obtains 80～95% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank.
3, method according to claim 2 is characterized in that, described one-level rectifying parameter comprises: 70% sulfur oxychloride is fed the one-level rectifying tower, and tower still temperature is at 110-130 ℃, and cat head obtains 92% sulfur oxychloride, the high boiling material S of tower still
2Cl
2Be discharged to storage tank.
4, method according to claim 1, it is characterized in that comprising 80～95% sulfur oxychlorides feeding two-stage rectification Tata still in described two-stage rectification, processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reaches 3/4 still liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 98-99%SOCl from cat head
2
5, method according to claim 4, it is characterized in that comprising 85～95% sulfur oxychlorides feeding two-stage rectification Tata still in described two-stage rectification, processing parameter is: tower still temperature is controlled at 78-89 ℃, when the tower still reaches 3/4 still liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still is discharged to one-level rectifying tower still, obtains 98-99%SOCl from cat head
2
6, method according to claim 1 is characterized in that described three grades of rectifying comprise the SOCl with 98-99%
2Join three grades of rectifying Tata stills, control tower still temperature is at 78-89 ℃, cat head 72-80 ℃, tower top pressure is-0.01～-the decompressing and continuous rectifying condition of 0.06MPa under, obtain purity 99.6-99.8% SOCl from cat head like this
2
7, method according to claim 6 is characterized in that described three grades of rectifying comprise the SOCl with 98-99%
2Join three grades of rectifying Tata stills, control tower still temperature is at 78-89 ℃, cat head 72-75 ℃, tower top pressure is-the decompressing and continuous rectifying condition of 0.03MPa under, obtain purity 99.6%-99.8% SOCl from cat head like this
2
8, method according to claim 1 is characterized in that, all places sulphur at the top of described one-level rectifying tower, two-stage rectification tower and three grades of rectifying tower.
9, method according to claim 1, the rectifier unit operational process that it is characterized in that described continuous three grades of rectifying are to carry out under the condition of-0.01MPa fully.
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|---|---|---|---|
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|---|---|---|---|
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| CN101920938B (en) * | 2010-08-12 | 2012-05-09 | 中平能化集团开封东大化工有限公司 | Method for rectifying thionyl chloride |
| CN103172031B (en) * | 2013-04-17 | 2015-02-11 | 天津大学 | Method and equipment for refining sulfoxide chloride |
| CN104229737A (en) * | 2014-09-18 | 2014-12-24 | 中盐工程技术研究院有限公司 | Method and device for producing bromine from brominated butyl rubber wastewater through steam distillation |
| CN109399577B (en) * | 2018-11-27 | 2020-10-09 | 江西世龙实业股份有限公司 | Method for refining thionyl chloride |
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