CN100480174C - Gas phase circulation method in synthesis of thionyl chloride - Google Patents
Gas phase circulation method in synthesis of thionyl chloride Download PDFInfo
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- CN100480174C CN100480174C CNB2008100047820A CN200810004782A CN100480174C CN 100480174 C CN100480174 C CN 100480174C CN B2008100047820 A CNB2008100047820 A CN B2008100047820A CN 200810004782 A CN200810004782 A CN 200810004782A CN 100480174 C CN100480174 C CN 100480174C
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Abstract
The invention relates to a method of gas phase in the synthesis of thionyl chloride and particularly includes synthesizing sulfur dichloride by adding chlorine to sulfur monochloride, synthesizing crude thionyl chloride gas of light concentration by adding chlorine and sulfur dioxide, then subjecting the thionyl chloride gas to condensation, desaeration, purification, sulfuration and distillation to obtain the sulfur monochloride, and then rectifying the sulfur monochloride, thus representing the method for all gases to enter the circulated use during the whole process.
Description
Technical field
What the present invention relates to is the gas phase circulation method of a kind of sulfur oxychloride in synthetic, concretely, comprise from sulfur monochloride and add the synthetic sulfur dichloride of chlorine, sulfur dichloride adds the crude product sulfur oxychloride gas of chlorine and the synthetic low concentration of sulfurous gas, purify through condensation, the degassing then and vulcanize and distillate sulfur monochloride and rectifying, in whole link, make whole gas enter the method that recycles.
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; This patent documentation also discloses and will react after the sulfur monochloride mixture that being mainly after over cure bed and the distillation comprises sulphur adds preheater A after passing through the chlorinator chlorination, begins 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, propose to adopt closed internal recycle method to produce though have,, as a heavy construction project, in view of this not open concrete technical scheme how closed internal recycle method is produced sulfur oxychloride, specially proposes the present invention.
Summary of the invention
The object of the present invention is to provide the gas phase circulation method of a kind of sulfur oxychloride in synthetic.
Purpose of the present invention can be achieved in the following manner:
A kind of sulfur dioxide gas is combined to the gas phase circulation method in the sulfur oxychloride, it is characterized in that: the circulation of described gas phase is the part of the gas got rid of of the gas deviate from the gas that will deviate from the crude product condenser, the crude product degassing purification still or rectifying tower as the synthesis gas raw material sources of sulfur oxychloride, enter the recycle of sulfur oxychloride synthesis reactor once more, send the sulfur oxychloride synthesis reactor back to by gas unidirectional conveying apparatus at least one in the described gas raw material source.
In the gas phase circulation method of the present invention, the gas of deviating from the described crude product condenser is sent the sulfur oxychloride synthesis reactor back to by gas unidirectional conveying apparatus.
Above-mentioned gas unidirectional conveying apparatus is a surge pump.
Among the present invention, the gas of deviating from the described crude product degassing purification still is that temperature by regulating crude product degassing purification still is so that its pressure that raises is sent the sulfur oxychloride synthesis reactor back to.
The gas of deviating from the described crude product degassing purification still is forced into by recirculation blower and is transported to the circulation gas surge tank about 0.12MPa, turns back to gas mixer then and uses for building-up reactions, thereby finish the gas phase circulation.Preferably, the gas of deviating from the described crude product degassing purification still is forced into 0.08Mpa by air pump and is delivered to the circulation gas surge tank through degassing separator, circulation gas basin, returns mixing tank then and uses for building-up reactions.
Among the present invention, the crude product sulfur oxychloride after the degassing is purified through described crude product degassing purification still carries out inexcessive sulfuration earlier, excessive sulfuration in rectifying again, and the gas delivery that will produce from rectifying tower is in the sulfur oxychloride synthesis reactor then.
Among the present invention, the purity of the crude product sulfur oxychloride after the degassing is purified through described crude product degassing purification still reaches 50-75%.Synthetic in order there to be enough gas circulation to participate in, it is important that the crude product sulfur oxychloride purity after the preferred described degassing is purified reaches about 63-68%.
Among the present invention, the mixed gas that comes from the bottom of the described sulfur oxychloride synthesis reactor still enters condensation in the crude product condenser, and the top expellant gas of described crude product condenser is non-condensable gases SO under the minute quantity normal temperature
2, chlorine, a spot of SCl
2Steam.
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 the about 63-68% of chlorination sulfoxide 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.
For clearer explanation the present invention, below the synthesis technique of sulfur oxychloride among the present invention described earlier:
(1) be that 68% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in the crude product sulfur still with sulfur oxychloride content, also comprise a spot of sulfur dichloride in the described crude product sulfur oxychloride, temperature in the crude product 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 required sulphur of sulfur dichloride complete reaction amount 80%, 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 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 crude product sulfur still to be carried out, and is also included within the sulfidation of carrying out in the rectifying tower.
Excessive sulphur it is to be noted that especially adding sulphur in crude product 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 reactant 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 crude product sulfur still can be independently, also can directly sulphur be joined in the crude product degassing purification still to vulcanize.
Need at the bottom of crude product sulfur still or rectifying Tata, 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 crude product 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, control enters the content of the sulfur oxychloride in the crude product condenser and the content of process crude product degassing purification still degassing purification post chlorization sulfoxide is very important.
If the purity of synthetic crude product sulfur oxychloride 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, and is specific as follows:
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains the sulfur oxychloride of 80-95%, in described one-level rectifying, adopt the interval 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: 78-80 ℃ of tower still temperature, cat head 72-75 ℃, reflux ratio 1:1, pressure-0.02～-carry out under the condition of 0.03MPa, can obtain the SOCl of purity more than 99.6% 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 spot 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, in the through 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 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) deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor, temperature in the sulfur oxychloride synthesis reactor is the 150-300 degree, 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 crude product condenser, from the gas of crude product degassing purification still 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 the crude product condenser, the actual conditions of condensation is≤40 ℃, the content of sulfur oxychloride is at 35-65% in the condensed product that obtains, sulfur dichloride content 15-25%, chlorine content is a small amount of, is that 70-90 ℃, pressure be 0.02-0.23Mpa condition under outgas purification in temperature with above-mentioned condensed product in degassing purification still, the content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the purification is 50-70%, 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
The a spot of SO that produces in that in working cycle, produce and the rectifying
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.
In the above-mentioned processing step, there is the gas in three places to can be used as the part of the synthesis gas raw material sources of sulfur oxychloride, enters the recycle of sulfur oxychloride synthesis reactor once more, thereby finish the gas phase circulation.Specific as follows:
(1) described in the step (5), the condensed product that the obtains purification that in degassing purification still, outgases, and non-condensable gases SO under the minute quantity normal temperature
2Content 40～50%, chlorine content 40～50% and a spot of SCl
2Then be pumped in the sulfur oxychloride synthesis reactor, thereby finish the gas phase circulation by gas unidirectional conveying apparatus such as pneumatic diaphragm;
(2) described in the step (5), the condensed product that obtains purifications that in degassing purification still, outgas, the crude product sulfur oxychloride that obtains after the purification carries out next circulation again, and the SO that from the purification still that outgases, deviates from
2Content 25～35%, chlorine content 25～35% and a spot of SOCl
2Utilize pressure difference to be conveyed in the sulfur oxychloride synthesis reactor, thereby finish the gas phase circulation;
(3) described in the step (2), crude product sulfur oxychloride after the sulfuration carries out rectifying in rectifying tower, obtain sulfur oxychloride and mix high boiling material and tail gas, contained gas has sulfurous gas (accounting for 45-55%) in this tail gas, sulfur oxychloride (accounting for 35-45%), chlorine (accounting for 2%), other non-condensable gases (accounting for 8%).Mix high boiling material and from tower, discharge, in the through still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, finish the liquid phase circulation.And tail gas mainly to be sulfurous gas and chlorine be pumped in the sulfur oxychloride synthesis reactor by gas unidirectional conveying apparatus such as pneumatic diaphragm, thereby finish the gas phase circulation.
Among the present invention, the gas that the gas deviate from the gas deviate from the crude product condenser, the crude product degassing purification still or rectifying tower are got rid of enters the recycle of sulfur oxychloride synthesis reactor once more as the part of the synthesis gas raw material sources of sulfur oxychloride.
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 gas phase circulation, almost do not have the gaseous contamination gas evolution, can not cause environmental pollution;
(4) on technology, can maximize, serialization, stable equipment operation is reliable, energy consumption is low.
Description of drawings
Accompanying drawing 1 is the preparation technology's of a sulfur oxychloride of the present invention basic flow sheet;
Accompanying drawing 2 is gas phase round-robin process flow sheets 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, crude product 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, gas unidirectional conveying apparatus 11.
Embodiment
Below be the specific embodiment of the present invention, described embodiment is in order to further describe the present invention, rather than restriction the present invention.
Present embodiment is the gas describing among the present invention to deviate from the crude product condenser part as the synthesis gas raw material sources of sulfur oxychloride, enters the recycle of sulfur oxychloride synthesis reactor once more, thereby finishes gas phase round-robin method, and this method 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 78 ℃ of the surplus temperature 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 required sulphur of sulfur dichloride complete reaction amount 80%, the crude product sulfur oxychloride after obtaining vulcanizing; Wherein the content of various compositions is in the crude product sulfur oxychloride: 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: the temperature control of tower still is between 110-130 ℃, cat head obtains 80% sulfur oxychloride, in described one-level rectifying, adopt the interval 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 between 70-105 ℃, when tower still temperature reaches certain liquid level and temperature and reaches 89 ℃, just the height of tower still is mixed thing and is discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: 78-80 ℃ of tower still temperature, cat head 72-75 ℃, reflux ratio be 1:1, pressure-0.02～-carry out under the condition of 0.03MPa, obtain the SOCl of purity 99.8% 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, in the through still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, feed chlorine again, mix sulfur monochloride in the high boiling material and excessive chlorine and under 70 ℃, the condition of pressure 0.02MPa, 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 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: 0.2, temperature in the sulfur oxychloride synthesis reactor is 300 degree, pressure is 0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 35% in the described mixed gas, sulfur dichloride 25%, chlorine 20%, sulfurous gas 20%.
(5) the sulfur oxychloride mixed gas that obtains is carried out condensation in the crude product condenser under 40 ℃ condition and obtain condensed product, the content of sulfur oxychloride is 65% in the described condensed product, sulfur dichloride content 25%, chlorine 10%, is that 90 ℃, pressure be 0.23Mpa condition under outgas purify obtain crude product sulfur oxychloride in temperature with above-mentioned condensed product in crude product degassing purification still, the content of sulfur oxychloride is 50% in the described crude product sulfur oxychloride, sulfur dichloride content is 20%, and sulfur monochloride content is 28%.Non-condensable gases then utilizes pressure difference to be conveyed in the sulfur oxychloride reactor under the normal temperature of deviating from from the crude product condenser, finishes the gas phase circulation, wherein SO in the non-condensable gases
2Content 40%, chlorine content 50% and 10% sulfur dichloride.
Present embodiment is the gas describing among the present invention to deviate from the purification still that crude product the outgased part as the synthesis gas raw material sources of sulfur oxychloride, enters recycle in the sulfur oxychloride synthesis reactor 2 once more, thereby finishes gas phase round-robin method.This method is specific as follows:
Described in embodiment 1 step (5), the sulfur oxychloride mixed gas carries out condensation under 38 ℃ condition in the crude product condenser, the content of sulfur oxychloride is 65% in the condensed product that obtains, sulfur dichloride content 25%, chlorine 10%, is that 90 ℃, pressure be the condition of 0.02Mpa under outgas purify obtain crude product sulfur oxychloride in temperature with described condensed product in crude product degassing purification still, and the crude product sulfur oxychloride carries out next circulation again.And the SO that from degassing purification still, deviates from
2Content 25%, chlorine content 35% and SOCl
216% of content is forced into by recirculation blower and is transported to the circulation gas surge tank about 0.12MPa, turns back to gas mixer then and is transported in the sulfur oxychloride reactor again and reacts, thereby finish the gas phase circulation.
Present embodiment is to describe the gas among the present invention rectifying tower the got rid of part as the synthesis gas raw material sources of sulfur oxychloride, enters the recycle of sulfur oxychloride synthesis reactor once more, thereby finishes gas phase round-robin method.This method is specific as follows:
Described in embodiment 1 step (2), crude product sulfur oxychloride after the sulfuration carries out rectifying in rectifying tower, obtain sulfur oxychloride and mix high boiling material and tail gas, contained gas has sulfurous gas (accounting for 45%) in this tail gas, sulfur oxychloride (accounting for 45%), chlorine (accounting for 2%), other non-condensable gases (accounting for 8%).Mix high boiling material and from tower, discharge, in the through still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, finish the liquid phase circulation.And tail gas mainly to be sulfurous gas and chlorine be pumped in the sulfur oxychloride synthesis reactor by gas unidirectional conveying apparatus such as pneumatic diaphragm, thereby finish the gas phase circulation.
Present embodiment is the gas describing among the present invention to deviate from the crude product condenser part as the synthesis gas raw material sources of sulfur oxychloride, enters the recycle of sulfur oxychloride synthesis reactor once more, thereby finishes gas phase round-robin method, and this method comprises:
(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 25% in the described crude product sulfur oxychloride, temperature in the sulfur still is 80 ℃ of the surplus temperature 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 required sulphur of sulfur dichloride complete reaction amount 88%, the crude product sulfur oxychloride after obtaining vulcanizing; Wherein 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%, and sulfur monochloride content is 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: the temperature control of tower still is between 110-130 ℃, cat head obtains 95% sulfur oxychloride, in described one-level rectifying, adopt the interval 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 between 70-105 ℃, when tower still temperature reaches certain liquid level and temperature and reaches 89 ℃, just the height of tower still is mixed thing and is discharged to the one-level rectifying tower, obtains SOCl about 98% from cat head
2
C, three grades of rectifying: 78-80 ℃ of tower still temperature, cat head 72-75 ℃, reflux ratio be 1:1 and pressure-0.02～-carry out under the condition of 0.03MPa, can obtain the SOCl of purity 99.7% 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, in the straight tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, feed chlorine again, mix sulfur monochloride in the high boiling material and excessive chlorine and under 90 ℃, the condition of pressure 0.23MPa, 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
2Discharge from the air outlet with the mixed gas of excessive Cl2, the pressure P 1 of described air outlet is 0.23MPa.Sulfur dichloride content 55% 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: 0.2, temperature in the sulfur oxychloride synthesis reactor is 150 degree, pressure is 0.02MPa, 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 40 ℃, the content of sulfur oxychloride is 65% in the condensed product that obtains, sulfur dichloride content 25%, chlorine 10%, is that 70 ℃, pressure be the condition of 0.02Mpa under outgas purification in temperature with above-mentioned condensed product in crude product degassing purification still, the content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the purification is 65%, sulfur dichloride content is 15%, and sulfur monochloride content is 25%.Non-condensable gases then utilizes pressure difference to be conveyed in the sulfur oxychloride reactor under the normal temperature of deviating from from the crude product condenser, finishes the gas phase circulation, wherein SO in the non-condensable gases
2Content 50%, chlorine content 40% and 10% sulfur dichloride.
Present embodiment is the gas describing among the present invention to deviate from the purification still that crude product the outgased part as the synthesis gas raw material sources of sulfur oxychloride, enters recycle in the sulfur oxychloride synthesis reactor 2 once more, thereby finishes gas phase round-robin method.This method is specific as follows:
Described in embodiment 1 step (5), the sulfur oxychloride mixed gas carries out condensation under 38 ℃ condition in the crude product condenser, the content of sulfur oxychloride is 65% in the condensed product that obtains, sulfur dichloride content 25%, chlorine 10%, is that 90 ℃, pressure be the condition of 0.02Mpa under outgas purify obtain crude product sulfur oxychloride in temperature with described condensed product in crude product degassing purification still, and the crude product sulfur oxychloride carries out next circulation again.And the SO that from crude product degassing purification still, deviates from
2Content 35%, chlorine content 25% and SOCl
216% of content is forced into 0.08Mpa by air pump and is delivered to the circulation gas surge tank through degassing separator, circulation gas basin, turns back to gas mixer then and is transported in the sulfur oxychloride reactor again and reacts, thereby finish the gas phase circulation.
Claims (8)
1, a kind of sulfur dioxide gas is combined to the gas phase circulation method in the sulfur oxychloride, it is characterized in that: the circulation of described gas phase is the part of the gas got rid of of the gas deviate from the gas that will deviate from the crude product condenser, the crude product degassing purification still or rectifying tower as the synthesis gas raw material sources of sulfur oxychloride, enter the recycle of sulfur oxychloride synthesis reactor once more, send the sulfur oxychloride synthesis reactor back to by gas unidirectional conveying apparatus at least one in the described gas raw material source.
2, gas phase circulation method according to claim 1 is characterized in that: the gas of deviating from the described crude product condenser is sent the sulfur oxychloride synthesis reactor back to by gas unidirectional conveying apparatus.
3, gas phase circulation method according to claim 2 is characterized in that: described gas unidirectional conveying apparatus is a surge pump.
4, gas phase circulation method according to claim 1 is characterized in that: the gas of deviating from the described crude product degassing purification still is that temperature by regulating crude product degassing purification still is so that its pressure that raises is sent the sulfur oxychloride synthesis reactor back to.
5, gas phase circulation method according to claim 1, it is characterized in that: the gas of deviating from the described crude product degassing purification still is forced into by recirculation blower and is transported to the circulation gas surge tank about 0.12MPa, turns back to gas mixer then and uses for building-up reactions.
6, gas phase circulation method according to claim 1, it is characterized in that: the crude product sulfur oxychloride after the degassing is purified through described crude product degassing purification still carries out inexcessive sulfuration earlier, excessive sulfuration in rectifying again, the gas delivery that will produce from rectifying tower is in the sulfur oxychloride synthesis reactor then.
7, method according to claim 6 is characterized in that: the purity of the crude product sulfur oxychloride after the degassing is purified through described crude product degassing purification still reaches 50-75%.
8, method according to claim 1, it is characterized in that: the gas of deviating from the described crude product degassing purification still is forced into 0.08Mpa by air pump and is delivered to the circulation gas surge tank through degassing separator, circulation gas basin, returns mixing tank then and uses for building-up reactions.
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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 |
| CN104108686B (en) * | 2014-07-31 | 2015-07-08 | 江西世龙实业股份有限公司 | Pressure-relief discharge, absorption, treatment and recycling method in production process of thionyl chloride |
| CN104445091A (en) * | 2014-12-12 | 2015-03-25 | 山东凯盛新材料有限公司 | Method for inhibiting generation of chlorosulfuric acid in thionyl chloride preparation process |
| 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 |
| CN109485019B (en) * | 2018-11-27 | 2020-11-13 | 江西世龙实业股份有限公司 | Gas phase circulating device and method for producing thionyl chloride |
| CN111453704B (en) * | 2019-01-18 | 2021-11-23 | 江西世龙实业股份有限公司 | Device and method for recycling tail gas generated in thionyl chloride production |
| CN111320140B (en) * | 2019-02-25 | 2021-08-13 | 江西世龙实业股份有限公司 | Thionyl chloride production system and driving method thereof |
| CN114314524A (en) * | 2022-01-04 | 2022-04-12 | 安徽金轩科技有限公司 | Method for improving synthesis yield by utilizing synthesis energy of thionyl chloride |
| CN114195104A (en) * | 2022-01-04 | 2022-03-18 | 安徽金轩科技有限公司 | Method for improving synthesis yield by detecting thionyl chloride gas |
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Denomination of invention: Gas phase circulation method in synthesis of thionyl chloride Effective date of registration: 20191226 Granted publication date: 20090422 Pledgee: Leping sub branch of Jiujiang Bank Co., Ltd Pledgor: Jiangxi Selon Industrial Co., Ltd. Registration number: Y2019990000807 |
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