CN101412504A - Thionyl chloride synthetic method with reflux pipes arranged at the front and back of pump - Google Patents
Thionyl chloride synthetic method with reflux pipes arranged at the front and back of pump Download PDFInfo
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- CN101412504A CN101412504A CNA2008100047816A CN200810004781A CN101412504A CN 101412504 A CN101412504 A CN 101412504A CN A2008100047816 A CNA2008100047816 A CN A2008100047816A CN 200810004781 A CN200810004781 A CN 200810004781A CN 101412504 A CN101412504 A CN 101412504A
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Abstract
The invention relates to a method for forming gas balance by arranging a return pipe in front of and behind a fan. In the prior art, when a fan is usually taken as a gas conveying device for producing thionyl chloride through a closed type internal circulation method, the pressure fluctuation in a synthesis kettle can result in the situation that the residue reclamation gas from a crude product condenser (3) and a deaeration purification kettle (4) is incapable of entering the synthesis kettle (2). According to the invention, the return pipe is arranged in front of and behind the fan for conveying the residue gas from the condenser and the deaeration device to the synthesis kettle, thereby returning part of gas during the pressure fluctuation in the synthesis kettle, balancing the pressure between the synthesis kettle and the crude product condenser (3) and the deaeration purification kettle (4), and maximally improving the continuity of the three devices and even the whole reaction process.
Description
Technical field
What the present invention relates to is a kind of method that return line forms mass balances that is provided with before and after fan, concretely, what the present invention relates to is in a kind of sulfur oxychloride synthesis technique, utilize fan to be recycled to synthesis reactor by discharging gas in condenser and the de-gassing vessel, for causing described reflux gas, the pressure surge that prevents synthesis reactor can't enter synthesis reactor, perhaps cause the pressure surge of de-gassing vessel or condenser, the present invention is provided with a return line in the front and back of fan.
Background technology
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 be utilize sulfurous gas with the monochloride of sulfur subchloride, dichloride with gac as making the sulfur oxychloride crude product with gas-phase reaction in the presence of the catalyzer, crude product and SULPHUR POWDER are distilled together again and make elaboration, concrete reactions steps has the purification of synthetic and crude product of synthetic, sulfur oxychloride of synthetic, the sulfur dichloride of disulphur dichloride.
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 and to react, begin new reaction after the sulfur monochloride mixture that being mainly after over cure bed and the distillation comprises sulphur adds preheater after passing through the chlorinator chlorination.
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 sum, 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 SOCl2;
(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:
But, in disclosed document, though proposition is arranged, adopt closed internal recycle method to produce, but, in these documents, not open, utilizing fan as air transporting arrangement when (be different from surge pump or other uniflux or have the e Foerderanlage of function of measuring), pressure surge in synthesis reactor may cause coming from crude product condenser 3, the remaining reuse gas of degassing purification still 4 can't enter synthesis reactor 2, and this phenomenon may influence crude product condenser 3, normal procedure in the degassing purification still 4, normally carry out special proposition the present invention in order to realize the production of described closed internal recycle method sulfur oxychloride.
Summary of the invention
The object of the present invention is to provide a kind of sulfur oxychloride synthesis technique, concretely, the present invention relates to provide a kind of in the sulfur oxychloride synthesis technique, for causing described reflux gas, the pressure surge that prevents synthesis reactor can't enter synthesis reactor, perhaps cause the pressure surge of de-gassing vessel or condenser, carry the fan front and back of residual gas to be provided with a return line to synthesis reactor at condenser and de-gassing vessel.
To achieve these goals, the technical solution used in the present invention is:
A kind of thionyl chloride synthetic method that is provided with return line may further comprise the steps:
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
(3) described sulfur oxychloride mixed gas is transported to and carries out condensation in the crude product condenser, obtains phlegma and uncooled property gas;
(4) described phlegma is admitted to crude product degassing purification still and outgases the gas that crude product sulfur oxychloride after obtaining outgasing and degassing purification still outgas out;
The pipeline of described condenser and de-gassing vessel emission gases is merged into a pipeline, and a fan is set on the pipeline after the merging, and the front and back position at fan is provided with a return line, and the gas by described pipeline is admitted to the sulfur oxychloride synthesis reactor with sulfur dioxide gas afterwards.
The unit capacity type selecting of the gas of fan described in the present invention is greater than the unit capacity from crude product condenser, degassing purification still real gas.
The unit capacity type selecting of the gas of fan described in the present invention is greater than from the 1.2-2.5 of the unit capacity of crude product condenser, degassing purification still real gas doubly.
The unit capacity type selecting of the gas of fan described in the present invention is greater than from the 1.4-1.8 of the unit capacity of crude product condenser, degassing purification still real gas doubly.
The gaseous tension of sulfur oxychloride synthesis reactor of the present invention, crude product condenser or degassing purification still fluctuates when big, and open return line and form and reflux, the temperature of re-adjustment crude product condenser, degassing purification still, thus reach balance.
One manual or electronic normal closed gate is set on the return line of the present invention.
One additional fan is set on the return line of the present invention, and under the situation of pressure-stabilisation, the gas that described incorporated fan is carried is consistent with the flow direction of fan delivering gas; Under the situation of pressure surge, the flow direction of the gas that incorporated fan is carried is opposite with the flow direction of fan delivering gas.
Fan of the present invention is a blade fan.
The chemical equation of synthesizing chlorinated sulfoxide is as follows in the prior art, that is:
1, synthetic sulfur monochloride (S
2Cl
2)
Chemical equation: 2S+Cl
2→ S
2Cl
2+ Q Q=58.1KJ/mol;
Reaction principle: the synthetic sulfur monochloride of the directly logical chlorine chlorination of powdery sulphur, reaction process is emitted heat.70～80 ℃ of temperature of reaction.
2, synthetic sulfur dichloride (SCl
2)
Sulfur dichloride is a kind of reddish-brown liquid, and pungent odour is arranged, molecular weight 103.02, and relative density 1.638 is heated and is decomposed more than 40 ℃, English name: Sulfur dichloride, molecular formula: SCl
2
Chemical equation: S
2Cl
2+ Cl
2→ 2SCl
2
Reaction principle: the further chlorination of the excessive logical chlorine of sulfur monochloride generates sulfur dichloride.70～90 ℃ of temperature of reaction;
3, synthesizing chlorinated sulfoxide (SOCl
2)
Sulfur oxychloride has another name called thionyl chloride, sulfurous oxychloride, and outward appearance is colourless or light yellow transparent liquid, and the strong impulse smell is arranged, and molecular formula is SOCl
2, molecular weight is 118.97, fusing point-105 ℃, 75.8 ℃ of boiling points, relative density 1.676g/m
3
Reaction equation:
Cl
2+S
2Cl
2→2SCl
2
SCl
2+Cl
2+SO
2→2SOCl
2
Side reaction: SO
2+ Cl
2→ SO
2Cl
2(SULPHURYL CHLORIDE)
This 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.
Rectifying enters subsider with bottom product after finishing, and pumps into S then
2Cl
2Storage tank passes through 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.
Synthetic sulfur monochloride (S
2Cl
2), obtaining the sulfur monochloride (S of q.s
2Cl
2) after, with described sulfur monochloride (S
2Cl
2), an amount of chlorine injects sulfur dichloride synthesis reactor 1, synthetic sulfur dichloride is main mixed gas, and then with itself and sulfurous gas and inject synthesis reactor from the residual gas of crude product condenser 3, degassing purification still 4 (contain chlorine, sulfurous gas, sulfur dichloride etc. in the described residual gas, specifically can referring to the relevant composition analysis in the aforementioned documents) and react and generate the mixed gas that contains about 40% sulfur oxychloride.
By in the crude product sulfur still, adding sulfur reaction, and derive in tower still bottom and to be rich in sulfur monochloride (S
2Cl
2) liquid enter the sulfur dichloride synthesis reactor again, and enter synthesis reactor from the residual gas recirculation that crude product condenser, degassing purification still can participate in the sulfur oxychloride building-up reactions, formed closed internal recycle method sulfur oxychloride production process.
Specifically, method of the present invention is specially:
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
Mixing high boiling material in the rectifying tower (mainly containing sulfur monochloride) is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, perhaps directly in the sulfur dichloride synthesis reactor, feed sulfur monochloride, feed chlorine again, sulfur monochloride and excessive chlorine are to react the Cl of feeding under the condition of 0.02MPa-0.23MPa at 70-90 ℃, pressure
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%.
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.
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is 150: 100: (0.2-0.25) 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%.
Synthesizing of crude product sulfur oxychloride, 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 ℃.
(3) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, the actual conditions of condensation is≤40 ℃, the content of sulfur oxychloride is 35～65% in the condensed product that obtains, sulfur dichloride content 15～25%, chlorine content is a small amount of, with purifications that in degassing purification still, outgas of above-mentioned condensed product, be that 70-90 ℃, pressure are to carry out under 0.02～0.23Mpa condition in temperature, through the degassing come out not with fixed attention property gas (major ingredient is SO
2And Cl
2, SCl
2) behind the degassing separator, circulation gas-reservoir, be forced into by recirculation blower and be transported to the circulation gas buffering more than the 0.02Mpa, turn back to gas mixer then and use for building-up reactions, circulate thereby finish gas phase.The content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the degassing is purified is 50～70%, and sulfur dichloride content is 15～25%, and sulfur monochloride content is 15-25%.
In order to be separated completely, must be with the low-boiling-point substance SCl in the crude product sulfur oxychloride
2(59 ℃ of boiling points) changes into high boiling material S
2Cl
2(137 ℃ of boiling points) can reflux a few hours then by adding S at rectifier, realizes above-mentioned effect, also can add sulphur in sulfur still and vulcanize.Component S Cl
2And Cl
2Carry out chemical reaction with S, generate S
2Cl
2Be back to liquid phase tower still, make the residual S of tower still
2Cl
2Enrichment.
Equation is as follows:
2S+Cl
2→S
2Cl
2；(S+SCl
2→S
2Cl
2)
In working cycle, produce and rectifying in a spot of SO of producing
2Cl
2, can be sent to the sulfur dichloride synthesis reactor with sulfur monochloride, and then same SCl
2Effect generates SOCl
2, concrete formula as follows:
SO
2Cl
2+SCl
2→2SOCl
2
Synthetic method of the present invention, improve crude product sulfur oxychloride purity by the degassing in the process and reach about 63-68%, so a lot of low-boiling-point substances such as sulfurous gas, sulfur dichloride and a spot of SULPHURYL CHLORIDE all can turn back to the sulfur oxychloride reactor by gas phase and participate in reaction generation sulfur oxychloride again.
(4) be that the crude product sulfur oxychloride that accounts for the 63-68% of crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprise sulfur dichloride 15～25% in the described crude product sulfur oxychloride, temperature in the sulfur still is Yu Wenwei≤80 ℃ of crude product sulfur oxychloride, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the 80-98% of amount of the required sulphur of sulfur dichloride complete reaction, the crude product sulfur oxychloride after obtaining vulcanizing; Each component is in the crude product sulfur oxychloride after the described sulfuration: the content of sulfur oxychloride is 50-65%, sulfur dichloride content position 5-15%, sulfur monochloride content position 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 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 at the bottom of sulfur still or rectifying tower, add how much sulphur to satisfy not complete cure reaction, promptly, it is inexcessive that the sulphur that adds at the bottom of sulfur still or tower is compared with the real reaction amount, can learn by the mode that detects, best, at the bottom of sulfur still or tower, the add-on of sulphur is 80-98% of a complete reaction requirement, is preferably 90-97%.
The sulfuration bed is set on the top of rectifying tower and adds certain sulphur therein, they carry out chemical reaction generation sulfur monochloride with sulfur dichloride that is evaporated and/or chlorine and are back to the tower still, make the residual sulfur monochloride component of tower still enrichment, the distillation procedure sulfur monochloride that finishes is delivered to header tank, used for synthesis, thus the liquid phase working cycle finished.
Discover that the purity of crude product sulfur oxychloride of the present invention needs emphasis to consider, the content with degassing post chlorization sulfoxide that control reaches the sulfur oxychloride of condenser is very important.
If synthetic crude product sulfur oxychloride purity is improved, certainly will cause in the crude product sulfur oxychloride Sulphur Monochloride and sulphur dichloride content low excessively, the total amount that consequently finally can offer sulfur dichloride synthetic sulfur monochloride makes output reduce very little.
Otherwise, if the purity of synthetic crude product sulfur oxychloride is too low, to cause in the crude product sulfur oxychloride Sulphur Monochloride and sulphur dichloride content too high, the total amount that consequently can offer sulfur dichloride synthetic sulfur monochloride is too many, needs other container deposit sulfur monochloride.
(5) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, importantly, in described one-level rectifying, what adopt is the intermittent type charging, so that have time enough to make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78-80 ℃, 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
2A high position, S
2Cl
2S in the high position
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.
In order to reduce or control the pressure fluctuation of sulfur oxychloride synthesis reactor, crude product condenser, three devices of degassing purification still, on described condenser and de-gassing vessel merging pipeline, a fan is set, in the front and back of fan one return line is set, certainly, but in the closed sulfur oxychloride continuous production processes other the device in reuse gas also incorporate described merging pipeline into by pipeline.
In the present invention, described fan is a blade fan, does not comprise the volume pump of the uniflux of surge pump.
In order to form normal backflow, simultaneously, can not cause alternative imbalance because of starting reflux, researchist of the present invention finds, the unit capacity of described fan is greater than being necessary from crude product condenser 3, degassing purification still 4 effective unit tolerance.
As requested, the unit capacity type selecting of described fan doubly is suitable greater than the 1.2-2.5 from crude product condenser, degassing purification still effective unit tolerance, and preferably 1.4-1.8 doubly.
As a kind of selection, when on return line, valve not being set, one additional fan is set on described return line, under the normal circumstances, the gas that described incorporated fan is carried flows to consistent with fan 10, under the situation of pressure surge, the flow direction of the flow direction of incorporated fan gas and fan gas is opposite to reflux so that form.
Select as another kind, during use, when the gaseous tension of sulfur oxychloride synthesis reactor, crude product condenser, degassing purification still fluctuates when big, unlatching is arranged on the manual or electronic normal closed gate on the return line, the pipe that refluxes under the effect of fan forms and refluxes, can reduce the pressure fluctuation of described three devices within a certain period of time, the temperature of re-adjustment crude product condenser, degassing purification still, thus reach in a basic balance.
As outstanding feature of the present invention, one return line simply is set, can be when the synthesis reactor pressure surge, a part of gas refluxes, make operator that the pressure between enough time balance sulfur oxychloride synthesis reactors and crude product condenser and the degassing purification still be arranged, can farthest improve between described three devices, so the continuity of entire reaction process.
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, fan 10, return line 11.
Embodiment
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
Mixing high boiling material in the rectifying tower (mainly containing sulfur monochloride) is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, perhaps directly in the sulfur dichloride synthesis reactor, feed sulfur monochloride, feed chlorine again, sulfur monochloride and excessive chlorine are to react the Cl of feeding under the condition of 0.15MPa at 90 ℃, pressure
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 55% in the described sulfur dichloride mixed gas, chlorine content 30%.
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.2, temperature in the sulfur oxychloride synthesis reactor is 300 ℃, pressure is 0.23MPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 55% in the described mixed gas, sulfur dichloride 15%, chlorine 15%, sulfurous gas 15%.
1., material process
Liquid chlorine, sulfur dioxide liquid are vaporized to 0.3MPa through vaporizer, deliver to the mist eliminator dehydration 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 88 ℃, and is used for synthesis.
2., synthesis procedure
Sulfurous gas, sulfur dichloride mix at mixing tank with circulation gas, after preheater is preheated to 200 ℃, enters reactor and carry out building-up reactions generation sulfur oxychloride mixed gas under 300 ℃.
(3) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, being condensed to temperature is 35 ℃, 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 purifications that in degassing purification still, outgas of above-mentioned condensed product, be that 90 ℃, pressure are to carry out under the 0.12Mpa condition in temperature, through the degassing come out not with fixed attention property gas (major ingredient is SO
2And Cl
2, SCl
2) use for building-up reactions by surge pump delivering gas mixing tank through degassing separator, thereby finish the gas phase circulation.The content that obtains sulfur oxychloride in the described crude product sulfur oxychloride after the degassing is purified is 70%, and sulfur dichloride content is 15%, and sulfur monochloride content is 15%.
(4) be that 68% the crude product sulfur oxychloride that accounts for crude product sulfur oxychloride total amount vulcanizes in sulfur still with sulfur oxychloride content, also comprise sulfur dichloride 15% in the described crude product sulfur oxychloride, temperature in the sulfur still is that the surplus temperature of crude product sulfur oxychloride is 80 ℃, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the required sulphur of sulfur dichloride complete reaction amount 98%, 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;
(5) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, importantly, in described one-level rectifying, what adopt is the intermittent type charging, so that have time enough to make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78-80 ℃, 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 crude product 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 sedimentation with bottom product after finishing, and pumps into S then
2Cl
2The storage, by transferpump with S
2Cl
2Be delivered to S
2Cl
2A high position, S
2Cl
2S in the high position
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.
In order to transport gas from crude product condenser and degassing purification still, one fan need be set (if adopt surge pump or similarly during volume pump on the transfer line after two-way gas merges, owing to there is not the possibility of backflow, therefore there is not this situation), but, if pressure surge may cause described reflux gas can't enter synthesis reactor, perhaps cause the gaseous tension fluctuation of de-gassing vessel or condenser, influence described closed internal recycle method sulfur oxychloride grown place continuity.
Present embodiment is given return line 11 is set before and after described fan, when the method that forms mass balances, concretely, what the present invention relates to is in a kind of sulfur oxychloride synthesis technique, utilizes fan to be recycled to synthesis reactor the present invention by discharge gas in condenser and the de-gassing vessel and is provided with a return line 11 in the front and back of fan.
When the synthesis reactor bottom pressure makes can't enter synthesis reactor from gases such as crude product condenser 3, degassing purification stills 4 time, the part residual gas is in the front and back of fan pump around circuit, therefore operator have the time of enough adjusting, and make the production of closed internal recycle method sulfur oxychloride continuity to carry out.
As aforementioned, in order to transport self cooling condenser or de-gassing vessel ground gas, one fan need be set (if adopt surge pump or similarly during volume pump on the transfer lime after the two merges, owing to do not have the possibility of backflow, therefore do not have this situation), still, if pressure surge, may cause described reflux gas can't enter synthesis reactor, perhaps cause the gaseous tension fluctuation of de-gassing vessel or condenser, influence described closed internal recycle method sulfur oxychloride grown place continuity.
The settling mode that present embodiment provides is, return line 11 is set before and after described fan, when the method that forms mass balances, concretely, what the present invention relates to is in a kind of sulfur oxychloride synthesis technique, utilizes fan to be recycled to synthesis reactor the present invention by discharge gas in condenser and the de-gassing vessel and is provided with a return line 11 in the front and back of fan.
When the synthesis reactor bottom pressure makes can't enter synthesis reactor from gases such as crude product condenser 3, degassing purification stills 4 time, the part residual gas is in the front and back of fan pump around circuit, provide the time that device or operator adjust, make the production of described closed internal recycle method sulfur oxychloride continuity to carry out.
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
Mixing high boiling material in the rectifying tower (mainly containing sulfur monochloride) is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, perhaps directly in the sulfur dichloride synthesis reactor, feed sulfur monochloride, feed chlorine again, sulfur monochloride and excessive chlorine are to react the Cl of feeding under the condition of 0.02MPa at 70 ℃, pressure
2With S liquid in the sulfur dichloride synthesis reactor
2Cl
2Volume ratio be 150: 0.2; Cl
2And S
2Cl
2In the sulfur dichloride synthesis reactor, react the SCl of generation
2With excessive Cl
2Mixed gas discharge from the air outlet, the pressure P 1 of described air outlet is 0.04MPa.Sulfur dichloride content 40% in the described sulfur dichloride mixed gas, chlorine content 40%.
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl2:SO in the synthesis reactor
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.25, temperature in the sulfur oxychloride synthesis reactor is 150 ℃, pressure is 0.02MPaMPa, obtain the sulfur oxychloride mixed gas behind synthetic the finishing, contain chlorination sulfoxide 35% in the described mixed gas, sulfur dichloride 25%, chlorine 20%, sulfurous gas 20%.
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 80 ℃, 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 ℃.
(3) 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 45% in the condensed product that obtains, sulfur dichloride content 20%, chlorine content is a small amount of, with purifications that in degassing purification still, outgas of above-mentioned condensed product, be that 90 ℃, pressure are to carry out under the 0.23Mpa condition in temperature, through the degassing come out not with fixed attention property gas (major ingredient is SO
2And Cl
2, SCl
2) 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%, and sulfur dichloride content is 25%, and sulfur monochloride content is 25%.
(4) be that 63% 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 Yu Wenwei≤80 ℃ of crude product sulfur oxychloride, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the 80-98% of amount of the required sulphur of sulfur dichloride complete reaction, the crude product sulfur oxychloride after obtaining vulcanizing;
(5) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, importantly, in described one-level rectifying, what adopt is the intermittent type charging, so that have time enough to make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78-80 ℃, 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 crude product 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 sedimentation with bottom product after finishing, and pumps into S then
2Cl
2The storage, by transferpump with S
2Cl
2Be delivered to S
2Cl
2A high position, S
2Cl
2S in the high position
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.
Though before and after described fan, be provided with return line 11, when the synthesis reactor bottom pressure makes can't enter synthesis reactor from gases such as crude product condenser 3, degassing purification stills 4 time, the part residual gas is in the front and back of fan pump around circuit, but, when the flow of fan less than from the generation of crude product condenser 3, degassing purification still 4 time, gas on the synthesis reactor can still influence the interior pressure of crude product condenser 3, degassing purification still 4 by the gap between the blade of return line or fan, causes the continuous process of producing.
If the flow of fan is excessive, may cause the air pressure fluctuation in crude product condenser 3, the degassing purification still 4 etc.; Open return line, equally also can influence the reaction pressure in the synthesis reactor, therefore, in this case, the flow of fan is 1.2-2.5 a times of tolerance such as actual crude product condenser 3, degassing purification still 4, and preferred 1.4-1.8 doubly.
During use, when the gaseous tension of synthesis reactor, crude product condenser 3, degassing purification still 4 fluctuates greatly, open return line and form backflow, this mode can reduce the pressure fluctuation of described three devices within a certain period of time, finely tune the temperature of crude product condenser 3, degassing purification still 4 again, progressively reach in a basic balance.
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
Mixing high boiling material in the rectifying tower (mainly containing sulfur monochloride) is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, perhaps directly in the sulfur dichloride synthesis reactor, feed sulfur monochloride, feed chlorine again, sulfur monochloride and excessive chlorine are to react the Cl of feeding under the condition of 0.16MPa at 80 ℃, pressure
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 50% in the described sulfur dichloride mixed gas, chlorine content 35%.
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.23, 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 45% in the described mixed gas, sulfur dichloride 20%, chlorine 15%, sulfurous gas 20%.
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 78 ℃, and is used for synthesis.
2., synthesis procedure
Sulfurous gas, sulfur dichloride mix at mixing tank with circulation gas, after preheater is preheated to 200 ℃, enters reactor and carry out building-up reactions generation sulfur oxychloride crude product synthetic gas under 250 ℃.
(3) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, the actual conditions of condensation is 25 ℃, the content of sulfur oxychloride is 55% in the condensed product that obtains, sulfur dichloride content 15%, chlorine content is a small amount of, with purifications that in degassing purification still, outgas of above-mentioned condensed product, be that 80 ℃, pressure are to carry out under the 0.02Mpa 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 60%, and sulfur dichloride content is 20%, and sulfur monochloride content is 20%.
(4) 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 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, crude product sulfur oxychloride after obtaining vulcanizing, wherein sulfur oxychloride content is 55%, sulfur dichloride content is 10%, and sulfur monochloride content is 35%;
(5) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, importantly, in described one-level rectifying, what adopt is the intermittent type charging, so that have time enough to make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78-80 ℃, 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.
Other identical with embodiment 1, different is before and after described fan return line 11 to be set, and a manual or electronic normal closed gate is set on the described return line.
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
Mixing high boiling material in the rectifying tower (mainly containing sulfur monochloride) is discharged from tower, to the tower still, by pump described mixing high boiling material is delivered to the sulfur dichloride synthesis reactor then, perhaps directly in the sulfur dichloride synthesis reactor, feed sulfur monochloride, feed chlorine again, sulfur monochloride and excessive chlorine are to react the Cl of feeding under the condition of 0.21MPa at 80 ℃, pressure
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 48% in the described sulfur dichloride mixed gas, chlorine content 36%.
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
With sulfur dichloride and excessive Cl
2Mixed gas is delivered to the sulfur oxychloride synthesis reactor, feeds sulfur dioxide gas in described synthesis reactor, gas Cl in the synthesis reactor
2: SO
2: S
2Cl
2The volume ratio of (liquid) is to deliver to the synthesizing chlorinated sulfoxide of sulfur oxychloride synthesis reactor at 150: 100: 0.25, 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 40% in the described mixed gas, sulfur dichloride 25%, chlorine 15%, sulfurous gas 20%.
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 80 ℃, 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 ℃.
(3) the sulfur oxychloride mixed gas that obtains is carried out condensation in condenser, the actual conditions of condensation is 20 ℃, the content of sulfur oxychloride is 35% in the condensed product that obtains, sulfur dichloride content 25%, chlorine content is a small amount of, with purifications that in degassing purification still, outgas of above-mentioned condensed product, be that 70 ℃, pressure are to carry out under the 0.16Mpa 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%, and sulfur dichloride content is 25%, and sulfur monochloride content is 25%.
(4) be that 66% 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 18% in the described crude product sulfur oxychloride, temperature in the sulfur still is that the surplus temperature of crude product sulfur oxychloride is 70 ℃, pressure is normal pressure, in described crude product sulfur oxychloride, add the inexcessive sulphur of sulfur dichloride with respect to wherein, the add-on of sulphur be with the crude product sulfur oxychloride in the 80-98% of amount of the required sulphur of sulfur dichloride complete reaction, crude product sulfur oxychloride after obtaining vulcanizing, wherein sulfur oxychloride content is 60%, sulfur dichloride 15%, sulfur monochloride 25%.
(5) the crude product sulfur oxychloride after will vulcanizing carries out rectifying, obtains sulfur oxychloride and mixes high boiling material, and described rectifying is carried out in rectifying tower, carries out three grades of rectifying;
A, one-level rectifying: tower still temperature is between 110-130 ℃, cat head obtains 80～95% sulfur oxychloride, importantly, in described one-level rectifying, what adopt is the intermittent type charging, so that have time enough to make a spot of excessive sulphur contact reacts of vulcanizing in the bed with the sulfur dichloride and the rectifying tower top of sulfur oxychloride gaseous volatilization change into sulfur monochloride, be back to then at the bottom of the tower;
B, two-stage rectification: tower still temperature is controlled at 70～105 ℃, and when tower still temperature reached certain liquid level and temperature and reaches 89 ℃, just the high boiling material with the tower still was discharged to the one-level rectifying tower, obtains 98% left and right sides SOCl from cat head
2
C, three grades of rectifying: tower still temperature is at 78-80 ℃, 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
Other is identical with embodiment 2, different is, return line 11 is set before and after described fan, one additional fan is set on the described return line, under the normal circumstances, the gas that described incorporated fan is carried is consistent with fan 10 flow directions, and under the situation of pressure surge, the flow direction of incorporated fan flows to opposite with fan 10.
Claims (8)
1, a kind of thionyl chloride synthetic method that is provided with return line before and after pump may further comprise the steps:
(1) in the sulfur dichloride synthesis reactor, feeds sulfur monochloride and excessive chlorine, obtain the mixed gas of sulfur dichloride and chlorine;
(2) mixed gas of sulfur dichloride of discharging from the sulfur dichloride synthesis reactor and chlorine and sulfur dioxide gas are sent in the sulfur oxychloride synthesis reactor, after reacting completely, obtain the sulfur oxychloride mixed gas;
(3) described sulfur oxychloride mixed gas is transported to and carries out condensation in the crude product condenser, obtains phlegma and reaches not property gas with fixed attention;
(4) described phlegma is admitted to crude product degassing purification still and outgases the gas that crude product sulfur oxychloride after obtaining outgasing and degassing purification still take off;
It is characterized in that, the pipeline of described condenser and de-gassing vessel emission gases is merged into a pipeline, and a fan is set on the pipeline after the merging, and the front and back position at fan is provided with a return line, and the gas by described pipeline is admitted to the sulfur oxychloride synthesis reactor with sulfur dioxide gas afterwards.
2, method according to claim 1, the unit capacity type selecting that it is characterized in that described fan gas are greater than the unit capacity from crude product condenser, degassing purification still real gas.
3, method according to claim 2, the unit capacity type selecting that it is characterized in that described fan gas is greater than from the 1.2-2.5 of the unit capacity of crude product condenser, degassing purification still real gas doubly.
4, method according to claim 3, the unit capacity type selecting that it is characterized in that described fan gas is greater than from the 1.4-1.8 of the unit capacity of crude product condenser, degassing purification still real gas doubly.
5, method according to claim 1, it is characterized in that the gaseous tension of described sulfur oxychloride synthesis reactor, crude product condenser or degassing purification still fluctuates when big, open return line and form and reflux, the temperature of re-adjustment crude product condenser, degassing purification still, thus reach balance.
6, method according to claim 1 is characterized in that, a manual or electronic normal closed gate is set on the described return line.
7, method according to claim 1 is characterized in that, an additional fan is set on the described return line, and under the situation of pressure-stabilisation, the gas that described incorporated fan is carried is consistent with the flow direction of fan (10) delivering gas; Under the situation of pressure surge, the flow direction of the gas that incorporated fan is carried is opposite with the flow direction of fan (10) delivering gas.
8, method according to claim 1 is characterized in that described fan is a blade fan.
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|---|---|---|---|
| CN2008100047816A CN101412504B (en) | 2008-01-30 | 2008-01-30 | Thionyl chloride synthetic method with reflux pipes arranged at the front and back of pump |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100047816A CN101412504B (en) | 2008-01-30 | 2008-01-30 | Thionyl chloride synthetic method with reflux pipes arranged at the front and back of pump |
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| CN101412504B CN101412504B (en) | 2011-03-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108686A (en) * | 2014-07-31 | 2014-10-22 | 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 |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108686A (en) * | 2014-07-31 | 2014-10-22 | 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 |
| 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 |
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