CN109485019A - A kind of thionyl chloride production gas phase circulator and method - Google Patents
A kind of thionyl chloride production gas phase circulator and method Download PDFInfo
- Publication number
- CN109485019A CN109485019A CN201811427355.3A CN201811427355A CN109485019A CN 109485019 A CN109485019 A CN 109485019A CN 201811427355 A CN201811427355 A CN 201811427355A CN 109485019 A CN109485019 A CN 109485019A
- Authority
- CN
- China
- Prior art keywords
- gas
- thionyl chloride
- crude product
- synthesis reactor
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4561—Compounds containing sulfur, halogen and oxygen only
- C01B17/4569—Thionyl fluoride (SOF2)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides a kind of thionyl chloride production gas phase circulator and methods, the gas phase circulation is delivered in gas separator for condenser, degassing are purified the incoagulable gas deviate from least one in kettle and rectifying device, chlorine after separation is passed through in sulfur dichloride synthesis reactor, and the sulfur dioxide after separation is passed into thionyl chloride crude product synthesis reactor.The present invention uses gas unidirectional conveying apparatus by condenser, the incoagulability tail gas generated in crude product receiving slit and rectifying device is delivered in gas separator, adsorbent equipment reconciliation adsorbent equipment is provided in gas separator, adsorbent equipment is used to absorb the sulfur dioxide in incoagulable gas, after incoagulable gas passes through gas separator, non-absorbent chlorine is passed directly in sulfur dichloride synthesis reactor, and sulfur dichloride is adsorbed device and fully absorbs, thus effectively chlorine and sulfur dioxide are distinguished, avoid pressure rise in thionyl chloride synthesis reactor, influence being normally carried out for reaction.
Description
Technical field
The present invention relates to chemical process field more particularly to a kind of thionyl chloride production gas phase circulator and method.
Background technique
The production method of thionyl chloride has ten several, and still, large-scale industrial production is substantially following three kinds of technique
Route: (1) phosphorus pentachloride is reacted with sulfur dioxide, simple process, but SOCl2With POCl3It is difficult to separate, is difficult to obtain high-purity
SOCl2；(2) with antimony chloride etc. for catalyst, sulfur chloride is reacted with chlorosulfonic acid, and the current country is widely used, complex process, investment
It is larger；(3) gas-phase catalysis produces thionyl chloride, using active carbon as catalyst, sulfur chloride and sulfur dioxide, chlorine reaction, and state
It generalling use outside, simple process, small investment and product purity are high, and closed circulation device can be used and produce, non-environmental-pollution,
Fundamental reaction formula is as follows:
(1)、
(2)、
As the Typical Representative of the above-mentioned prior art (3), US2431823, which is disclosed, utilizes disulphur dichloride (S2Cl2) and chlorine
Solid/liquid/gas reactions, the sulfur dichloride (SCl of generation2) and excessive chlorine and sulfur dioxide and the chlorine of the importing gas under activated carbon catalysis
Phase reaction obtains thionyl chloride through distillation；The document also discloses that by predominantly wrapping through over cure bed and after distilling after reaction
Preheater A is added in the sulfur monochloride mixture for including sulphur after chlorinator chlorination, starts new reaction.But in the disclosure
In document, come after the gas merging of condenser and degasser to be transported to thionyl chloride synthesis reactor using fan, it is this
Mode brings many problems, for example, the set-up mode of the document may cause to come under the pressure oscillation of synthesis reactor
The gas of condenser and degasser cannot be introduced into synthesis reactor, or lead to the pressure oscillation of degasser or condenser, although
It is proposed in another patent application of researcher of the invention and is provided with a return pipe before and after fan, but still can
Quantity-produced can be caused to be difficult to carry out.In addition to this, prior art CN103043620A also discloses a kind of thionyl chloride gas
The operation of phase closed cycle, but the gas compression conveying machinery used is liquid-piston compressor, liquid-piston compressor used
Although, in order to carry out fluid-tight and cooling in use, being needed in thionyl chloride production process convenient for automatically controlling
The existing materials of one or two as working media, thereby resulted in the waste of partial material in production process.But it is existing
In the operation of the thionyl chloride gas phase closed cycle of technology CN101412502B, using a kind of gas unidirectional conveying apparatus by chlorination
The gas dissolved in sulfoxide crude product sends thionyl chloride back to by adjusting the temperature of crude product degassing purification kettle to increase its pressure
Synthesis reactor, it is this by improving temperature of charge to make gas deviate from since the boiling point of thionyl chloride is lower and easy decomposition
The degassing method for returning to thionyl chloride synthesis reactor will cause partial oxidation sulfoxide products and lose, in addition, differentiation is not added in tail gas
And be delivered directly in thionyl chloride synthesis reactor and easily lead to synthesis reactor pressure and gradually rise, reaction mass ratio is unbalance, and reaction is not
It can be normally carried out or even the circulatory system terminates, influence entire process flow, or even very big security risk occur.In addition to this
The method of thionyl chloride production gas phase circulation is not isolated tail gas and is recycled directly to thionyl chloride synthesis in the prior art
In kettle, but in addition to comprising multiple gases, such as sulfur dichloride, sulfur dioxide and chlorine in tail gas, and chlorine is applied not only to
Thionyl chloride is closed, the synthesis of sulfur dichloride is also used to, therefore tail gas is not isolated operation and is passed directly to thionyl chloride
May cause the insufficient raw material of thionyl chloride and thionyl chloride in circulation production process in synthesis reactor influences entire continuous production
Process, carry out influence product yield.And separated and recovered tail gas in prior art CN106145059A, but separate
Recycle SO2Mode it is complicated, need SO2First condensation is collected and is regasified, due to SO2Boiling point is lower, and condensing condition requirement is high,
Need to consume more resource, cost is larger, and waste of resource, causes sulphoxide chloride product yield low.
In view of this, the present invention is specifically proposed.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of thionyl chloride produce gas phase circulation method, the purpose of the present invention it
One be effectively by incoagulability tail gas chlorine and sulfur dioxide distinguish, avoid pressure liter in thionyl chloride synthesis reactor
Height influences being normally carried out for reaction, and second object of the present invention is that liquid injection apparatus is arranged, using fluid dynamics,
It extracts gas and realizes gas-liquid separation in thionyl chloride crude product dump tank, to feed gas into thionyl chloride synthesis reactor
The method of recycling improves raw material availability.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of thionyl chloride production gas phase circulation method, the gas phase circulation are by condenser, degassing purification kettle and essence
It evaporates the incoagulable gas deviate from least one in equipment to be delivered in gas separator, the chlorine after separation is passed through dichloride
In sulphur synthesis reactor, the sulfur dioxide after separation is passed into thionyl chloride crude product synthesis reactor.
Preferably, setting adsorbent equipment conciliates adsorbent equipment, setting in the adsorbent equipment inside the gas separator
Adsorbent described in adsorbent is used to absorb the sulfur dioxide in incoagulable gas, and the desorption adsorption device will adsorb sulfur dioxide
Adsorbent desorption afterwards.
Preferably, the adsorbent in the adsorbent equipment is solid or liquid phase adsorption agent, and the liquid phase adsorption agent is full
With at least one of saline solution or organic alcohol amine solution.
Preferably, the liquid phase adsorption agent for adsorbing sulfur dioxide, which is passed into ultrasonic processing apparatus, to be de-gassed, then
Secondary abjection sulfur dioxide
Preferably, thionyl chloride production process includes:
(1) it the synthesis of sulfur dichloride: is reacted in sulfur dichloride synthesis reactor using the sulfur monochloride of liquid with chlorine, dichloro
The gas outlet pressure P1 for changing sulphur synthesis reactor is 0.01-0.02MPa；
(2) synthesis of thionyl chloride crude product: the mixed gas that sulfur dichloride synthesis reactor is discharged is passed into thionyl chloride and is closed
At in kettle, while the sulfur dioxide gas after metering, thionyl chloride crude product synthesis reactor are passed through into thionyl chloride crude product synthesis reactor
Gas outlet pressure P2 be 0.01-0.02MPa；
(3) it is thick that the mixed gas that thionyl chloride synthesis reactor generates the condensation of thionyl chloride crude product: is passed into thionyl chloride
In product condenser, condensed product is obtained, wherein incoagulable gas is sent into gas separator；
(4) thionyl chloride crude product receives: the condensed product generated in thionyl chloride crude product condenser being passed into crude product and is connect
It receives in slot, obtains crude product thionyl chloride after degassing purification, low-boiling-point substance is drawn into gas using gas unidirectional conveying apparatus and is separated
In device；
(5) match reaction of Salmon-Saxl: the crude product receiving slit purified product that purification kettle generates that deaerates being passed into in sulphur kettle, normal pressure shape
It is carried out under state with reaction of Salmon-Saxl, the additional amount of sulphur is the 70-80% of sulfur content needed for reacting completely；
(6) rectification and purification: the product with reaction of Salmon-Saxl being passed into rectifier unit and carries out rectification and purification, while being filled in rectifying
The excessive vulcanization of middle progress is set, thionyl chloride finished product is finally obtained.
Preferably, the gas outlet pressure P1 of sulfur dichloride synthesis reactor is greater than the gas outlet pressure of thionyl chloride crude product synthesis reactor
P2, the height of sulfur dichloride synthesis reactor are higher than the height of thionyl chloride synthesis reactor, and the position of thionyl chloride crude product receiving slit is high
Match sulphur kettle in crude product.
The position of the gas separator is higher than the position of thionyl chloride synthesis reactor and the position of sulfur dichloride synthesis reactor.
Preferably, described is that first selection sulfur in lump form is spare, then by the sulfur in lump form of selection with the method that sulphur is added in sulphur kettle
It is crushed together with desiccant calcium chloride granules, smashed particle reaches 30~50 mesh, then smashed mixed-powder is sent into
It carries out to matching in sulphur kettle with reaction of Salmon-Saxl.
Preferably, the gas unidirectional conveying apparatus is set as liquid injection apparatus, and the liquid injection apparatus is at least set
One is set, the incoagulable gas of extraction is passed into gas separator by the liquid injection apparatus, the gas separator.
The present invention also provides a kind of thionyl chlorides to produce gas phase circulator, including sulfur dichloride synthesis reactor, protochloride
Sulfone synthesis reactor matches sulphur kettle, crude product condenser, crude product receiving slit, liquid injection apparatus and gas separator, the gas separator
Inside setting adsorbent equipment conciliates adsorbent equipment.
Method of the present invention can effectively prevent the fluctuation between condenser and thionyl chloride synthesis reactor.
1, using technique of the present invention, the consumption of raw material is reduced, for the feeding intake of opposite raw material, high income,
Utilization rate of raw materials is up to 99.0% or more；Under process conditions of the present invention, control appropriate, sulphur and chlorine are carried out
(the most important reactant from the point of view of economy) is to the conversion ratio of thionyl chloride close to 100%.
2, using the totally-enclosed technique of complete alternation, the SO being detached from gas2And Cl2The chlorine that mixed gas and each station generate
Changing the liquid product other than sulfoxide can be recycled at corresponding charging, so that package unit substantially no three wastes liquid gas is outside
Discharge.
3. the present invention uses gas unidirectional conveying apparatus by condenser, crude product in the whole production technology of thionyl chloride
The incoagulability tail gas generated in receiving slit and rectifying device is delivered in gas separator, and absorption is provided in gas separator
Device conciliates adsorbent equipment, and adsorbent equipment is used to absorb the sulfur dioxide in incoagulable gas, but does not absorb in incoagulable gas
Chlorine.After incoagulable gas passes through gas separator, non-absorbent chlorine is passed directly in sulfur dichloride synthesis reactor,
And sulfur dichloride is adsorbed device and fully absorbs, and thus effectively distinguishes chlorine and sulfur dioxide, and thionyl chloride is avoided to close
At pressure rise in kettle, being normally carried out for reaction is influenced.
4, using technique of the present invention, maintenance cost is reduced, for opposite Primordial Qi phase circulator and technique, maintenance
Cost can be ignored；Under process conditions of the present invention, production run is more steady, and production capacity is compared with Primordial Qi phase circulation technology
5% or more is improved, production scale can be made to expand and be easy to carry out.
Detailed description of the invention
Attached drawing 1 is the basic flow chart of thionyl chloride production gas phase circulation method of the present invention；
Attached drawing 2 is gas fractionation unit schematic diagram of the present invention；
Attached drawing 3 is rectifier unit thermostatic control system schematic diagram of the present invention.
1- sulfur dichloride synthesis reactor, 2- thionyl chloride synthesis reactor, 3- match sulphur kettle, 4- crude product condenser, 5- gas-liquid separator,
6- crude product receiving slit, 7- liquid injection apparatus, 8- circulating pump, 9- rectifying still, 10- rectifying column, 11- finished product condenser, 12- gas
Separator, 13- adsorbent equipment, 14- desorb adsorption device, 15- intake line, 16- connecting line, 17- chlorine output pipe, 18-
Sulfur dioxide output pipe, 19- constant temperature control box, 20- heating device, 21- low temperature liquid reserve tank, the first valve of 22-, 23- second
Valve, 24- liquid outlet, the first temperature detector of 25-, 26- second temperature detector
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under that premise of not paying creative labor
Embodiment shall fall within the protection scope of the present invention.
The purpose of the present invention is to provide a kind of gas discharge outlets in thionyl chloride condenser, and liquid injection apparatus is arranged,
Using fluid dynamics, extracts gas and realize gas-liquid separation in thionyl chloride crude product receiving slit, to feed gas into chlorine
Change the method that sulfoxide synthesis reactor recycles.To form the closed circulating production process of thionyl chloride.
The purpose of the present invention can be achieved in the following manner: below such as to the synthesis process description of thionyl chloride
Under, it may be assumed that
1, sulfur monochloride (S is synthesized2Cl2)；
2, sulfur dichloride (SCl is synthesized2)；
3, synthesizing chlorinated sulfoxide (SOCl2)；
4, thionyl chloride rectifying；
Thionyl chloride produce during, have several devices can generate can reuse gas, first is that crude product thionyl chloride exists
After condensing unit is cooling, the low-boiling gas in part can be with reuse；Second is that thionyl chloride crude product receiving slit is after degassing purification
Part incoagulable gas can be generated；Third is that the devices such as similar rectifying column also have portion gas can be with reuse.
If these mixed gas are released, it is possible to it wastes and pollutes, be more importantly, it is of the invention to be related to
A kind of totally-enclosed complete alternation production technology of thionyl chloride, in order to enable production in almost complete absence of excess waste emptying,
Production cycle is not entered back into, needs the reuse amount of conscious increase liquid or gas, therefore, the reuse of gas, and
Thionyl chloride synthesis reactor, the pressure of crude product condenser how is kept not to be become one by interference each other mutually in reuse
A important problem.
Solution proposed by the present invention is at least one the gas in crude product condenser, crude product receiving slit and rectifying column
Gas extraction is sent by body discharge outlet setting gas unidirectional conveying apparatus after processing specifically, can be liquid injection apparatus
The method that synthesis reactor recycles, to form the closed circulating production process of thionyl chloride of the present invention.
In the present invention, gas phase circulation is will deviate from least one in condenser, crude product receiving slit and rectifying device
Incoagulable gas is delivered in gas separator, and the chlorine after separation is passed through in sulfur dichloride synthesis reactor, two after separation
Sulfur chloride is passed into thionyl chloride crude product synthesis reactor.
Setting adsorbent equipment conciliates adsorbent equipment inside gas separator of the invention, setting absorption in the adsorbent equipment
Agent, the adsorbent is used to absorb the sulfur dioxide in incoagulable gas, after the desorption adsorption device will adsorb sulfur dioxide
Adsorbent desorption.
Adsorbent in adsorbent equipment of the invention is solid or liquid phase adsorption agent, and the solid absorbent can be oxygen
Change magnesium, the liquid phase adsorption agent is at least one of saturated salt solution or organic alcohol amine solution.
Sulfur dioxide is precipitated by washing or heating regeneration in solid-phase adsorbent after absorption of the invention, adsorbs dioxy
The liquid phase adsorption agent for changing sulphur, which is passed into ultrasonic processing apparatus, to be de-gassed, and deviates from sulfur dioxide again.
Specific thionyl chloride production process includes: in the present invention
(1) it the synthesis of sulfur dichloride: is reacted in sulfur dichloride synthesis reactor using the sulfur monochloride of liquid with chlorine, dichloro
The gas outlet pressure P1 for changing sulphur synthesis reactor is 0.01-0.02MPa；
(2) synthesis of thionyl chloride crude product: the mixed gas that sulfur dichloride synthesis reactor is discharged is passed into thionyl chloride and is closed
At in kettle, while the sulfur dioxide gas after metering, thionyl chloride crude product synthesis reactor are passed through into thionyl chloride crude product synthesis reactor
Gas outlet pressure P2 be 0.01-0.02MPa；
(3) it is thick that the mixed gas that thionyl chloride synthesis reactor generates the condensation of thionyl chloride crude product: is passed into thionyl chloride
In product condenser, condensed product is obtained, wherein incoagulable gas is sent into gas separator；
(4) thionyl chloride crude product receives: the condensed product generated in thionyl chloride crude product condenser being passed into crude product and is connect
It receives in slot, obtains crude product thionyl chloride after degassing purification, low-boiling-point substance is drawn into gas using gas unidirectional conveying apparatus and is separated
In device；
(5) match reaction of Salmon-Saxl: the crude product receiving slit purified product that purification kettle generates that deaerates being passed into in sulphur kettle, normal pressure shape
It is carried out under state with reaction of Salmon-Saxl, the additional amount of sulphur is the 70-80% of sulfur content needed for reacting completely；
(6) rectification and purification: the product with reaction of Salmon-Saxl being passed into rectifier unit and carries out rectification and purification, while being filled in rectifying
The excessive vulcanization of middle progress is set, thionyl chloride finished product is finally obtained.
The gas outlet pressure P1 of sulfur dichloride synthesis reactor is greater than the gas outlet pressure P2 of thionyl chloride crude product synthesis reactor, dichloro
The height for changing sulphur synthesis reactor is higher than the height of thionyl chloride synthesis reactor, and the position of thionyl chloride crude product receiving slit is matched higher than crude product
The position of sulphur kettle, the gas separator is higher than the position of thionyl chloride synthesis reactor and the position of sulfur dichloride synthesis reactor.
Gas-liquid separator is reached in the present invention after the condensation of thionyl chloride crude product, gas unidirectional conveying apparatus extracts gas-liquid separation
Incoagulable gas in device, and after the incoagulable gas being drawn into is passed into again in thionyl chloride crude product receiving slit, gas
Unidirectional conveying apparatus extracts the merging of the incoagulable gas in crude product receiving slit again and is delivered in gas separator.
The gas unidirectional conveying apparatus is set as liquid injection apparatus, and the liquid injection apparatus is at least arranged one,
The incoagulable gas of extraction is passed into gas separator by the liquid injection apparatus.
Embodiment 1
The present embodiment is in the description present invention using the gas deviate from crude product condenser as the synthetic gas of thionyl chloride
A part of raw material sources is again introduced into thionyl chloride synthesis reactor and recycles, thus the method for completing gas phase circulation, it should
Method includes:
(1) by thionyl chloride content be account for 68% crude product thionyl chloride of crude product thionyl chloride total amount in sulphur kettle into
Row matches sulphur, also includes sulfur dichloride 15% in the crude product thionyl chloride, is more than crude product thionyl chloride with the temperature in sulphur kettle
78 DEG C of temperature, pressure are normal pressure, are added in Xiang Suoshu crude product thionyl chloride relative to the not excessive sulphur of sulfur dichloride therein, sulphur
Additional amount is the 80% of the amount of sulphur needed for reacting completely with the sulfur dichloride in crude product thionyl chloride, so that the crude product protochloride
Other materials in sulfone in addition to thionyl chloride are converted to sulfur monochloride, the crude product thionyl chloride after being vulcanized.
(2) rectifying will be carried out with the crude product thionyl chloride after sulphur, obtains thionyl chloride and mixing high-boiling components, the rectifying
It is carried out in rectifying column, carries out three-level rectifying；
A, level-one rectifying: tower reactor temperature control system is between 110-130 DEG C, and tower top obtains 80% thionyl chloride, described
It in level-one rectifying, is fed using clearance-type, so that at the top of a small amount of sulfur dichloride and rectifying column with thionyl chloride gaseous volatilization
Excessive sulphur haptoreaction in vulcanization bed is converted to sulfur monochloride, is then refluxed for tower bottom；
B, two-stage rectification: bottom temperature controls between 70-105 DEG C, when bottom temperature reaches certain liquid level and temperature reaches
When to 89 DEG C, the height of tower reactor is just mixed into object and is discharged to level-one rectifying column, obtains 98% or so SOCl from tower top2；
C, three-level rectifying: in 78-80 DEG C of bottom temperature, 72-75 DEG C of tower top, reflux ratio 1:1, pressure 0.02-0.03MPa
Under conditions of carry out, obtain the SOCl of purity 99.8% from tower top2。
(3) the mixing high-boiling components are reacted with excessive chlorine, obtains sulfur dichloride mixed gas；
Mixing high-boiling components in rectifying column are discharged from tower, in the kettle that goes directly, then by pumping the mixing high-boiling components
It send to sulfur dichloride synthesis reactor, then is passed through chlorine, mix the sulfur monochloride in high-boiling components with excessive chlorine in 70 DEG C, pressure
It is reacted under conditions of 0.02MPa, the Cl being passed through2With the S of liquid in sulfur dichloride synthesis reactor2Cl2Volume ratio be 150:
0.2；Cl2And S2Cl2It is reacted in sulfur dichloride synthesis reactor, the SCl of generation2With excessive Cl2Mixed gas from gas outlet arrange
Out, the pressure P1 of the gas outlet is 0.02MPa.
(4) by sulfur dichloride and excessive Cl2Mixed gas is sent to thionyl chloride synthesis reactor, anti-toward the synthesis
It answers and is passed through sulfur dioxide gas in device, gas Cl in synthesis reactor2: SO2: S2Cl2The volume ratio of (liquid) be 150: 100: 0.2 send to
The synthesizing chlorinated sulfoxide of thionyl chloride synthesis reactor, the temperature in thionyl chloride synthesis reactor are 250 degree, pressure 0.10MPa, conjunction
Thionyl chloride mixed gas is obtained after.
(5) obtained thionyl chloride mixed gas is condensed in crude product condenser, the actual conditions of condensation are 35
DEG C or so, the content of thionyl chloride is 68% in obtained condensed product, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide
3%, wherein incoagulable gas is extracted by gas unidirectional conveying apparatus such as liquid injection apparatus and is sent into thionyl chloride synthesis instead
It answers in device, to complete gas phase circulation.
In order to maintain circulation of the gas in entire production process, the gas from crude product condenser is defeated due to gas unidirectional
It send device to form and irreversibly delivers gas, therefore, the gas phase circulation that can preferably push thionyl chloride to produce.
In order to reduce the consumption and possible leakage of the pumping bring energy, the present invention is also by the position of crude product condenser
It is positioned above the place of crude product dump tank, the position of thionyl chloride crude product receiving slit is positioned above the place with sulphur kettle,
Preferably, the liquid phase discharge gate position of crude product condenser is positioned above the liquid phase feeding mouth place of crude product dump tank, so as to shape
Allow liquid is without hindrance to convey at pressure difference.
Embodiment 2
The present embodiment is that the gas for excluding rectifying column in the description present invention comes as the synthetic gas raw material of thionyl chloride
The a part in source is again introduced into thionyl chloride synthesis reactor and recycles, thus the method for completing gas phase circulation.This method tool
Body is as follows:
As described in 1 step of embodiment (2), the crude product thionyl chloride after vulcanization carries out rectifying in rectifying column, obtains chlorine
Change sulfoxide and mixing high-boiling components and tail gas, gas contained in the tail gas has sulfur dioxide (accounting for about 45%), and thionyl chloride is (about
It accounts for 48%), sulfur dichloride (accounts for about 5%), and chlorine (accounts for about 2%).Mixing high-boiling components are discharged from tower, go directly in kettle, then lead to
It crosses pump to send the mixing high-boiling components to sulfur dichloride synthesis reactor, completes liquid phase circulation.And tail gas is mainly sulfur dioxide and chlorine
Gas is sent into thionyl chloride synthesis reactor by gas unidirectional conveying apparatus such as liquid injection apparatus, is followed to complete gas phase
Ring.
Embodiment 3
The present embodiment is the incoagulable gas deviate from thionyl chloride crude product receiving slit in the description present invention as protochloride
A part of the synthetic gas raw material sources of sulfone is again introduced into thionyl chloride synthesis reactor and recycles, to complete gas phase
The method of circulation.This method is specific as follows:
Thionyl chloride mixed gas is condensed in crude product condenser, and the actual conditions of condensation are 35 DEG C or so, is obtained
Condensed product in thionyl chloride content 68%, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide 3% will condense
Product, which is passed into thionyl chloride crude product receiving slit, is de-gassed purification, and the incoagulable gas that degassing purification generates passes through gas list
It is sent into thionyl chloride synthesis reactor to conveying device to such as liquid injection apparatus, to complete gas phase circulation.
Embodiment 4
The present embodiment describes to separate the gas deviate from crude product condenser in embodiment 1, is separated into dioxy
Change sulphur and chlorine, the chlorine that the sulfur dioxide after separation is passed into thionyl chloride synthesis reactor, after separation are passed through dichloro
Change in sulphur synthesis reactor, thus the method for completing gas phase circulation, this method comprises:
Wherein step (1) is identical with embodiment 1 to step (4)；
(5) obtained thionyl chloride mixed gas is condensed in crude product condenser, the actual conditions of condensation are 35
DEG C or so, the content of thionyl chloride is 68% in obtained condensed product, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide
3%, wherein incoagulable gas is extracted and is sent into gas separator by gas unidirectional conveying apparatus such as liquid injection apparatus,
Be provided in gas separator adsorbent equipment reconciliation adsorbent equipment, by gas unidirectional conveying apparatus convey incoagulable gas into
Enter into adsorbent equipment, without absorbing chlorine, thus the adsorbent in adsorbent equipment absorbs the sulfur dioxide in incoagulable gas
Sulfur dioxide and chlorine are separated, chlorine is passed directly in sulfur dichloride synthesis reactor after passing through adsorbent equipment, and is adsorbed
The adsorbent of sulfur dioxide periodically enters into desorption adsorption device, and desorption adsorption device passes through ultrasonic method for the dioxy of absorption
Change sulphur abjection, then the sulfur dioxide of desorption abjection enters in thionyl chloride synthesis reactor, to complete gas phase circulation.
Wherein, adsorbent described in the present embodiment is liquid phase adsorption agent, and specially saturated salt solution or organic alcohol amine is molten
At least one of liquid.
Embodiment 5
The present embodiment describes for the gas that rectifying column excludes to be passed into gas separator, and is separated into dioxy
Change sulphur and chlorine, the sulfur dioxide after separation are passed into thionyl chloride synthesis reactor, the chlorine after separation is passed through sulfur dichloride
In synthesis reactor, so that the method for completing gas phase circulation, this method are specific as follows:
As described in 1 step of embodiment (2), the crude product thionyl chloride after vulcanization carries out rectifying in rectifying column, obtains chlorine
Change sulfoxide and mixing high-boiling components and tail gas, gas contained in the tail gas has sulfur dioxide (accounting for about 45%), and thionyl chloride is (about
It accounts for 48%), sulfur dichloride (accounts for about 5%), and chlorine (accounts for about 2%).Mixing high-boiling components are discharged from tower, go directly in kettle, then lead to
It crosses pump to send the mixing high-boiling components to sulfur dichloride synthesis reactor, completes liquid phase circulation.And tail gas is mainly sulfur dioxide and chlorine
Gas is sent into gas separator by gas unidirectional conveying apparatus such as liquid injection apparatus, is provided with absorption in gas separator
Device conciliates adsorbent equipment, is entered in adsorbent equipment by the incoagulable gas that gas unidirectional conveying apparatus conveys, absorption dress
Adsorbent in setting absorbs the sulfur dioxide in incoagulable gas without absorbing chlorine, thus separates sulfur dioxide and chlorine
It opens, chlorine is passed directly in sulfur dichloride synthesis reactor after passing through adsorbent equipment, and adsorbs the adsorbent period of sulfur dioxide
Property enter in desorption adsorption device, desorption adsorption device is deviate from the sulfur dioxide of absorption by the method for ultrasound, then desorption
The sulfur dioxide of abjection enters in thionyl chloride synthesis reactor, to complete gas phase circulation.
Wherein, adsorbent described in the present embodiment is liquid phase adsorption agent, and specially saturated salt solution or organic alcohol amine is molten
At least one of liquid.
Embodiment 6
The present embodiment describes for the incoagulable gas deviate from thionyl chloride crude product receiving slit to be passed into gas separation
In device, and it is separated into sulfur dioxide and chlorine, the sulfur dioxide after separation is passed into thionyl chloride synthesis reactor, separation
Chlorine afterwards is passed through in sulfur dichloride synthesis reactor, so that the method for completing gas phase circulation, this method are specific as follows:
Thionyl chloride mixed gas is condensed in crude product condenser, and the actual conditions of condensation are 35 DEG C or so, is obtained
Condensed product in thionyl chloride content 68%, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide 3% will condense
Product, which is passed into thionyl chloride crude product receiving slit, is de-gassed purification, and the incoagulable gas that degassing purification generates passes through gas list
It is sent in adsorbent equipment to conveying device such as liquid injection apparatus, the adsorbent in adsorbent equipment absorbs in incoagulable gas
Thus sulfur dioxide separates sulfur dioxide and chlorine without absorbing chlorine, chlorine is passed directly to after passing through adsorbent equipment
In sulfur dichloride synthesis reactor, and the adsorbent for adsorbing sulfur dioxide periodically enters into desorption adsorption device, desorbs adsorption device
The sulfur dioxide of absorption is deviate from by the method for ultrasound, then the sulfur dioxide of desorption abjection enters thionyl chloride synthesis
In kettle, to complete gas phase circulation.
Wherein, adsorbent described in the present embodiment is liquid phase adsorption agent, and specially saturated salt solution or organic alcohol amine is molten
At least one of liquid.
Embodiment 7
The present embodiment is the incoagulability gas that crude product condenser, rectifying column and the crude product receiving slit in the description present invention generate
Body is all used as a part in gas raw material source, and merging is passed into gas separator, and the sulfur dioxide after separation is passed through chlorination
Sulfoxide synthesis reactor, the chlorine after separation are passed through in sulfur dichloride synthesis reactor, thus the method for completing gas phase circulation, this method
It is specific as follows:
A, thionyl chloride mixed gas is condensed in crude product condenser, and the actual conditions of condensation are 35 DEG C or so, is obtained
To condensed product in thionyl chloride content 68%, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide 3%, wherein
Incoagulable gas is extracted and is sent into gas separator by gas unidirectional conveying apparatus such as liquid injection apparatus；
B, the crude product thionyl chloride after vulcanization carries out rectifying in rectifying column, obtain thionyl chloride and mixing high-boiling components and
Tail gas, gas contained in the tail gas have sulfur dioxide (accounting for about 45%), and thionyl chloride (accounts for about 48%), and sulfur dichloride (accounts for about
5%), chlorine (accounting for about 2%).Mixing high-boiling components are discharged from tower, in the kettle that goes directly, are then sent the mixing high-boiling components by pumping
To sulfur dichloride synthesis reactor, liquid phase circulation is completed.And tail gas is mainly that sulfur dioxide and chlorine pass through gas unidirectional conveying apparatus
As liquid injection apparatus is sent into gas separator；
C, thionyl chloride mixed gas is condensed in crude product condenser, and the actual conditions of condensation are 35 DEG C or so, is obtained
To condensed product in thionyl chloride content 68%, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide 3% will be cold
Solidifying product, which is passed into thionyl chloride crude product receiving slit, is de-gassed purification, and the incoagulable gas that degassing purification generates passes through gas
Unidirectional conveying apparatus to such as liquid injection apparatus is sent into gas separator；
After the incoagulable gas that three generates is passed into gas separator, the suction in adsorbent equipment in gas separator
Thus the attached dose of sulfur dioxide absorbed in incoagulable gas separates sulfur dioxide and chlorine without absorbing chlorine, chlorine is logical
It is passed directly in sulfur dichloride synthesis reactor after crossing adsorbent equipment, and the adsorbent for adsorbing sulfur dioxide periodically enters into solution
In adsorbent equipment, desorption adsorption device is deviate from the sulfur dioxide of absorption by the method for ultrasound, then the dioxy of desorption abjection
Change sulphur to enter in thionyl chloride synthesis reactor, to complete gas phase circulation.
Wherein, adsorbent described in the present embodiment is liquid phase adsorption agent, and specially saturated salt solution or organic alcohol amine is molten
At least one of liquid.
Embodiment 8
The present embodiment describes gas unidirectional conveying apparatus and leads to the incoagulable gas being drawn into from crude product condenser
It crosses crude product receiving slit to return in gas unidirectional conveying apparatus, and then realizes the abundant extraction to incoagulable gas, to complete gas
Mutually the method for circulation, this method are specific as follows:
Enter gas-liquid separator after the condensation of thionyl chloride crude product, gas unidirectional conveying apparatus extracts in gas-liquid separator not
Solidifying property gas, and after the incoagulable gas being drawn into is passed into again in thionyl chloride crude product receiving slit, then by gas unidirectional
Conveying device extracts the incoagulable gas merging in crude product receiving slit and is delivered in gas separator.
This incoagulable gas by gas-liquid separator is re-introduced into crude product receiving slit, to incoagulable gas and slightly
Liquid phase has carried out the process of gas-liquid mass transfer exchange again in product receiving slit, so that the incoagulability gas extracted from gas-liquid separator
The thionyl chloride adulterated in body is by the liquid phase scrubbing in crude product receiving slit, and a small amount of sulfur dioxide and chlorine in crude product receiving slit
Gas, which is passed into incoagulable gas therein, to be taken out of be delivered in gas separator together, is provided with absorption in gas separator
Device conciliates adsorbent equipment, is entered in adsorbent equipment by the incoagulable gas that gas unidirectional conveying apparatus conveys, absorption dress
Adsorbent in setting absorbs the sulfur dioxide in incoagulable gas without absorbing chlorine, thus separates sulfur dioxide and chlorine
It opens, chlorine is passed directly in sulfur dichloride synthesis reactor after passing through adsorbent equipment, and adsorbs the adsorbent period of sulfur dioxide
Property enter in desorption adsorption device, desorption adsorption device is deviate from the sulfur dioxide of absorption by ultrasound or the method for washing, then
The sulfur dioxide of desorption abjection enters in thionyl chloride synthesis reactor, to complete gas phase circulation.
Reciprocation cycle of the gas unidirectional conveying apparatus among crude product condenser and crude product receiving slit is utilized as a result, sufficiently
It is extracted the incoagulable gas generated in thionyl chloride production process, convenient for controlling the Rectification column pressure of subsequent rectification and purification, is mentioned
High raw material availability.
Embodiment 9
The advantages of in order to illustrate using gas phase circulator and method production thionyl chloride of the invention, the present embodiment description
Start since raw material investment to entire thionyl chloride production process circulation 72h, specific method is described as follows:
(1) sulfur monochloride (S is synthesized2Cl2): sulphur powder is added in gas-solid synthesizer, then is passed through chlorine, liquid is made
Sulfur monochloride, wherein reactor temperature control is at 30~80 DEG C；
(2) sulfur dichloride (SCl is synthesized2): it is reacted in sulfur dichloride synthesis reactor using the sulfur monochloride of liquid with chlorine,
The wherein product that liquid sulfur monochloride a part generates in sulfur monochloride reaction kettle, another part are deviate from from rectifying column
Liquid phase high-boiling components component, the volume ratio of chlorine and liquid sulfur monochloride are 150:(0.15-0.25), reaction temperature control for 60~
85 DEG C, the SCl of generation2With excessive Cl2Mixed gas from gas outlet be discharged, control sulfur dichloride synthesis reactor in pressure be
0.01MPa-0.10MPa, the gas outlet pressure P1 of sulfur dichloride synthesis reactor are 0.01-0.02MPa；
(3) synthesizing chlorinated sulfoxide (SOCl2): the mixed gas that sulfur dichloride synthesis reactor is discharged is passed into thionyl chloride and is closed
At in kettle, while the sulfur dioxide gas after metering is passed through into thionyl chloride crude product synthesis reactor, specifically, not occurring wherein anti-
The sulfur dichloride of the chlorine and generation answered and sulfur dioxide after metering are by Cl2: SO2: S2Cl2For the ratio of 150:100:0.20
Example is added in thionyl chloride synthesis reactor, and at 160~250 DEG C, pressure control is 0.10MPa-0.25MPa for reaction temperature control,
The gas outlet pressure P2 of thionyl chloride crude product synthesis reactor is 0.01-0.02MPa；
(4) it is thick that the mixed gas that thionyl chloride synthesis reactor generates the condensation of thionyl chloride crude product: is passed into thionyl chloride
In product condenser, and condensation temperature is set into Zhi as≤35 DEG C, condensed crude product enters gas-liquid separator, and then condense out
Liquid phase chlorination sulfoxide crude product enters thionyl chloride crude product receiving slit, and the uncooled incoagulable gas to get off is conveyed by gas unidirectional
Device is sent into gas separator；
(5) thionyl chloride crude product receives: the condensed product thionyl chloride crude product that will be generated in thionyl chloride crude product condenser
It being passed into crude product receiving slit, at 60-80 DEG C, pressure control is 0.10MPa-0.25MPa for the temperature control of crude product receiving slit,
Purification is de-gassed to thionyl chloride crude product in crude product receiving slit, obtains thionyl chloride after purification, is conveyed and is filled using gas unidirectional
It sets and low-boiling-point substance is drawn into gas separator；
(6) match reaction of Salmon-Saxl: the purified product that degassing purification kettle generates being passed into in sulphur kettle, is matched under normal pressure state
Reaction of Salmon-Saxl is 60-80 DEG C with the temperature control in sulphur kettle, carries out under normal pressure state that the additional amount of sulphur is sulphur needed for reacting completely
The 70-80% of amount.
Wherein contain a large amount of sulfur dichloride gas in the condensed product of crude product, but the boiling point of sulfur dichloride is lower
(59 DEG C), are difficult to separate with thionyl chloride, thus need to convert low-boiling sulfur dichloride to the higher sulfur monochloride of boiling point,
It is convenient to be separated with thionyl chloride；It is being reacted with addition sulphur in sulphur kettle with sulfur dichloride, sulfur monochloride can converted by sulfur dichloride,
But in the sulphur of industrial production usually include moisture, and thionyl chloride meet water easily decompose, so if match reaction of Salmon-Saxl when sulphur
Include moisture in sulphur, then be easy to cause the decomposition of thionyl chloride, influences the purity and yield of thionyl chloride.Thus, it is desirable to right
Sulphur when with reaction of Salmon-Saxl is dried.Adding Way provided in this embodiment with sulphur in sulphur kettle are as follows: by the sulphur of selection
Sulphur block crushes together with desiccant calcium chloride granules, and smashed particle reaches 30~50 mesh, then by smashed mixed-powder
It is sent to match and be carried out in sulphur kettle with reaction of Salmon-Saxl.Preferably, the weight ratio of the desiccant and sulfur in lump form is (3~5): 1.
(7) rectification and purification: the product with reaction of Salmon-Saxl being passed into rectifier unit and carries out rectification and purification, while being filled in rectifying
The excessive vulcanization of middle progress is set, wherein incoagulable gas is delivered in gas separator by gas unidirectional conveying apparatus, after condensation
Liquid phase be thionyl chloride finished product.
The present invention carries out rectification and purification to the product with reaction of Salmon-Saxl by the way of three-level rectifying, higher to obtain purity
Reaction product, specific rectifying mode are identical with embodiment 1.
Embodiment 10
The present embodiment is the incoagulability gas that crude product condenser, rectifying column and the crude product receiving slit in the description present invention generate
Body is all used as a part in gas raw material source, and merging is passed into gas separator, and the sulfur dioxide after separation is passed through chlorination
Sulfoxide synthesis reactor, the chlorine after separation are passed through in sulfur dichloride synthesis reactor, thus the method for completing gas phase circulation, other mistakes
Journey is identical with embodiment 9, and the specific method is as follows:
Enter gas-liquid separator after crude product condensation, gas unidirectional conveying apparatus extracts the incoagulability gas in gas-liquid separator
Body, and after the incoagulable gas being drawn into is passed into again in thionyl chloride crude product receiving slit, gas unidirectional conveying apparatus is taken out
It takes the incoagulable gas in crude product receiving slit to merge to be delivered in gas separator.
This incoagulable gas by gas-liquid separator is re-introduced into crude product receiving slit, to incoagulable gas and slightly
Liquid phase has carried out the process of gas-liquid mass transfer exchange again in product receiving slit, so that the incoagulability gas extracted from gas-liquid separator
The thionyl chloride adulterated in body is by the liquid phase scrubbing in crude product receiving slit, and a small amount of sulfur dioxide and chlorine in crude product receiving slit
Gas, which is passed into incoagulable gas therein, to be taken out of be delivered in gas separator together, is provided with absorption in gas separator
Device conciliates adsorbent equipment, is entered in adsorbent equipment by the incoagulable gas that gas unidirectional conveying apparatus conveys, absorption dress
Adsorbent in setting absorbs the sulfur dioxide in incoagulable gas without absorbing chlorine, thus separates sulfur dioxide and chlorine
It opens, chlorine is passed directly in sulfur dichloride synthesis reactor after passing through adsorbent equipment, and adsorbs the adsorbent period of sulfur dioxide
Property enter in desorption adsorption device, desorption adsorption device is deviate from the sulfur dioxide of absorption by ultrasound or the method for washing, then
The sulfur dioxide of desorption abjection enters in thionyl chloride synthesis reactor, to complete gas phase circulation.
Comparative example 1
According to the cycle production process of prior art CN10142502B, crude product condenser, rectifying column and crude product are received
The incoagulable gas that slot generates all is used as a part in gas raw material source, is not isolated and is passed directly into thionyl chloride synthesis
Reactor cycles utilize, thus the method for completing gas phase circulation.This method is specific as follows:
A, thionyl chloride mixed gas is condensed in crude product condenser, and the actual conditions of condensation are 35 DEG C or so, is obtained
To condensed product in thionyl chloride content 68%, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide 3%, wherein
Incoagulable gas is extracted and is sent into thionyl chloride synthesis reactor by gas unidirectional conveying apparatus such as liquid injection apparatus；
B, the crude product thionyl chloride after vulcanization carries out rectifying in rectifying column, obtain thionyl chloride and mixing high-boiling components and
Tail gas, gas contained in the tail gas have sulfur dioxide (accounting for about 45%), and thionyl chloride (accounts for about 48%), and sulfur dichloride (accounts for about
5%), chlorine (accounting for about 2%).Mixing high-boiling components are discharged from tower, in the kettle that goes directly, are then sent the mixing high-boiling components by pumping
To sulfur dichloride synthesis reactor, liquid phase circulation is completed.And tail gas is mainly that sulfur dioxide and chlorine pass through gas unidirectional conveying apparatus
As liquid injection apparatus is sent into thionyl chloride synthesis reactor；
C, thionyl chloride mixed gas is condensed in crude product condenser, and the actual conditions of condensation are 35 DEG C or so, is obtained
To condensed product in thionyl chloride content 68%, sulfur dichloride content 25%, chlorine 4%, sulfur dioxide 3% will be cold
Solidifying product, which is passed into thionyl chloride crude product receiving slit, is de-gassed purification, and the incoagulable gas that degassing purification generates passes through gas
Unidirectional conveying apparatus is sent into thionyl chloride synthesis reactor, to complete gas phase circulation.
The gas unidirectional conveying apparatus used in the prior art is diaphragm pump.
Comparative example 2
The logical embodiment 10 of the production technology of the present embodiment description is similar, the difference is that: to in the sulphur kettle plus side of sulphur
Formula is different, and the specific method is as follows:
Purified product that degassing purification kettle generates is passed into carrying out matching sulphur with reaction of Salmon-Saxl in sulphur kettle, under normal pressure state
Temperature control in kettle is 60-80 DEG C, and sulfur in lump form is added thereto, and the additional amount of sulphur is the 70- of sulfur content needed for reacting completely
80%, the sulfur dichloride and sulphur contained after vulcanization reaction in crude product, which reacts, generates the higher sulfur monochloride of boiling point.
Embodiment 11
As depicted in figs. 1 and 2, a kind of thionyl chloride production gas phase circulator is present embodiments provided, specifically, including
Following device:
Sulfur dichloride synthesis reactor 1, matches sulphur kettle 3, crude product condenser 4, gas-liquid separator 5, crude product at thionyl chloride synthesis reactor 2
Receiving slit 6, liquid injection apparatus 7, circulating pump 8, rectifying still 9, rectifying column 10, finished product condenser 11 and gas separator 12, institute
It states and the reconciliation adsorbent equipment 14 of adsorbent equipment 13 is set inside gas separator 12, the adsorbent equipment includes absorption cell, input pipe
Road 15, connecting line 16, chlorine output pipe 17 and sulfur dioxide output pipe 18 are provided with adsorbent in absorption cell, wherein
15 one end of intake line connects gas unidirectional conveying apparatus, and the other end connects absorption cell, and the connection of 17 one end of chlorine output pipe is inhaled
Receives pond, the other end connect sulfur dichloride synthesis reactor；16 one end of connecting line connects absorption cell, other end connection desorption adsorption device
14；In desorption adsorption device, the adsorbent of absorption cell discharge is by desorption abjection sulfur dioxide gas, and by abjection
Sulfur dioxide gas is delivered in thionyl chloride synthesis reactor.
Preferably, the gas unidirectional conveying apparatus that the present embodiment uses is liquid injection apparatus device.
Preferably, constant temperature control box 19 is arranged in the external of rectifying column 10 in the present embodiment, and constant temperature control box 19 and finished product are cold
Condenser is connected, and the condensed fluid excluded in finished product condenser 11 is passed into constant temperature control box 19, on constant temperature control box 19 also
Heating device 20 and temperature detector are set, are also connected with low temperature liquid reserve tank 21 on constant temperature control box 19.Preferably, constant temperature control box
19 be cyclic structure, is wrapped in the middle part of rectifying column 10, and the height of constant temperature control box 19 is less than the height of rectifying column 10.
Preferably, constant temperature control box 19 is connected with condenser, connecting portion is provided with the first valve 22, while in constant temperature
On control cabinet 19 be provided near 11 junction of finished product condenser cryogenic liquid inlet and control cryogenic liquid enter perseverance
Second valve 22 of warm control cabinet, so that low temperature liquid reserve tank 21 is connected with constant temperature control box 19, far from cryogenic liquid inlet
Side be provided with liquid outlet 24, be provided with temperature control equipment on constant temperature control box.Temperature control equipment includes that there are two temperature
Detector and heating device 20 are spent, wherein the first temperature detector 25 is arranged in the portion among constant temperature control box 19 close to rectifying column
Position, second temperature detector 26 are arranged in the connecting portion of constant temperature control box and condenser.
Under normal circumstances, 78~85 DEG C are set by the constant temperature rectification temperature range at position among rectifying column, when the first temperature
When the temperature that degree detector detects is lower than 78 DEG C, heating device starts to heat the liquid in constant temperature control box.It is preferred that
, while the second detector also will start the temperature detection to condensed fluid, when the temperature for detecting condensed fluid is higher than first
When the temperature that temperature detector detects, temperature control equipment can control the first valve opening, and condensed fluid enters thermostatic control
For the fluid temperature in regulating thermostatic control cabinet in case, i.e. temperature in constant temperature control box can pass through the condensed fluid of high temperature
It is increased to adjust, can also be controlled and be increased by heating device.When the temperature that the first temperature detector detects is higher than 85 DEG C,
Second valve is opened, and cryogenic liquid enters in constant temperature control box, thus real for reducing the temperature of liquid in constant temperature control box
The temperature of liquid can be always held in the range of setting in existing constant temperature control box, and then realize the high-efficiency precision of thionyl chloride finished product
It evaporates.
Further, include: using the rate-determining steps of above-mentioned constant-temperature control method
S1: by spot temperature T1 among the first temperature detector detection rectifying column, and judge spot temperature among rectifying column
Whether T1 is less than preset temperature threshold Ta, if it is, S21 is thened follow the steps, if it has not, thening follow the steps S22；
S21: if spot temperature T1 is less than preset temperature threshold T among the first temperature detector detection rectifying columna, then constant temperature
Control cabinet controls heating device and heats to the liquid in constant temperature control box, while starting second temperature detector；
S22: constant temperature control box keeps first state；
S3: detecting condensed fluid temperature T2 by second temperature detector, and judge whether condensed fluid temperature T2 is greater than T1,
If it is, S31 is thened follow the steps, if it has not, thening follow the steps S32；
S31: if second temperature detector detection condensed fluid temperature T2 is greater than T1, constant temperature control box can control the first valve
Door is opened, and condensed fluid enters in constant temperature control box；
S32: if second temperature detector detection condensed fluid temperature T2 is not more than T1, the first valve is remained turned-off；
S4: by spot temperature T1 among the first temperature detector detection rectifying column, and judge spot temperature among rectifying column
Whether T1 is greater than preset temperature threshold Tb, if it is, S51 is thened follow the steps, if it has not, thening follow the steps S52；
S51: if the first temperature detector detects that spot temperature T1 is greater than preset temperature threshold T among rectifying columnb, then
Two valves are opened, and cryogenic liquid enters inside constant temperature control box；
S52: if the first temperature detector detects that spot temperature T1 is no more than preset temperature threshold T among rectifying columnb, permanent
Warm control cabinet keeps first state.
Further, the first state is that the liquid in constant temperature control box remains unchanged, heating device and all valves
It remains turned-off.
Further, the preset temperature threshold TaAnd TbIt is determined according to the temperature control range that rectifier unit needs, it is preferred that
The TaValue be 78 DEG C, the TbValue be 85 DEG C.
Thionyl chloride production gas phase circulator provided in this embodiment can not only effectively improve the production effect of thionyl chloride
Rate and raw material availability, at the same it is again easy to operate, facilitate maintenance, totally enclosed circulation production process is integrally formed, it will not be right
Environment pollutes, and is conducive to promote and apply.
Influence of 1-incoagulability of experimental example tail gas separation to pressure size in thionyl chloride synthesis reactor is probed into
This experimental example is right after thionyl chloride production gas phase circulator is opened, gas phase circulation technology carries out 72 hours
The yield of pressure change, thionyl chloride and the purity of thionyl chloride in thionyl chloride synthesis reactor are measured, and are counted
According to as shown in table 1:
Table 1
By the comparison of this experimental example it is found that by incoagulable gas by each leading into sulfur dichloride synthesis reactor after separation
And in thionyl chloride synthesis reactor, the phenomenon that avoiding the occurrence of in thionyl chloride synthesis reactor hypertonia or insufficient raw material, so that
Pressure in thionyl chloride synthesis reactor keeps stablizing during long-term production, avoids the occurrence of security risk, while can be substantially
Degree improves the yield of thionyl chloride.
The recycle circuit of 3-gas unidirectional conveying apparatus of experimental example is studied
Sensing equipment opens each index after 72h, specific detection method are as follows:
(1) sulfur dioxide: wherein the measurement of content of sulfur dioxide is measured using the method for national standard GB/T16128-1995,
(2) chlorine content measures: using liquid chromatography, specific steps are as follows:
A. the chlorine in mixed gas is absorbed with aniline-water solution；
B. using methanol, phosphoric acid as mobile phase, C18 column is splitter, the aniline and 1 in separate absorbent liquid, 3- diphenyl urea,
Wavelength is that 254nm carries out liquid-phase chromatographic analysis, and the peak area of 1,3- diphenyl urea is directly proportional to chlorine content；
C. it is measured using external standard method.
Table 2
By being compared above as can be seen that being connect using gas unidirectional conveying apparatus in crude product condenser and thionyl chloride crude product
The reciprocation cycle among slot is received, the incoagulable gas content before rectifying in thionyl chloride crude product is effectively reduced, improves rectifying
Efficiency not will lead to significantly alterring for pressure in rectifying device, convenient for control rectifying pressure, and then guarantee entire process for refining
Stability.
Research of the experimental example 4- with sulphur Adding Way in reaction of Salmon-Saxl
Table 3
Content with each component in the mixture after reaction of Salmon-Saxl in comparative example 10 and comparative example 2 is found, in comparative example 2
The content of thionyl chloride is substantially reduced, it is seen that the moisture when matching reaction of Salmon-Saxl in sulphur can be such that thionyl chloride decomposes, and lead to chlorination
The content of sulfoxide reduces.And sulphur is mixed to addition with desiccant, it avoids the addition with sulphur and introduces moisture, reduce chlorine
Change the possibility that sulfoxide decomposes.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the embodiment of the present invention can have various modifications and variations.All within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc. should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of thionyl chloride produces gas phase circulation method, it is characterised in that: the gas phase circulation is by crude product condenser, crude product
The incoagulable gas deviate from least one in receiving slit and rectifying device is delivered in gas separator, the chlorine after separation
Gas is passed through in sulfur dichloride synthesis reactor, and the sulfur dioxide after separation is passed into thionyl chloride crude product synthesis reactor.
2. a kind of thionyl chloride according to claim 1 produces gas phase circulation method, it is characterised in that: the gas separation
Setting adsorbent equipment conciliates adsorbent equipment inside device, adsorbent is arranged in the adsorbent equipment, the adsorbent is for absorbing not
Sulfur dioxide in solidifying property gas, the desorption adsorption device will adsorb sulfur dioxide after adsorbent desorption.
3. a kind of thionyl chloride according to claim 1 produces gas phase circulation method, it is characterised in that: the adsorbent equipment
Interior adsorbent is that perhaps the liquid phase adsorption agent liquid phase adsorption agent is in saturated salt solution or organic alcohol amine solution to solid
It is at least one.
4. a kind of thionyl chloride according to claim 3 produces gas phase circulation method, it is characterised in that: adsorbed titanium dioxide
The liquid phase adsorption agent of sulphur, which is passed into ultrasonic processing apparatus, to be de-gassed, and deviates from sulfur dioxide again.
5. a kind of thionyl chloride according to claim 3 produces gas phase circulation method, it is characterised in that: thionyl chloride production
Process includes:
(1) it the synthesis of sulfur dichloride: is reacted in sulfur dichloride synthesis reactor using the sulfur monochloride of liquid with chlorine, sulfur dichloride
The gas outlet pressure P1 of synthesis reactor is 0.01-0.02MPa；
(2) mixed gas that sulfur dichloride synthesis reactor is discharged the synthesis of thionyl chloride crude product: is passed into thionyl chloride synthesis reactor
In, while the sulfur dioxide gas after metering is passed through into thionyl chloride crude product synthesis reactor, thionyl chloride crude product synthesis reactor goes out
Outlet pressure P2 is 0.01-0.02MPa；
(3) it is cold that the mixed gas that thionyl chloride synthesis reactor generates the condensation of thionyl chloride crude product: is passed into thionyl chloride crude product
In condenser, condensed product is obtained, wherein incoagulable gas is sent into gas separator；
(4) thionyl chloride crude product receives: the condensed product generated in thionyl chloride crude product condenser is passed into crude product receiving slit
In, crude product thionyl chloride is obtained after degassing purification, low-boiling-point substance is drawn into gas separator using gas unidirectional conveying apparatus；
(5) match reaction of Salmon-Saxl: the crude product receiving slit purified product that purification kettle generates that deaerates being passed into in sulphur kettle, under normal pressure state
It carries out with reaction of Salmon-Saxl, the additional amount of sulphur is the 70-80% of sulfur content needed for reacting completely；
(6) rectification and purification: the product with reaction of Salmon-Saxl is passed into rectifier unit and carries out rectification and purification, while in rectifier unit
Excessive vulcanization is carried out, thionyl chloride finished product is finally obtained.
6. a kind of thionyl chloride according to claim 5 produces gas phase circulation method, it is characterised in that: sulfur dichloride synthesis
The gas outlet pressure P1 of kettle is greater than the gas outlet pressure P2 of thionyl chloride crude product synthesis reactor, and the height of sulfur dichloride synthesis reactor wants high
In the height of thionyl chloride synthesis reactor, the position of thionyl chloride crude product receiving slit is higher than crude product and matches sulphur kettle.
7. a kind of thionyl chloride according to claim 5 produces gas phase circulation method, it is characterised in that: the gas separation
The position of device is higher than the position of thionyl chloride synthesis reactor and the position of sulfur dichloride synthesis reactor.
8. a kind of thionyl chloride according to claim 5 produces gas phase circulation method, it is characterised in that: described in sulphur kettle
The method that sulphur is added is that first selection sulfur in lump form is spare, then crushes the sulfur in lump form of selection together with desiccant calcium chloride granules,
Smashed particle reaches 30~50 mesh, then smashed mixed-powder is sent to being carried out in sulphur kettle with reaction of Salmon-Saxl.
9. a kind of thionyl chloride according to claim 5 produces gas phase circulation method, it is characterised in that: the gas unidirectional
Conveying device is set as liquid injection apparatus, and the liquid injection apparatus is at least arranged one, and the liquid injection apparatus will be taken out
The incoagulable gas taken is passed into gas separator.
10. a kind of thionyl chloride produces gas phase circulator, it is characterised in that: including sulfur dichloride synthesis reactor (1), thionyl chloride
Synthesis reactor (2) matches sulphur kettle (3), crude product condenser (4), crude product receiving slit (6), liquid injection apparatus (7) and gas separator
(12), adsorbent equipment (14) are conciliate in setting adsorbent equipment (13) inside the gas separator (12).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811427355.3A CN109485019B (en) | 2018-11-27 | 2018-11-27 | Gas phase circulating device and method for producing thionyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811427355.3A CN109485019B (en) | 2018-11-27 | 2018-11-27 | Gas phase circulating device and method for producing thionyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109485019A true CN109485019A (en) | 2019-03-19 |
| CN109485019B CN109485019B (en) | 2020-11-13 |
Family
ID=65697800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811427355.3A Active CN109485019B (en) | 2018-11-27 | 2018-11-27 | Gas phase circulating device and method for producing thionyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109485019B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431823A (en) * | 1946-02-16 | 1947-12-02 | Pittsburgh Plate Glass Co | Manufactruing thionyl chloride |
| CN101284653A (en) * | 2008-01-30 | 2008-10-15 | 江西电化精细化工有限责任公司 | Gas phase circulation method in synthesis of thionyl chloride |
| CN101412502A (en) * | 2008-01-18 | 2009-04-22 | 江西世龙实业股份有限公司 | Method for using gas unidirectional conveying apparatus in thionyl chloride cycle production process |
| CN103043620A (en) * | 2012-12-31 | 2013-04-17 | 山东凯盛新材料股份有限公司 | Method for recycling tail gas during thionyl chloride preparation |
| CN205634893U (en) * | 2016-05-06 | 2016-10-12 | 新乡瑞诚科技股份有限公司 | Synthetic for thionyl chloride mother liquor recycling utilize system |
| CN106145059A (en) * | 2016-07-04 | 2016-11-23 | 汇智工程科技有限公司 | A kind of thionyl chloride reclaims, in producing, the method that sulfur dioxide recycles |
-
2018
- 2018-11-27 CN CN201811427355.3A patent/CN109485019B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431823A (en) * | 1946-02-16 | 1947-12-02 | Pittsburgh Plate Glass Co | Manufactruing thionyl chloride |
| CN101412502A (en) * | 2008-01-18 | 2009-04-22 | 江西世龙实业股份有限公司 | Method for using gas unidirectional conveying apparatus in thionyl chloride cycle production process |
| CN101284653A (en) * | 2008-01-30 | 2008-10-15 | 江西电化精细化工有限责任公司 | Gas phase circulation method in synthesis of thionyl chloride |
| CN103043620A (en) * | 2012-12-31 | 2013-04-17 | 山东凯盛新材料股份有限公司 | Method for recycling tail gas during thionyl chloride preparation |
| CN205634893U (en) * | 2016-05-06 | 2016-10-12 | 新乡瑞诚科技股份有限公司 | Synthetic for thionyl chloride mother liquor recycling utilize system |
| CN106145059A (en) * | 2016-07-04 | 2016-11-23 | 汇智工程科技有限公司 | A kind of thionyl chloride reclaims, in producing, the method that sulfur dioxide recycles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109485019B (en) | 2020-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100480173C (en) | Liquid phase circulation method in synthesis of thionyl chloride | |
| CN103724155B (en) | A kind of production technique of propenyl chloride | |
| CN104445272B (en) | A kind of conversion gas phlegma comprehensive reutilization method containing ammonia, carbonic acid gas | |
| CN100480174C (en) | Gas phase circulation method in synthesis of thionyl chloride | |
| CN101412503B (en) | Method for synthesizing thionyl chloride with crude product thionyl chloride as raw material | |
| CN104843650B (en) | A kind of Gas Purification Factory low-sulfur high-carbon acid gas sulfur recovery technology and device | |
| CN106242961A (en) | Production of chloroacetic acid equipment | |
| CN104876792A (en) | Method for producing high-purity chloropropene | |
| CN101781164B (en) | Preparation method of difluoromono-chloroethane | |
| CN101747176A (en) | Method for preparation of trifluoro acetyl chloride with trifluoroethane chlorinated mixture | |
| CN103012054A (en) | Device and method for preparing ultra-high purity difluoromono-chloroethane | |
| CN103012053A (en) | Method for preparing ultra-high purity difluoromono-chloroethane | |
| CN109319736A (en) | Ammonia tank periodic off-gases recyclable device and its technique | |
| CN109485019A (en) | A kind of thionyl chloride production gas phase circulator and method | |
| CN206328142U (en) | A kind of preparation system of anhydrous hydrogen chloride | |
| CN100497164C (en) | Multistage rectification process for high-purity thionyl chloride | |
| CN109231168B (en) | Method and device for reducing sulfuric acid content in hydrochloric acid and acetic acid by-products in chloroacetic acid production | |
| CN217313451U (en) | Tower type continuous preparation device for bis (fluorosulfonyl) imide | |
| CN208130781U (en) | The system for handling polycrystalline silicon reduction exhaust | |
| CN106745066B (en) | Produce, purify the safe technology and system of hydrogen cyanide | |
| CN106220491A (en) | Production of chloroacetic acid method | |
| CN203007173U (en) | Preparation device of ultra-high-purity difluoromonochloroethane | |
| CN109456431B (en) | Clean closed-loop production method and system for polyolefin | |
| CN100480172C (en) | Method for conveying crude product of thionyl chloride form low pressure to high pressure by high potential difference | |
| CN106621715A (en) | Device for recovering chlorine hydride in PVC production process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |