CN100480173C - Liquid phase circulation method in synthesis of thionyl chloride - Google Patents
Liquid phase circulation method in synthesis of thionyl chloride Download PDFInfo
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- CN100480173C CN100480173C CNB2008100047801A CN200810004780A CN100480173C CN 100480173 C CN100480173 C CN 100480173C CN B2008100047801 A CNB2008100047801 A CN B2008100047801A CN 200810004780 A CN200810004780 A CN 200810004780A CN 100480173 C CN100480173 C CN 100480173C
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- sulfur oxychloride
- oxychloride
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Abstract
The invention relates to a liquid phase circulation method for synthesizing thionyl chloride. Specifically, the method comprises a process that the condensate of a crude product of the thionyl chloride and the purified mixed liquid of the crude product of the thionyl chloride in a degassing device are vulcanized and distilled, and then the distilled tower bottom residual liquid is again pumped to the sulfur dichloride for synthesis, thereby forming the the fully-closed and full-circulation method for synthesizing the thionyl chloride.
Description
Technical field
What the present invention relates to is the synthetic middle liquid phase round-robin method of a kind of sulfur oxychloride, concretely, described method comprises from the phlegma of crude product sulfur oxychloride, crude product sulfur oxychloride mixing liquid after the purification of de-gassing vessel, vulcanize again and rectifying, residual solution is pumped to the synthetic process of sulfur dichloride again at the bottom of the tower of rectifying, thereby forms the synthetic method of described totally-enclosed recycle to extinction sulfur oxychloride.
Background technology
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.
The document that directly relates to the synthesizing chlorinated sulfoxide of sulfurous gas gas phase method has: US2431823, DE842041;
Be that the document that initiator produces the synthesizing chlorinated sulfoxide of sulfur monochloride has US1861900, US2420623 with sulphur;
In the prior art, the method for synthesizing chlorinated sulfoxide has tens kinds, and still, large-scale industrial production is following three kinds of operational paths basically:
(1) phosphorus pentachloride and sulfurous gas reaction, technology is simple, but SOCl
2With POCl
3Be difficult to separate, be difficult to obtain high purity SOCl
2
(2) be catalyzer with antimony chloride etc., sulfur subchloride and chlorsulfonic acid reaction, domestic extensive employing at present, complex process is invested bigger;
(3) the synthesizing chlorinated sulfoxide of gas-phase catalysis is a catalyzer with the gac, sulfur subchloride and sulfurous gas, chlorine reaction, abroad generally adopt, technology is simple, less investment and product purity height, can adopt closed internal circulation apparatus production, non-environmental-pollution, the primitive reaction formula is as follows:
1、
2、
But, in disclosed document,, adopt closed internal recycle method to produce though proposition is arranged,, as a heavy construction project, not open how closed internal recycle method is produced the concrete technical scheme of sulfur oxychloride, in view of this, specially proposes the present invention.
Summary of the invention
The object of the present invention is to provide the synthetic middle liquid phase round-robin method of a kind of sulfur oxychloride.
Purpose of the present invention can be achieved in the following manner:
A kind of sulfur dioxide gas is combined to the liquid phase circulation means in the sulfur oxychloride, and described method comprises:
(1) the crude product sulfur oxychloride is vulcanized the crude product sulfur oxychloride after obtaining vulcanizing;
(2) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material;
(3) with described mixing high boiling material and excessive chlorine reaction, obtain the sulfur dichloride mixed gas;
(4) with sulfur dichloride mixed gas and sulfur dioxide gas precursor reactant, obtain the sulfur oxychloride mixed gas;
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation,, obtain the crude product sulfur oxychloride described in the step (1), enter next circulation then the condensed product purification that outgases.
The content of sulfur oxychloride is 50～70% in the crude product sulfur oxychloride after the sulfuration described in the step among the present invention (1).
Condensed product in the step of the present invention (5) utilizes the gravity transfer of high potential difference formation to de-gassing vessel; In the described step (2), the mixing high boiling material that produces after the rectifying by pump delivery to S
2Cl
2Header tank.
In the mixing high boiling material that produces after the rectifying of the present invention, S
2Cl
2Content account for and mix 93% of high boiling material gross weight, SOCl
2Content accounts for and mixes 1～2% of high boiling material gross weight, and S content accounts for and mixes 5% of high boiling material gross weight.
The content of sulfur oxychloride is 40～45% of described crude product gross weight in the condensed sulfur oxychloride crude product of the present invention.
It is that 70～90 ℃, gauge pressure pressure are to carry out under 0.02MPa to the 0.23MPa condition that the degassing of the present invention is purified in temperature; The content of sulfur oxychloride accounts for 50～72% of described crude product gross weight in the crude product sulfur oxychloride of degassing purification back gained.
Crude product sulfur oxychloride among the present invention after the degassing is purified carries out in sulfur still or rectifying tower when vulcanizing.
In the described sulfidation add-on of sulphur be with the crude product sulfur oxychloride in the 80-98% of amount of sulfur dichloride and the required sulphur of chlorine complete reaction.
Among the present invention, add excessive sulphur in the sulfuration bed at rectifying tower top, make sulfur dichloride and chlorine and sulphur react, the sulfur monochloride of generation is back to rectifier bottoms, thereby finishes the liquid phase working cycle.
Among the present invention, sulphur that rectifier bottoms adds for the crude product sulfur oxychloride in sulfur dichloride compare with the amount of the required sulphur of chlorine complete reaction inexcessive.
Specifically, a kind of sulfur dioxide gas of the present invention is combined to the liquid phase circulation means in the sulfur oxychloride:
In order to be illustrated more clearly in technical scheme of the present invention, 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.
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, 70～90 ℃ 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.
4, sulfur oxychloride rectifying, 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.
Key of the present invention is, and is different with prior art, the sulfur monochloride (S among the present invention
2Cl
2), can use conventional methods and produce a certain amount of at the production initial stage, also can directly purchase sulfur monochloride, perhaps the crude product that contains chlorination sulfoxide about 63～68% with sulfur dichloride, chlorine, sulfurous gas method synthetic gets final product, can reach the demand of sulfur monochloride and the running balance of turnout aborning later on, promptly described sulfur monochloride is from the rectifying tower still.
Need to prove that the pressure described in the present invention is gauge pressure pressure.
Specifically, liquid phase round-robin method during sulfur oxychloride of the present invention is synthetic comprises:
(1) be that 63～68% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprise sulfur dichloride 15～25% in the described crude product sulfur oxychloride, temperature in the sulfur still is Yu Wenwei≤80 ℃ of crude product sulfur oxychloride, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the 80-98% of amount of the required sulphur of sulfur dichloride complete reaction, the crude product sulfur oxychloride after obtaining vulcanizing; Its each component is: the content of sulfur oxychloride is 50-65%, and sulfur dichloride content is 5-15%, and sulfur monochloride content is 25-35%.
Because the fusing point of liquid sulfur is 112 ℃, the boiling point that has surpassed sulfur oxychloride, may cause the part sulfur oxychloride to decompose, therefore, selection of the present invention is to add the sheet solid sulphur at normal temperature and pressure to react, this reaction is for thermopositive reaction and need not add catalyzer, SCl in the crude product sulfur oxychloride after the sulfuration
2Content descends, S
2Cl
2Content raises.
Described sulfuration is included in the sulfuration of carrying out in the sulfur still, also comprises the sulfidation of carrying out in the rectifying tower.
Excessive sulphur it is to be noted that especially adding sulphur in sulfur still or rectifier bottoms must be not enough reacting weight, because can cause the intact sulphur blocking pipe of unreacted, pump etc.Finally, excessive sulphur is placed on the top of rectifying tower, and during rectifying, with other unreacted reactants of part of sulfur oxychloride gasification and the reaction of Salmon-Saxl of rectifier, reactant presents liquid state, falls back at the bottom of the tower, makes SCl
2The basic complete reaction of gas generate sulfur monochloride.
Described sulfur still can be independently, also can directly sulphur be joined in the degassing purification still to vulcanize.
Need at the bottom of sulfur still or rectifying tower, add how much sulphur to satisfy not complete cure reaction, promptly, it is inexcessive that the sulphur that adds at the bottom of sulfur still or tower is compared with the real reaction amount, can learn by the mode that detects, best, at the bottom of sulfur still or tower, the add-on of sulphur is 80～98% of a complete reaction requirement, is preferably 90～97%.
The sulfuration bed is set on the top of rectifying tower and adds certain sulphur therein, they carry out chemical reaction generation sulfur monochloride with sulfur dichloride that is evaporated and/or chlorine and are back to the tower still, make the residual sulfur monochloride component of tower still enrichment, the distillation procedure sulfur monochloride that finishes is delivered to header tank, used for synthesis, thus the liquid phase working cycle finished.
Discover that the purity of crude product sulfur oxychloride of the present invention needs emphasis to consider, the content with degassing post chlorization sulfoxide that control reaches the sulfur oxychloride of condenser is very important.
If synthetic crude product sulfur oxychloride purity is improved, certainly will cause in the crude product sulfur oxychloride Sulphur Monochloride and sulphur dichloride content low excessively, the total amount that consequently finally can offer sulfur dichloride synthetic sulfur monochloride makes output reduce very little.
Otherwise, if the purity of synthetic crude product sulfur oxychloride is too low, to cause in the crude product sulfur oxychloride Sulphur Monochloride and sulphur dichloride content too high, the total amount that consequently can offer sulfur dichloride synthetic sulfur monochloride is too many, needs other container deposit sulfur monochloride.
(2) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110～130 ℃, cat head obtains 80～95% sulfur oxychloride, importantly, in described one-level rectifying, what adopt is the intermittent type charging, so that have time enough to make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78～80 ℃, 72～75 ℃ of cats head, and reflux ratio is 1:1 ,-0.02～-carry out under the condition of 0.03MPa, can obtain purity 99.6% above SOCl from cat head
2
In the method for the present invention, the rectifying a spot of low-boiling-point substance (SULPHURYL CHLORIDE etc.) that comes out is adopted to the crude product groove and reused.All the other a small amount of non-condensable gasess are made subsequent product hydrochloric acid and S-WAT after absorbing by exhaust gas absorption cell.
Rectifying enters subsider with bottom product after finishing, and pumps into S then
2Cl
2Storage tank, by transferpump with S
2Cl
2Be delivered to S
2Cl
2Header tank, S
2Cl
2S in the header tank
2Cl
2Mixed solution is after the spinner-type flowmeter metering, quantitatively to SCl
2Synthetic SCl is made in the synthesis reactor charging
2Use, thereby finish the liquid phase circulation.
(3) with described mixing high boiling material and excessive chlorine reaction, obtain the sulfur dichloride mixed gas;
Mixing high boiling material in the rectifying tower is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, feed chlorine again, mix under the condition that sulfur monochloride in the high boiling material and excessive chlorine are 0.02～0.23MPa at 70～90 ℃, pressure and react the Cl of feeding
2With S liquid in the sulfur dichloride synthesis reactor
2Cl
2Volume ratio be 150: 0.2; Cl
2And S
2Cl
2In the sulfur dichloride synthesis reactor, react the SCl of generation
2With excessive Cl
2Mixed gas discharge from the air outlet, the pressure P 1 of described air outlet is 0.02～0.23MPa.Sulfur dichloride content 40～55% in the described sulfur dichloride mixed gas, chlorine content 30～40%.
(4) with sulfur dichloride mixed gas and sulfur dioxide gas precursor reactant, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is 150: 100: (0.2～0.25) delivers to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor, temperature in the sulfur oxychloride synthesis reactor is 150～300 ℃, pressure is 0.02MPa～0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 35～55% in the described mixed gas, sulfur dichloride 15～25%, chlorine 15～30%, sulfurous gas 15-25%.
Process description of the present invention is as follows, by the high boiling material sulfur monochloride that the rectifying tower still is discharged, gets to header tank with pump, and is added to the sulfur dichloride reactor by metering, feeds chlorine simultaneously, generates the gaseous state sulfur dichloride, and makes chlorine excessive.Excessive purpose has two to make chlorine, and the one, with S
2Cl
2All change into SCl
2, and vaporize by temperature control.The 2nd, when synthetic crude product sulfur oxychloride, to replenish chlorine and participate in reaction.
Described sulfur monochloride feeds the sulfur dichloride synthesis reactor and excessive chlorine reacts, and the about 80-90 of temperature of reaction ℃, pressure is 0.02Mpa～0.23MPa; Cl
2, S
2Cl
2(liquid) ratio is 150: 0.2 (volume ratio).Cl
2And S
2Cl
2In the sulfur dichloride synthesis reactor, react, feed excessive chlorine, generate SCl fully
2With excessive Cl
2Mixed gas, air outlet pressure P 1〉0.02Mpa.
Carry out the synthetic of crude product sulfur oxychloride then, with the mixed gas of excessive chlorine and sulfur monochloride reaction generation sulfur dichloride and chlorine, merging enters the sulfur oxychloride synthesis reactor with sulfurous gas then earlier, and its reaction formula is as follows:
3Cl
2+2SO
2+S
2Cl
2＝4SOCl
2
Can draw from Theoretical Calculation, the mol ratio of the reaction between this three is 3: 2: 1;
But researchist of the present invention finds, adopts following ratio can bring suitable more reaction result, generally Cl
2, SO
2, S
2Cl
2The volume ratio of (liquid) is 150: 100: (0.2～0.25); As optimal way, can make SO
2Excessive slightly.
Come from the mixed gas of sulfur dichloride synthesis reactor, mix from the gas of condenser, from the gas of crude product de-gassing vessel and be preheated to 200 ℃ and enter the sulfur oxychloride synthesis reactor, 220 ℃ of the temperature of the building-up reactions of sulfur oxychloride, pressure P 2 is 0.02Mpa to 0.23MPa in the synthesis reactor.
The Cl that comes out in the sulfur dichloride synthesis reactor
2And SCl
2Temperature is 70～90 ℃, SO
2Normal temperature, recycle gas is a normal temperature, and the temperature of mixing laggard preheater indirect utilization thermal oil is heated to 200 ℃, and thermal oil is introduced between the crude product reactor tube by the pump pressurization, fills catalyst in the reactor tube, enters between the preheater tubulation again.
Synthetic crude product sulfur oxychloride process is thermopositive reaction, when reaction with the heat transferred thermal oil.Thermal oil removes the preheating reactant gases again.
The driving for the first time and the back driving of stopping all need electric boosting thermal oil, and the crude product reactor is heated to more than 180 ℃.
Concrete, sulfur oxychloride of the present invention is synthetic can be following mode:
1., material process
Liquid chlorine, sulfur dioxide liquid to 0.2～0.3MPa, are delivered to the mist eliminator dehydration through the vaporizer vaporization respectively.Then, sulfurous gas enters mixing tank after the spinner-type flowmeter metering used for synthesis, and chlorine enters the sulfur dichloride synthesis reactor after the spinner-type flowmeter metering, generate sulfur dichloride with sulfur monochloride mixed solution contact reacts under 60～100 ℃, and is used for synthesis.
2., synthesis procedure
Sulfurous gas, sulfur dichloride mix at mixing tank with circulation gas, after preheater is preheated to 180～200 ℃, enters reactor and carry out building-up reactions generation sulfur oxychloride crude product synthetic gas under 200～250 ℃.
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, the actual conditions of condensation is≤40 ℃, the content of sulfur oxychloride is 35～65% in the condensed product that obtains, sulfur dichloride content 15～25%, chlorine content is a small amount of, with purifications that in degassing purification still, outgas of above-mentioned condensed product, be that 70～90 ℃, pressure are to carry out under 0.02～0.23Mpa condition in temperature, through the degassing come out not with fixed attention property gas (major ingredient is SO
2And Cl
2, SCl
2) behind the degassing separator, circulation gas basin, be forced into by recirculation blower and be transported to the circulation gas surge tank more than the 0.02Mpa, turn back to gas mixer then and use for building-up reactions, circulate thereby finish gas phase.The content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the degassing is purified is 50～70%, and sulfur dichloride content is 15～25%, and sulfur monochloride content is 15-25%.
In order to be separated completely, must be with the low-boiling-point substance SCl in the crude product sulfur oxychloride
2(59 ℃ of boiling points) changes into high boiling material S
2Cl
2(137 ℃ of boiling points) can reflux a few hours then by adding S at rectifier, realizes above-mentioned effect, also can add sulphur in sulfur still and vulcanize.Component S Cl
2And Cl
2Carry out chemical reaction with S, generate S
2Cl
2Be back to liquid phase tower still, make the residual S of tower still
2Cl
2Enrichment.
Equation is as follows:
2S+Cl
2→S
2Cl
2；(S+SCl
2→S
2Cl
2
In working cycle, produce and rectifying in a spot of SO of producing
2Cl
2, can be sent to the sulfur dichloride synthesis reactor with sulfur monochloride, and then same SCl
2Effect generates SOCl
2, concrete formula as follows:
SO
2Cl
2+SCl
2→2SOCl
2
Synthetic method of the present invention, improve crude product sulfur oxychloride purity by the degassing in the process and reach about 63～68%, so a lot of low-boiling-point substances such as sulfurous gas, sulfur dichloride and a spot of SULPHURYL CHLORIDE all can turn back to the sulfur oxychloride reactor by gas phase and participate in reaction generation sulfur oxychloride again.
Beneficial effect of the present invention is as follows:
(1) industrial scale expansion is carried out easily;
(2) all starting material are all fully used;
(3) owing to adopted the liquid phase circulation, but make the technology serialization carry out, stable equipment operation is reliable, and energy consumption is low.
Description of drawings
Fig. 1 is the preparation technology's of a sulfur oxychloride of the present invention basic flow sheet;
Fig. 2 is a gas phase round-robin process flow sheet of the present invention;
In order to clearly demonstrate the present invention, special numbering with component names in the accompanying drawing and correspondence is listed sulfur dichloride synthesis reactor 1, sulfur oxychloride synthesis reactor 2, crude product condenser 3, degassing purification still 4, crude product sulfur still 5, rectifying condenser 6, rectifying tower 7, tower still 8, sulfur monochloride transferpump 9, crude product discharge port 10.
Embodiment
Embodiment one
Liquid phase round-robin method during a kind of sulfur oxychloride is synthetic comprises:
(1) be that 68% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprise sulfur dichloride 15% in the described crude product sulfur oxychloride, temperature in the sulfur still is that the surplus temperature of crude product sulfur oxychloride is 80 ℃, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the required sulphur of sulfur dichloride complete reaction amount 80%, the crude product sulfur oxychloride after obtaining vulcanizing; Its each component is: the content of sulfur oxychloride is 50%, and sulfur dichloride content is 15%, and sulfur monochloride content is 35%.
(2) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, in described one-level rectifying, adopt the intermittent type charging, make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78～80 ℃, 72～75 ℃ of cats head, and reflux ratio is 1:1 ,-0.02～-carry out under the condition of 0.03MPa, can obtain purity 99.6% above SOCl from cat head
2
(3) with described mixing high boiling material and excessive chlorine reaction, obtain the sulfur dichloride mixed gas;
Mixing high boiling material in the rectifying tower is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, feed chlorine again, mix under the condition that sulfur monochloride in the high boiling material and excessive chlorine are 0.02MPa at 70 ℃, pressure and react the Cl of feeding
2With S liquid in the sulfur dichloride synthesis reactor
2Cl
2Volume ratio be 150: 0.2; Cl
2And S
2Cl
2In the sulfur dichloride synthesis reactor, react the SCl of generation
2With excessive Cl
2Mixed gas discharge from the air outlet, the pressure P 1 of described air outlet is 0.04MPa.Sulfur dichloride content 55% in the described sulfur dichloride mixed gas, chlorine content 40%.
(4) with sulfur dichloride mixed gas and sulfur dioxide gas precursor reactant, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.2, temperature in the sulfur oxychloride synthesis reactor is 300 ℃, pressure is 0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 55% in the described mixed gas, sulfur dichloride content is 15%, and chlorine content is 15%, and content of sulfur dioxide is 15%.
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, be condensed to 40 ℃, the content of sulfur oxychloride is 55% in the condensed product that obtains, sulfur dichloride content 20%, chlorine content is a small amount of, with the purification that outgases in degassing purification still of above-mentioned condensed product, in temperature is that 90 ℃, pressure are under the 0.23Mpa condition, the content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the purification is 60%, and sulfur dichloride content is 20%, and sulfur monochloride content is 20%.
Embodiment two
(1) be that 65% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprise sulfur dichloride 20% in the described crude product sulfur oxychloride, temperature in the sulfur still is that the surplus temperature of crude product sulfur oxychloride is 60 ℃, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the required sulphur of sulfur dichloride complete reaction amount 88%, make other material except that the chlorination sulfoxide in the described crude product sulfur oxychloride change into sulfur monochloride, crude product sulfur oxychloride after obtaining vulcanizing, in the crude product sulfur oxychloride after the described sulfuration, its each component is: the content of sulfur oxychloride is 65%, sulfur dichloride content is 10%, and sulfur monochloride content is 25%.
(2) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110～130 ℃, cat head obtains 80～95% sulfur oxychloride, in described one-level rectifying, adopt the intermittent type charging, make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78～80 ℃, 72～75 ℃ of cats head, and reflux ratio is 1:1 ,-0.02～-carry out under the condition of 0.03MPa, can obtain purity 99.6% above SOCl from cat head
2
(3) with described mixing high boiling material and excessive chlorine reaction, obtain the sulfur dichloride mixed gas;
Mixing high boiling material in the rectifying tower is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, feed chlorine again, mix under the condition that sulfur monochloride in the high boiling material and excessive chlorine are 0.23MPa at 90 ℃, pressure and react the Cl of feeding
2With S liquid in the sulfur dichloride synthesis reactor
2Cl
2Volume ratio be 150: 0.25; Cl
2And S
2Cl
2In the sulfur dichloride synthesis reactor, react the SCl of generation
2With excessive Cl
2Mixed gas discharge from the air outlet, the pressure P 1 of described air outlet is 0.23MPa.Sulfur dichloride content 55% in the described sulfur dichloride mixed gas, chlorine content 30%.
(4) with sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.25, temperature in the sulfur oxychloride synthesis reactor is 150 ℃, pressure is 0.02MPaMPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 35% in the described mixed gas, sulfur dichloride content is 25%, and chlorine content is 25%, and content of sulfur dioxide is 15%.
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, the actual conditions of condensation is 30 ℃, the content of sulfur oxychloride is 35% in the condensed product that obtains, sulfur dichloride content 25%, chlorine content is a small amount of, with the purification that outgases in degassing purification still of above-mentioned condensed product, is that 70 ℃, pressure are under the 0.13Mpa condition in temperature, the content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the purification is 50%, and sulfur dichloride content is 25% sulfur monochloride 25%.
Embodiment three
Liquid phase round-robin method during a kind of sulfur oxychloride is synthetic comprises:
(1) be that 68% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprise sulfur dichloride 25% in the described crude product sulfur oxychloride, temperature in the sulfur still is that the surplus temperature of crude product sulfur oxychloride is 70 ℃, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the required sulphur of sulfur dichloride complete reaction amount 98%, other material except that the chlorination sulfoxide in the described crude product sulfur oxychloride changes into sulfur monochloride, crude product sulfur oxychloride after obtaining vulcanizing, each component is in the crude product sulfur oxychloride after the described sulfuration: the content of sulfur oxychloride is 60%, sulfur dichloride content is 15%, and sulfur monochloride content is 25%.
(2) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110～130 ℃, cat head obtains 80～95% sulfur oxychloride, in described one-level rectifying, adopt the intermittent type charging, make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78～80 ℃, 72～75 ℃ of cats head, and reflux ratio is 1:1 ,-0.02～-carry out under the condition of 0.03MPa, can obtain purity 99.6% above SOCl from cat head
2
(3) with described mixing high boiling material and excessive chlorine reaction, obtain the sulfur dichloride mixed gas;
Mixing high boiling material in the rectifying tower is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, feed chlorine again, mix under the condition that sulfur monochloride in the high boiling material and excessive chlorine are 0.15MPa at 80 ℃, pressure and react the Cl of feeding
2With S liquid in the sulfur dichloride synthesis reactor
2Cl
2Volume ratio be 150: 0.2; Cl
2And S
2Cl
2In the sulfur dichloride synthesis reactor, react the SCl of generation
2With excessive Cl
2Mixed gas discharge from the air outlet, the pressure P 1 of described air outlet is 0.20MPa.Sulfur dichloride content 50% in the described sulfur dichloride mixed gas, chlorine content 35%.
(4) with sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.25, temperature in the sulfur oxychloride synthesis reactor is 250 ℃, pressure is 0.02MPa～0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 45% in the described mixed gas, sulfur dichloride 25%, chlorine 15%, sulfurous gas 15%.
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, the actual conditions of condensation is 25 ℃, the content of sulfur oxychloride is 65% in the condensed product that obtains, sulfur dichloride content 15%, chlorine content is a small amount of, with the purification that outgases in degassing purification still of above-mentioned condensed product, in temperature is that 90 ℃, pressure are under the 0.23Mpa condition, the content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the purification is 70%, and sulfur dichloride content is 15%, sulfur monochloride content 15%.
Embodiment four
Present embodiment relates generally to the degassing of crude product sulfur oxychloride and purifies.
The degassing of the described crude product of present embodiment is purified and is carried out in degassing purification still, is 70～90 ℃, pressure in temperature〉under the 0.02MPa condition; The back purity sulfur oxychloride content in crude product of purifying is about 50～70%.
The gas outlet pressure P5 of described degassing purification still〉P1; The gas outlet pressure of degassing purification still can be regulated by temperature at the bottom of regulating degassing purification still.
Degasification process of the present invention is the degassing of charging limit, limit, and when expecting to advance to expire, degassing still temperature reaches requirement and just material is put in the crude product storage tank
It below is the degassing of the present invention back crude product sulfur oxychloride analytical data
Annotate: with distillation method analysis (100 ℃ of heating in water bath)
Illustrate: 1, SCl
259 ℃ of boiling points
2, SO
2Cl
269.1 ℃ of boiling points
3, SOCl
279 ℃ of boiling points
4, S
2Cl
2136.8 ℃ of boiling points
From last surface analysis situation: SO as if
2Cl
2Still than higher, but from the situation of reality, SO
2Cl
2Be can content not high, trace just.SCl
2Amount should be many, SCl in the time of can only illustrating 69～74.5 ℃
2And SOCl
2Formation azeotrope.
80～92 ℃ content is also than higher, and this is because SOCl
2And S
2Cl
2The azeotrope that is split into.
Residual solution should major part all be S
2Cl
2
The sulfur oxychloride crude product is after the crude product condenser condenses, liquid enters the operation that outgases of degassing still, elaboration liquid after the degassing finishes enters rectification working process, uncooled property gas is forced into by surge pump through degassing separation and is delivered to the circulator surge tank more than the 0.08Mpa, returns mixing tank then and uses for building-up reactions.Thereby finish the gas phase working cycle.
Claims (7)
1, a kind of sulfur dioxide gas is combined to the liquid phase circulation means in the sulfur oxychloride, it is characterized in that, described method comprises:
(1) the crude product sulfur oxychloride is vulcanized the crude product sulfur oxychloride after obtaining vulcanizing;
(2) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material;
(3) with described mixing high boiling material and excessive chlorine reaction, obtain the sulfur dichloride mixed gas;
(4) with sulfur dichloride mixed gas and sulfur dioxide gas precursor reactant, obtain the sulfur oxychloride mixed gas;
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation,, obtain the crude product sulfur oxychloride described in the step (1), enter next circulation then the condensed product purification that outgases;
Crude product sulfur oxychloride after the degassing is purified carries out in sulfur still or rectifying tower when vulcanizing, in the sulfuration bed at rectifying tower top, add excessive sulphur, make sulfur dichloride and chlorine and sulphur react, the sulfur monochloride that generates is back to rectifier bottoms, thereby finish the liquid phase working cycle, sulphur that sulfur still or rectifier bottoms add for the crude product sulfur oxychloride in sulfur dichloride compare with the amount of the required sulphur of chlorine complete reaction inexcessive.
2, method according to claim 1 is characterized in that, the content of sulfur oxychloride accounts for 50～70% of crude product gross weight in the crude product sulfur oxychloride after the sulfuration described in the step (1).
3, method according to claim 1 and 2 is characterized in that, the condensed product in the described step (5) utilizes the gravity transfer of high potential difference formation to de-gassing vessel; In the described step (2), the mixing high boiling material that produces after the rectifying by pump delivery to S
2Cl
2Header tank.
4, method according to claim 3 is characterized in that, in the mixing high boiling material that produces after the rectifying, and S
2Cl
2Content account for and mix 93% of high boiling material gross weight, SOCl
2Content accounts for and mixes 1～2% of high boiling material gross weight, and S content accounts for and mixes 5% of high boiling material gross weight.
5, method according to claim 1 is characterized in that, the content of sulfur oxychloride is 40～45% of described crude product gross weight in the condensed sulfur oxychloride crude product.
6, method according to claim 1 is characterized in that, it is that 65～90 ℃, gauge pressure pressure are to carry out under 0.02MPa to the 0.23MPa condition that the described degassing is purified in temperature; The content of sulfur oxychloride accounts for 50～72% of described crude product gross weight in the crude product sulfur oxychloride of degassing purification back gained.
7, method according to claim 1 is characterized in that, in the described sulfidation add-on of sulphur be with the crude product sulfur oxychloride in sulfur dichloride and the required sulphur of chlorine complete reaction amount 80～98%.
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| CN104133498B (en) * | 2014-07-31 | 2015-09-23 | 江西世龙实业股份有限公司 | A kind of DCS of employing controls the method for mass flow in thionyl chloride synthesis process automatically |
| CN106185809B (en) * | 2016-07-04 | 2017-05-03 | 汇智工程科技有限公司 | Method and apparatus for high-effectively utilizing chlorine in production of sulfoxide chloride |
| CN106395761A (en) * | 2016-08-29 | 2017-02-15 | 山东凯盛新材料股份有限公司 | Preparation technology of thionyl chloride |
| CN106348254A (en) * | 2016-08-29 | 2017-01-25 | 山东凯盛新材料股份有限公司 | Preparing method of thionyl chloride |
| CN106315519A (en) * | 2016-08-29 | 2017-01-11 | 山东凯盛新材料股份有限公司 | Method for preparing thionyl chloride |
| CN106335881A (en) * | 2016-08-29 | 2017-01-18 | 山东凯盛新材料股份有限公司 | Technology for preparing thionyl chloride |
| CN106629626B (en) * | 2017-01-23 | 2019-03-15 | 山东凯盛新材料股份有限公司 | The production technology of thionyl chloride |
| CN106744712B (en) * | 2017-01-23 | 2019-05-21 | 山东凯盛新材料股份有限公司 | The method for producing thionyl chloride |
| CN106672916B (en) * | 2017-01-23 | 2019-03-12 | 山东凯盛新材料股份有限公司 | The production technology of thionyl chloride |
| CN106853958B (en) * | 2017-01-23 | 2019-05-21 | 山东凯盛新材料股份有限公司 | The production method of thionyl chloride |
| CN106698364B (en) * | 2017-01-23 | 2019-03-15 | 山东凯盛新材料股份有限公司 | The production method of thionyl chloride |
| CN107954400B (en) * | 2017-11-30 | 2020-10-30 | 山东凯盛新材料股份有限公司 | Method for optimizing thionyl chloride production process |
| CN108467017B (en) * | 2018-06-05 | 2021-07-30 | 中国天辰工程有限公司 | Sulfur dioxide vaporization process for producing thionyl chloride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431823A (en) * | 1946-02-16 | 1947-12-02 | Pittsburgh Plate Glass Co | Manufactruing thionyl chloride |
-
2008
- 2008-01-30 CN CNB2008100047801A patent/CN100480173C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431823A (en) * | 1946-02-16 | 1947-12-02 | Pittsburgh Plate Glass Co | Manufactruing thionyl chloride |
Non-Patent Citations (4)
| Title |
|---|
| 氯化亚砜的生产与应用. 李晓平.化工中间体，第2期. 2006 |
| 氯化亚砜的生产与应用. 李晓平.化工中间体，第2期. 2006 * |
| 氯化亚砜的生产现状及其发展前景. 纪罗军.化学工业与工程技术，第25卷第3期. 2004 |
| 氯化亚砜的生产现状及其发展前景. 纪罗军.化学工业与工程技术，第25卷第3期. 2004 * |
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