CN101412503A - Method for synthesizing thionyl chloride with crude product thionyl chloride as raw material - Google Patents
Method for synthesizing thionyl chloride with crude product thionyl chloride as raw material Download PDFInfo
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- CN101412503A CN101412503A CNA2008100047799A CN200810004779A CN101412503A CN 101412503 A CN101412503 A CN 101412503A CN A2008100047799 A CNA2008100047799 A CN A2008100047799A CN 200810004779 A CN200810004779 A CN 200810004779A CN 101412503 A CN101412503 A CN 101412503A
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- oxychloride
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Abstract
The invention relates to a method for synthesizing thionyl chloride which takes a crude thionyl chloride product as an initial point. The method is a totally closed circulating process comprising the following steps: other materials in the synthesized crude thionyl chloride product is used to react with sulfur so as to mainly produce a sulfur monochloride product; the other materials comprises sulfur monochloride, sulfur dichloride, thionyl chloride, a small amount of chlorine and sulfur dioxide; and then the sulfur monochloride product is used to synthesize thionyl chloride together with chlorine, sulfur dichloride, and a gas product from the condenser after thionyl chloride synthesis and the crude product purification process.
Description
Technical field
The present invention relates to be a kind of be the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride, concretely, the present invention is the sulfur monochloride that generates in other material in a kind of crude product sulfur oxychloride that utilizes after synthetic and the rectifying tower, cooperates chlorine, sulfurous gas then and the totally-enclosed working cycle of the synthesizing chlorinated sulfoxide of gaseous product of the condenser after synthetic and crude product purification process from sulfur oxychloride.
Background technology
Sulfur oxychloride is agricultural chemicals, medicine, sensitive materials and the important intermediate raw material of superpolymer intermediate synthetic, 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:
The present invention is on the basis of above document, improved feeding manner, adding inexcessive sulphur in the crude product sulfur oxychloride vulcanizes, with the crude product sulfur oxychloride is starting point, utilize other material in the crude product sulfur oxychloride, described other material comprises sulfur monochloride, sulfur dichloride, a spot of chlorine and sulfurous gas, they and reaction of Salmon-Saxl, generation is mainly the sulfur monochloride product, cooperate chlorine then, sulfurous gas and from sulfur oxychloride the condenser after synthetic and the gaseous product of crude product purification process, synthesizing chlorinated sulfoxide forms a totally-enclosed working cycle.
Summary of the invention
The object of the present invention is to provide a kind of is the method for the synthesizing chlorinated sulfoxide of starting point with the crude product sulfur oxychloride.
Provided by the invention a kind of be the method for the synthesizing chlorinated sulfoxide of starting point with the crude product sulfur oxychloride, comprise that sulfur monochloride and chlorine reaction generate sulfur dichloride, the sulfur dichloride that generates and the mixture of chlorine are with the sulfurous gas and the synthetic crude product sulfur oxychloride mixture of gaseous phase materials of purifying from crude product condenser and the crude product degassing.Drop into sulphur, SO in described sulphur and the crude product to described crude product sulfur oxychloride
2Cl
2With unreacted SCl
2, S
2Cl
2And be partly dissolved therein Cl
2And SO
2, generate sulfur monochloride.
Wherein, above-mentioned crude product sulfur oxychloride is meant sulfur oxychloride content at 50-70%, and the sulphur of adding can be liquid, can be solid-state, perhaps powdered; SO in sulphur and the crude product
2Cl
2With unreacted SCl
2, S
2Cl
2And be partly dissolved therein Cl
2And SO
2, generating these reactions of sulfur monochloride, can independently carry out in the reactor; At this moment, the temperature of reaction needed relies on the waste heat of crude product sulfur oxychloride in the reactor independently to carry out; In addition, these reactions can also be carried out in the bottom of rectifying tower independently, and at this moment, reaction is to rely on the heat that gives in the rectifying to carry out.
After the above-mentioned reaction, the sulfur monochloride of generation is transported to the reaction raw materials of sulfur dichloride synthesis reactor as sulfur dichloride.
Purpose of the present invention can be achieved in the following manner:
A kind of is the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride,
(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 described crude product sulfur oxychloride the condensed product purification that outgases;
In the described step (1), in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, make that other material except that the chlorination sulfoxide in the described crude product sulfur oxychloride changes into sulfur monochloride.
Adding of the present invention is with respect to wherein the inexcessive sulphur of sulfur dichloride, is meant the 80-98% that adds with the amount of wherein the required sulphur of sulfur dichloride complete reaction; The preferred sulphur that adds is the 90-97% of the amount of the required sulphur of complete reaction.
Inexcessive sulphur of the present invention adds in sulfur still or at the bottom of the rectifying tower.
Adding the sulphur inexcessive with respect to sulfur dichloride wherein among the present invention is solid sulphur, described sulfuration is carried out in sulfur still, preferred described sulfuration is independently being carried out in the sulfur still, carry out in the sulfur still that vulcanization reaction is temperature required to be the surplus temperature of crude product sulfur oxychloride, preferred described surplus temperature is≤80 ℃.
The content of sulfur oxychloride is 30～70% in the condensed product described in the step of the present invention (5), and the content of sulfur oxychloride is 45～75% in the crude product sulfur oxychloride that the described degassing obtains after purifying.
Rectifying described in the step among the present invention (2) is carried out under 75～130 ℃ temperature, and the content of sulfur oxychloride is more than 99.6% in the product that obtains after the rectifying.
Rectifying of the present invention comprises:
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 one-level rectifying tower still, 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
Method of the present invention comprises also excessive sulphur is placed in the sulfuration bed on top of rectifying tower that 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 during rectifying.
Mixing high boiling material described in the step among the present invention (3) feeds the sulfur dichloride synthesis reactor, feeds chlorine again, mixes under the condition that sulfur monochloride in the high boiling material and excessive chlorine are 0.02MPa～0.23MPa at 70～90 ℃, pressure and reacts the Cl of feeding
2S with liquid state
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 0.02Mpa-0.23MPa. Then with the mixed gas of the sulfur dichloride of excessive chlorine and generation and chlorine with Cl
2: SO
2: S
2Cl
2The volume ratio of (liquid) is 150: 100: the synthesizing chlorinated sulfoxide of (0.2～0.25) mode, preferred described SO2's is excessive slightly.
The mixed gas that to discharge from the air outlet in the step among the present invention (4) mixes with sulfur dioxide gas, makes Cl
2: SO
2: liquid S
2Cl
2Volume ratio be 150: 100: (0.2～0.25), react then and obtain sulfur oxychloride gas.
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, 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.
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 50～70% 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.
Specifically, of the present invention be a kind of be the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride, comprising:
(1) is that 50～70% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprises 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, 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, its component is: the content of sulfur oxychloride is 50-65%, sulfur dichloride content is 5-15%, sulfur monochloride content position 25-35%;
Because the fusing point of liquid sulfur is 112 ℃, has surpassed the boiling point of sulfur oxychloride, may cause the part sulfur oxychloride to decompose, therefore, selection of the present invention is usually to press the solid-state sulphur of adding sheet to react, and 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 sulfur still to be carried out, and 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 add how much sulphur to satisfy not complete cure reaction to sulfur still or rectifying tower still, 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 dense, the distillation procedure sulfur monochloride that finishes is delivered to a high position, 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, control reaches the crude product sulfur oxychloride of condenser and the content of degassing post chlorization sulfoxide 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: the tower still 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 degree is controlled at 70～105 ℃, and when the tower bottoms position reached 3/4 still liquid level and degree 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 ℃, and cat head 72-75 ℃, 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 0.02MPa-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 0.02Mpa-0.23MPa.Sulfur dichloride content 40～55% in the described sulfur dichloride mixed gas, chlorine content 30～40%.
(4) with sulfur dichloride and excessive Cl
2Mixed gas and sulfur dioxide gas are delivered to the sulfur oxychloride 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) deliver 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 70-90 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 70～90 ℃, 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 0.02～0.2Mpa condition in temperature, through the degassing come out not with fixed attention property gas (major ingredient is SO
2And Cl
2, SCl
2) be transported to gas mixer for the building-up reactions use through degassing separator by surge pump, thus the gas phase circulation finished.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, and make the production cost of sulfur oxychloride reduce, and have reduced environmental pollution;
(3) on technology, can maximize, serialization, stable equipment operation is reliable, 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;
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
A kind of is the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride, comprising:
(1) is that 60% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprises sulfur dichloride 18% in the described crude product sulfur oxychloride, sulfur monochloride 20%.Temperature in the sulfur still is that the surplus temperature of crude product sulfur oxychloride is 65 ℃, 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%, make other material except that the chlorination sulfoxide in the described crude product sulfur oxychloride change into sulfur monochloride, the crude product sulfur oxychloride after obtaining vulcanizing; The content of various compositions is in the crude product sulfur oxychloride: the content of sulfur oxychloride is 65%, and sulfur dichloride content is 5%, sulfur monochloride 30%.
(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 ℃, and cat head 72-75 ℃, 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 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 0.02MPa.Sulfur dichloride content 40% in the described sulfur dichloride mixed gas, chlorine content 40%.
(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 0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 55% in the described mixed gas, sulfur dichloride 15%, 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 40 ℃, the content of sulfur oxychloride is 50% 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 0.02Mpa 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%, and sulfur monochloride content is 15%.
Embodiment two
A kind of is the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride, comprising:
(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 Yu Wenwei≤80 ℃ of crude product sulfur oxychloride, pressure is 0.12MPa, 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, the content of various compositions is in the crude product sulfur oxychloride: the content of sulfur oxychloride is 50%, sulfur dichloride content is 15%, sulfur monochloride 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 ℃, and cat head 72-75 ℃, 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: 0.2; 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 0.16MPa.Sulfur dichloride content 55% 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: 0.2, temperature in the sulfur oxychloride synthesis reactor is 300 ℃, pressure is 0.18MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 35% in the described mixed gas, sulfur dichloride 35%, 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 38 ℃, 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 50%, and sulfur dichloride content is 25%, and sulfur monochloride content is 25%.
Embodiment three
A kind of is the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride, comprising:
(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 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, 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, the content of various compositions is in the crude product sulfur oxychloride: the content of sulfur oxychloride is 60%, sulfur dichloride content is 15%, sulfur monochloride 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 ℃, and cat head 72-75 ℃, 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 0.21MPa 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 0.23MPa.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 150 ℃, pressure is 0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 45% in the described mixed gas, sulfur dichloride 20%, chlorine 15%, sulfurous gas 20%.
(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 60% in the condensed product that obtains, sulfur dichloride content 25%, chlorine content is a small amount of, with the purification that in degassing purification still, outgases of above-mentioned condensed product, in temperature is 70～90 ℃, pressure is under the 0.2MPa condition, the content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the purification is 60%, sulfur dichloride content is 20%, and sulfur monochloride content is 20%.
Claims (10)
1, a kind of is the method for the synthesizing chlorinated sulfoxide of raw material with the crude product sulfur oxychloride, comprising:
(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 described crude product sulfur oxychloride the condensed product purification that outgases;
It is characterized in that, in the described step (1), in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, make that other material except that the chlorination sulfoxide in the described crude product sulfur oxychloride changes into sulfur monochloride.
2, method according to claim 1 is characterized in that, described adding is with respect to wherein the inexcessive sulphur of sulfur dichloride, be meant add with the crude product sulfur oxychloride in the 80-98% of amount of contained sulfur dichloride and the required sulphur of chlorine complete reaction; The preferred sulphur that adds is the 90-97% of the amount of the required sulphur of complete reaction.
3, method according to claim 2 is characterized in that, described inexcessive sulphur in sulfur still or the rectifying tower still add.
4, method according to claim 1 and 2, it is characterized in that, the adding sulphur inexcessive with respect to sulfur dichloride wherein is solid sulphur, described sulfuration is carried out in sulfur still, preferred described sulfuration is independently being carried out in the sulfur still, carry out in the sulfur still that vulcanization reaction is temperature required to be the surplus temperature of crude product sulfur oxychloride, preferred described surplus temperature is≤80 ℃.
5, method according to claim 1 is characterized in that, the content of sulfur oxychloride is 35～65% in the condensed product described in the described step (5), and the content of sulfur oxychloride is 50～70% in the crude product sulfur oxychloride that the described degassing obtains after purifying.
6, method according to claim 1 is characterized in that, the rectifying described in the step (2) is carried out under 75～130 ℃ temperature, and the content of sulfur oxychloride is more than 99.6% in the product that obtains after the rectifying.
7, method according to claim 6 is characterized in that, described rectifying comprises:
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 to change into sulfur monochloride, be back to then at the bottom of the tower with the sulfur dichloride of sulfur oxychloride gaseous volatilization and the excessive sulphur contact reacts in the rectifying tower top sulfuration bed;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached 89 ℃, just the mixing high boiling material with the tower still was discharged to the one-level rectifying tower, obtained 98% above SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78-80 ℃, and cat head 72-75 ℃, reflux ratio is 1:1 ,-0.02～-carry out under the condition of 0.03MPa, obtain purity 99.6% above SOCl from cat head
2
8, method according to claim 2, it is characterized in that described method also comprises is placed on excessive sulphur in the sulfuration bed on top of rectifying tower, other unreacted reactants of part that gasify with sulfur oxychloride during rectifying, reaction of Salmon-Saxl with rectifier, products therefrom presents liquid state, falls back at the bottom of the tower.
9, method according to claim 1, it is characterized in that, mixing high boiling material described in the step (3) feeds the sulfur dichloride synthesis reactor, feed chlorine again, mix under the condition that sulfur monochloride in the high boiling material and excessive chlorine are 0.02MPa-0.23MPa at 70-90 ℃, pressure and react the Cl of feeding
2S with liquid state
2Cl
2Volume ratio be 150: (0.2-0.25); 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 0.02MPa-0.23MPa; Then with the mixed gas of the sulfur dichloride of excessive chlorine and generation and sulfurous gas with Cl
2: SO
2: S
2Cl
2The volume ratio of (liquid) is 150: 100: (0.2-0.25) the synthesizing chlorinated sulfoxide of mode.
According to claim 1 or 9 described methods, it is characterized in that 10, the mixed gas that will discharge from the air outlet in the step (4) mixes with sulfur dioxide gas, make Cl
2: SO
2: liquid S
2Cl
2Volume ratio be 150: 100: (0.2-0.25), react then and obtain sulfur oxychloride gas.
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