CN108557775A - Exhaust gas treating method, the system of implementation this method in chlorosulfonic acid preparation process and the preparation method of chlorosulfonic acid - Google Patents
Exhaust gas treating method, the system of implementation this method in chlorosulfonic acid preparation process and the preparation method of chlorosulfonic acid Download PDFInfo
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- CN108557775A CN108557775A CN201810632199.8A CN201810632199A CN108557775A CN 108557775 A CN108557775 A CN 108557775A CN 201810632199 A CN201810632199 A CN 201810632199A CN 108557775 A CN108557775 A CN 108557775A
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- 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
- C01B17/46—Compounds containing sulfur, halogen, hydrogen, and oxygen
- C01B17/466—Chlorosulfonic acid (ClSO3H)
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- 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
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/775—Liquid phase contacting processes or wet catalysis processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention provides a kind of exhaust gas treating method in chlorosulfonic acid preparation process, implements the system of this method and the preparation method of chlorosulfonic acid.The exhaust gas treating method includes the following steps：Acid pickling step：The SO in the tail gas is absorbed using absorbent3Gas；Water-washing step：The HCl gases in the tail gas are absorbed using water, obtain hydrochloric acid；Drying steps：Utilize the SO in tail gas described in desiccant dryness2Gas.The tail gas generated in the preparation process of the chlorosulfonic acid of the present invention, utilizes appropriate sorption enhanced processing mode, abundant recycling; lye absorption is not needed, so that whole process only generates chlorosulfonic acid, hydrochloric acid and sulfuric acid, does not generate waste water, exhaust gas; while economizing on resources, environmental protection.
Description
Technical field
The present invention relates to the systems and chlorine sulphur of exhaust gas treating method, implementation this method in a kind of chlorosulfonic acid preparation process
The preparation method of acid, belongs to chemical process technical field.
Background technology
Chlorosulfonic acid is a kind of important inorganic acid, is mainly used for the sulfonation of organic compound, manufacture sulfa drugs, saccharin
And the sulfonating agent as dyestuff intermediate, it is also used for manufacture pesticide, detergent, ion exchange resin, plastic cement etc., is used as in military affairs
Screening smoke.
The production process of chlorosulfonic acid is with dry HCl gases and SO3Gas is raw material, is closed by synthetic tower and stand-by still
At reaction, condenses and be made using cold point.Its synthesize process be a continuous process, during synthesis often due to
Tolerance is unstable, and leads to HCl gases and SO3The ratio of gas is deviated, and a large amount of SO are still contained in tail gas3、SO2、HCl
Equal sour gas accomplish qualified discharge for environmental protection, need to absorb by lye.
Using lye to the mixing of some such as sulfate, sulphite, chlorate saliferous can be obtained after tail gas absorption
Object.Then the mixture of above-mentioned salt is detached again.It, generally can be right but since the mixture of above-mentioned salt is not readily separated
It carries out processing discharge.Or hydrochloric acid can be produced to the reuse of tail gas part, remaining absorbs to obtain the mixture of saliferous simultaneously with lye
Processing discharge.But be prepared be salt mixture, the purity of single salt component is too low, and causing cannot be fully by tail gas recycle
It utilizes, and will produce a large amount of waste water, cause the waste of resource.
Patent application CN106800276A discloses a kind of industrialization using sterling sulfur trioxide vapor- phase synthesis chlorosulfonic acid
Production method, including a, with the SO in one turn of flue gas3Produce 40% oleum；B, sterling SO is produced in evaporation3Gas；C, hydrochloric acid
Desorption produces sterling HCl；D, with HCl gases and sterling SO3Gas synthesis rents product chlorosulfonic acid；E, chlorosulfonic acid is refined；With f, tail
The processing of gas and etc..This method needs to obtain the sulfur trioxide of sterling, and preparation method is complicated, obtains difficulty height, required cost
It is higher.
Invention content
Problems to be solved by the invention
The purpose of the present invention is to provide in a kind of chlorosulfonic acid preparation process exhaust gas treating method, implement this method and be
The preparation method of system and chlorosulfonic acid.The tail gas generated in the preparation process of the chlorosulfonic acid of the present invention is turned using appropriate absorption
Change processing mode, byproduct is hydrochloric acid and sulfuric acid, tail gas can be made to reach zero-emission, and there is certain economic benefit and environmental protection to imitate
Benefit meets the requirement of green chemical industry.
Further, by process conditions appropriate and rational measure, the resource between each process is made to make full use of, produced
The chlorosulfonic acid of high concentration.
The solution to the problem
The present invention provides the exhaust gas treating method in a kind of chlorosulfonic acid preparation process, includes the following steps：
Acid pickling step：The SO in the tail gas is absorbed using absorbent3Gas；
Water-washing step：The HCl gases in the tail gas are absorbed using water, obtain hydrochloric acid；
Drying steps：Utilize the SO in tail gas described in desiccant dryness2Gas.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein the salt that the water-washing step obtains
A concentration of 28-34%, preferably 28-32% of acid.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein the temperature of the acid pickling step exists
70 DEG C or less；The absorbent includes sulfuric acid, it is preferable that a concentration of 93%-100% of the sulfuric acid, preferably 97.5%-
98.5%.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein the temperature of the drying steps exists
70 DEG C or less；The drier includes sulfuric acid, it is preferable that a concentration of 93-100% of the sulfuric acid, preferably 97.5-
98.5%.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein also wrapped after the drying steps
It includes：
Step of converting：Under the effect of the catalyst, by the SO in the tail gas after drying2Gas is converted into SO3Gas obtains
Containing SO3Tail gas.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein the temperature control of the step of converting
System is between 380-450 DEG C, preferably between 400-420 DEG C.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein after the drying steps, institute
Before stating step of converting, contain SO using what is obtained in chlorosulfonic acid preparation process3Admixture of gas to after drying tail gas carry out
Preheating, wherein described to contain SO3Admixture of gas temperature between 400-500 DEG C, preferably between 420-480 DEG C；
After preheating, contain SO3Admixture of gas temperature between 150-200 DEG C；The temperature of tail gas after preheating exists
Between 250-350 DEG C.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, wherein further include：
Contain SO using described3Tail gas exchange heat to the tail gas after the preheating of next group；Preferably, the tail gas after heat exchange
Temperature between 340-430 DEG C, preferably between 370-400 DEG C.
The present invention also provides a kind of preparation methods of chlorosulfonic acid, include the following steps：
HCl gas preparation processes：HCl gases will be generated after resolving hydrochloric acid；
SO3Gas preparation process：The furnace gas generated after sulphur is burned obtains containing SO using catalyst conversion production3Gas
Body mixture；
Chlorosulfonic acid preparation process：The HCl gases are contained into SO with described3Admixture of gas mixed, obtain chlorine sulphur
Acid gas；
Vent gas treatment step：Exhaust gas treating method according to the present invention handles tail gas.
The preparation method of chlorosulfonic acid according to the present invention, the chlorosulfonic acid preparation process further include：
Cooling step：The chlorosulfonic acid gas is cooled down；
Recycling step：The unreacted HCl gases are contained into SO with described3Admixture of gas recycling.
The preparation method of chlorosulfonic acid according to the present invention, wherein the SO3Gas preparation process is obtained to contain SO3Gas
In body mixture, SO3Content is 8-11%, SO2Content is 0.5-2%；
Preferably, described to contain SO3Admixture of gas temperature between 400-500 DEG C, preferably 420-480 DEG C it
Between.
The present invention also provides a kind of system for implementing the exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention,
Including：
Pickling tower absorbs the SO in the tail gas using absorbent3Gas；
Water scrubber absorbs the HCl gases in the tail gas using water, obtains hydrochloric acid；
Drying tower utilizes the SO in tail gas described in desiccant dryness2Gas.
System according to the present invention, wherein the system also includes：
Converter is used for the SO in the tail gas after drying2Gas is converted into SO3Gas.
The system according to the present invention, wherein the system also includes：Preheater, heat exchanger, heater, economizer and suction
Receive the combination of one or more of tower.
The system according to the present invention, wherein the equipment for preparing the chlorosulfonic acid includes：
Resolving hydrochloric acid device is used to that HCl gases will to be generated after resolving hydrochloric acid；
Sulfuric acid production plant, the furnace gas generated after being used to burn in sulphur obtain containing SO using catalyst conversion production3
Admixture of gas；
Chlorosulfonic acid process units is used to the HCl gases containing SO with described3Admixture of gas mixed, obtain
To chlorosulfonic acid gas.
The system according to the present invention, the chlorosulfonic acid process units include：Synthetic tower, cold point of tower and stand-by still, wherein
The synthetic tower is used to the HCl gases containing SO with described3Admixture of gas mixed, to obtain chlorine sulphur
Acid gas；
The cold point of tower is for cooling down to obtained chlorosulfonic acid gas；
The stand-by still is used to the unreacted HCl gases containing SO with described3Admixture of gas recycling.
The effect of invention
The tail gas generated in the preparation process of the chlorosulfonic acid of the present invention, using appropriate sorption enhanced processing mode, fully
Recycling does not need lye absorption so that whole process only generates chlorosulfonic acid, hydrochloric acid, sulfuric acid, do not generate waste water,
Exhaust gas, while economizing on resources, environmental protection.
Further, by process conditions appropriate and rational measure, the resource between each process is made to make full use of.
Further, SO3Heat in gas conversion process can make full use of, and the preheating before tail gas conversion need not be outer
Portion's heat supply, energy saving consumption.
Description of the drawings
Fig. 1 shows preparation and the tail gas treatment process flow chart of the chlorosulfonic acid of the embodiment of the present invention 1.
Specific implementation mode
It will be detailed below various exemplary embodiments, feature and the aspect of the present invention.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Any embodiment here as illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiment.
In addition, in order to better illustrate the present invention, numerous details is given in specific implementation mode below.
It will be appreciated by those skilled in the art that without certain details, the present invention can equally be implemented.In other example,
Method well known to those skilled in the art, means, equipment and step are not described in detail, in order to highlight the master of the present invention
Purport.
<First embodiment>
The first embodiment of the present invention provides the exhaust gas treating method in chlorosulfonic acid preparation process, includes the following steps：
Acid pickling step：The SO in the tail gas is absorbed using absorbent3Gas；
Water-washing step：The HCl gases in the tail gas are absorbed using water, obtain hydrochloric acid；
Drying steps：Utilize the SO in tail gas described in desiccant dryness2Gas obtains dry tail gas.
In the present invention, the complete SO of unreacted is contained in tail gas3, the complete HCl of unreacted and have neither part nor lot in reaction
SO2, in addition, other gas components that may be present, such as air etc. can also be contained in tail gas.In the present invention, pickling walks
Suddenly, drying steps can also be carried out with being carried out in same reactor in different reactors, such as：It can be respectively dry
It is carried out in dry tower or pickling tower.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, the hydrochloric acid that the water-washing step obtains it is dense
Degree is 28-34%, preferably 28-32%.The hydrochloric acid being prepared when vent gas treatment of the present invention can be back to the preparation of HCl gases
In step, resolving hydrochloric acid is carried out, to prepare HCl gases.
In the acid pickling step of the present invention, the absorbent can be sulfuric acid, and the concentration of sulfuric acid can be 93%-
100%, it is preferable that sulfuric acid concentration can be 97.5%-98.5%, and the temperature of the acid pickling step is at 70 DEG C hereinafter, preferably
55-65℃.In addition, in the drying steps of the present invention, the drier may be sulfuric acid, and the concentration of sulfuric acid may be
93%-100%, it is preferable that sulfuric acid concentration can be 97.5%-98.5%；The temperature of the drying steps at 70 DEG C hereinafter,
Preferably 55-65 DEG C.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, the drying steps further include later：Turn
Change step：Under the effect of the catalyst, by the SO in the tail gas after drying2Gas is converted into SO3Gas, to obtain containing SO3
Tail gas.The catalyst can be phosphorus/vanadium catalyst, such as vanadium pentoxide etc..What is obtained contains SO3Tail gas can recycle
Absorbent absorbs SO therein3Then gas is back in sulfuric acid production plant to prepare chlorosulfonic acid.In general, inverted
What device converted contains SO3Tail gas temperature be 440-480 DEG C.
In general, in chlorosulfonic acid preparation process, SO is being prepared3When gas, temperature is generally obtained at 400-500 DEG C
Between, contain SO preferably between 420-480 DEG C3Admixture of gas.The temperature range can be utilized contains SO3Gas it is mixed
It closes object and the pre-heat treatment is carried out to the tail gas after drying steps, before step of converting.To make to contain SO3Admixture of gas temperature drop
Down to 150-200 DEG C, in favor of preparing chlorosulfonic acid gas；And the temperature of the tail gas after can making drying steps, before step of converting
Degree is increased between 250-350 DEG C, preferably between 290-320 DEG C, to be conducive to the progress of step of converting.
By using containing SO3Admixture of gas to after drying steps, before step of converting tail gas carry out the pre-heat treatment,
Make SO3The heat of gas in the conversion process can be fully used, so as to further save the energy.
After preheated, can the tail gas of preheating be subjected to heat exchange processing again, the inverted step of last consignment of can be utilized to convert
What is obtained afterwards contains SO3Tail gas exchange heat.In general, the tail gas of preheating can be exchanged heat to 340-430 DEG C, as excellent
Choosing, can exchange heat to 370-400 DEG C.Above-mentioned heating process does not use external heating, energy saving can consume.
After heat exchange, the tail gas after drying steps, before step of converting can be added by heater (heating wire) again
Heat.Then the temperature of the tail gas after drying steps, before step of converting is heated to 380-450 DEG C again, preferably, dry step
The temperature of tail gas after rapid, before step of converting is heated to 400-420 DEG C.
Exhaust gas treating method in chlorosulfonic acid preparation process according to the present invention, what the step of converting obtained contains SO3's
Tail gas contains SO after heat exchange3Tail gas temperature reduce, generally between 380-400 DEG C, can further utilize save coal
Device, which reduces, contains SO3Tail gas temperature, such as be cooled to 150-190 DEG C.And then acid pickling step can be carried out again and (also referred to as inhaled
Receive step), i.e.,：The SO for converting and obtaining is absorbed using absorbent3Gas.In acid pickling step, the absorbent preferably wraps
Include sulfuric acid, a concentration of 93%-100% of used sulfuric acid, it is preferable that a concentration of 97.5%-98.5% of the sulfuric acid；Acid
The temperature for washing step is controlled at 70 DEG C hereinafter, preferably 55-65 DEG C, in acid pickling step, can be sprayed by using absorbent
Cross-flow absorbs.
In the present invention, the sulfuric acid finally generated can be back in the present invention, drying, tail gas recycle for HCl gases
Acid pickling step, drying steps and step of converting in step etc..In addition, the dry step in the tail gas recycle step of the present invention
Suddenly, the sulfuric acid in acid pickling step, step of converting can be used as needed, not generate Waste Sulfuric Acid, can not external complement
Sulfuric acid.
The exhaust gas treating method in chlorosulfonic acid preparation process through the invention, can be prepared sulfuric acid, hydrochloric acid, to
It is back in the preparation process of chlorosulfonic acid.
<Second embodiment>
Second embodiment of the present invention provides a kind of preparation method of chlorosulfonic acid, includes the following steps：
HCl gas preparation processes：HCl gases will be generated after resolving hydrochloric acid；
SO3Gas preparation process：The furnace gas generated after sulphur is burned obtains containing SO using catalyst conversion production3Gas
Body mixture；
Chlorosulfonic acid preparation process：The HCl gases are contained into SO with described3Admixture of gas mixed, obtain chlorine sulphur
Acid gas；
Vent gas treatment step：Exhaust gas treating method according to the present invention handles tail gas.
In the present invention, resolving hydrochloric acid can be existing arbitrary analytic method, for example, salt acidolysis of the invention
Analysis can pass through high temperature HCl gas and water vapour of the concentrated hydrochloric acid in the Analytic Tower of low-voltage high-temperature with process reboiler heating
Continuously contact with countercurrent mass transfer, heat transfer process, concentrated hydrochloric acid declines along filler surface by gravity, contacted with the gas of rising,
To make HCl gas contents in uprising gas be continuously increased, the HCl gases containing saturated water are obtained in tower top, it is cold through room temperature level-one
But it cools down to obtain HCl gases with deep cooling two level, and bottom of tower obtains barostat control.Barostat control boils in the Analytic Tower of high pressure-temperature with broken
Agent solution mixes, and using the principle for breaking azeotropic point, HCl gases is again separate out to come, broken to boil agent solution after processing and follow
Ring uses.
The concentration of HCl gases after present invention parsing is higher, can generally reach 99.5% or more.In general, making
It after obtaining HCl gases, needs that processing is dried to HCl gases, to obtain dry HCl gases, to be conducive to prepare
Chlorosulfonic acid gas.
In the preparation method of the chlorosulfonic acid of the present invention, in the HCl gases preparation process, drier can be utilized to described
HCl gases are dried processing, and the temperature of the drying is at 70 DEG C hereinafter, preferably 55-65 DEG C；It is highly preferred that the drying
Agent can be sulfuric acid, a concentration of 93%-100% of the sulfuric acid, it is further preferred that a concentration of 97.5%- of the sulfuric acid
98.5%.
In the preparation method of the chlorosulfonic acid of the present invention, the SO3Gas preparation process is obtained to contain SO3Mixed gas
In, SO3Content is 8-11%, SO2Content is 0.5-2%, and surplus is generally air.What is be prepared contains SO3Mixed gas without
It needs to handle, is used directly for production chlorosulfonic acid.
Preferably, the SO3In gas preparation process, what is obtained contains SO3Admixture of gas temperature at 400-500 DEG C
Between, preferably between 420-480 DEG C.
In the present invention, it is however generally that, the temperature of chlorosulfonic acid preparation process is at 100-180 DEG C, preferably 120-150 DEG C.
Preferably, the chlorosulfonic acid preparation process further includes：Cooling step：The chlorosulfonic acid gas is cooled down, to obtain
Liquid chlorosulfonic acid, convenient for collecting application；Recycling step：The unreacted HCl gases are contained into SO with described3Admixture of gas
Recycling makes the unreacted HCl gases contain SO with described3Admixture of gas mix again, to being further prepared
Chlorosulfonic acid gas.In general, the temperature of recycling step is generally at 30-80 DEG C, preferably 40-60 DEG C.
<Third embodiment>
In a kind of implementation according to the first embodiment of the invention of third embodiment of the present invention offer or with second in fact
The system for applying the exhaust gas treating method in the chlorosulfonic acid preparation process in mode comprising：
Pickling tower absorbs the SO in the tail gas using absorbent3Gas；
Water scrubber absorbs the HCl gases in the tail gas using water, obtains hydrochloric acid；
Drying tower utilizes the SO in tail gas described in desiccant dryness2Gas.
System according to the present invention, the system also includes：
Converter is used for the SO in the tail gas after drying2Gas is converted into SO3Gas.
System according to the present invention, the system also includes preheater, heat exchanger, heater, economizer and absorptions
The combination of one or more of tower.
The preheater can after the drying step, before carrying out step of converting, for being preheated to tail gas；It is described
Heat exchanger can be used for carrying out heat exchange heating to the tail gas after preheating, and the heat exchanger can be also used for containing to what is obtained after conversion
SO3Tail gas carry out heat exchange cooling；The heater (such as：Electric furnace) can be used for heat exchanging heating after tail gas added again
Heat, to be conducive to the progress of step of converting, what the economizer can be used for obtaining after cooling down to conversion contains SO3Tail gas again
Cool down, 150~190 DEG C can be cooled to, to be conducive to the progress of acid pickling step (also referred to as absorption step).It is described
Absorption tower be used to absorb using absorbent obtain after the conversion contain SO3Tail gas in SO3Gas.
System according to the present invention, the equipment for preparing the chlorosulfonic acid include：
Resolving hydrochloric acid device is used to that HCl gases will to be generated after resolving hydrochloric acid；
Sulfuric acid production plant, the furnace gas generated after being used to burn in sulphur obtain containing SO using catalyst conversion production3
Admixture of gas；
Chlorosulfonic acid process units is used to the HCl gases containing SO with described3Admixture of gas mixed, obtain
To chlorosulfonic acid gas.
In the present invention, processing can be dried to the HCl gases of generation using drying tower；Using preheater and/or
Heat exchanger is to containing SO3Admixture of gas carry out heat exchange cooling, then by dry HCl gases with heat exchange cooling after SO3Gas
Mixing, is prepared chlorosulfonic acid gas.
In the present invention, the chlorosulfonic acid process units includes synthetic tower, cold point of tower and stand-by still, wherein the conjunction
It is used to the HCl gases containing SO with described at tower3Admixture of gas mixed, to prepare chlorosulfonic acid gas.It is general and
The temperature of speech, synthetic tower controls between 100-180 DEG C, preferably between 120-150 DEG C.The cold point of tower is used for gained
To chlorosulfonic acid gas cool down, to obtain liquid chlorosulfonic acid；The stand-by still is used for the unreacted HCl gases
Contain SO with described3Admixture of gas recycling, it is however generally that, the temperature of stand-by still controls between 30-80 DEG C, preferably in 40-
Between 60 DEG C.
As shown in Figure 1, in fact, in synthetic tower, SO3It is usually excessive, after stand-by still recycles, meeting in stand-by still
Contain SO containing excessive3Gas, dry HCl gases can be conveyed to a part at this time in stand-by still, and it is unreacted
The HCl gases contain SO with described3Admixture of gas mixed, and be delivered to synthetic tower again to synthesize chlorosulfonic acid.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
Fig. 1 shows preparation and the tail gas treatment process flow chart of a kind of chlorosulfonic acid.As shown in Figure 1, the chlorosulfonic acid
It prepares and tail gas treatment process includes the following steps：
Step 1) will generate HCl gases in resolving hydrochloric acid device after resolving hydrochloric acid, it is 98% then to utilize mass fraction
Sulfuric acid be dried, and the HCl gases after drying are delivered in the synthetic tower of chlorosulfonic acid process units.
Step 2) is in sulfuric acid production plant, the furnace gas generated after sulphur is burned, and conversion production obtains containing SO3Gas
Mixture, wherein contain SO3Admixture of gas in, SO3Content is 10.5%, SO2Content is 0.8%.Containing SO3Gas it is mixed
The temperature for closing object is 440-450 DEG C.Then contain SO using this3Admixture of gas to it is preceding a batch production chlorosulfonic acid generate warp
Tail gas after drying is preheated, and after preheating, contains SO3Admixture of gas temperature control at 160-170 DEG C, then will cooling
Afterwards contain SO3Admixture of gas be delivered in the synthetic tower of chlorosulfonic acid process units.
SO of the step 3) by dry HCl gases and after cooling down3Gas synthesizes chlorosulfonic acid gas, synthetic tower in synthetic tower
Temperature is controlled at 120-130 DEG C.
The chlorosulfonic acid gas of step 4) synthesis is delivered to cold point of tower and carries out after cooling down, and chlorosulfonic acid liquid is made.And it will not
The HCl gases of reaction contain SO with unreacted3Admixture of gas be delivered to stand-by still and recycled, wherein stand-by still temperature
50-60 DEG C of control, further prepares chlorosulfonic acid gas.
Step 5) passes through circulated sprinkling in pickling tower by tail gas caused by chlorosulfonic acid is produced using 97.8% sulfuric acid
Absorb the SO in tail gas3Gas.
Step 6) absorbs the HCl gases in the tail gas using water circulated sprinkling in water scrubber, dense to be prepared
The hydrochloric acid that degree is 28%.
Step 7) dries the sulfuric acid of remaining waste gas utilization 98% to remove moisture removal；Then it is prepared into using step 3)
That arrives contains SO3Admixture of gas preheated, the tail gas after drying is preheated to temperature between 280-290 DEG C；Then again
Contain SO using what inverted device in last consignment of tail gas converted3Tail gas exchange heat, exchange heat to 380-390 DEG C；Then again
It is heated to 400-410 DEG C using electric furnace, then this is heated to 400-410 DEG C of tail gas be delivered to converter, after heating
SO in tail gas2Gas is converted into SO3Gas, what inverted device converted contains SO3Tail gas temperature be 455 DEG C -465 DEG C.
What the inverted device of step 8) converted contains SO3Waste gas utilization next group pass through contain SO3Admixture of gas preheating
Tail gas carries out heat exchange cooling, is cooled to 380-390 DEG C, then cools down using economizer, is cooled to 160-170 DEG C.After cooling,
98% sulfuric acid absorption is utilized in absorption tower, wherein the temperature on absorption tower is controlled at 55-65 DEG C.
Embodiment 2
Step 1) will generate HCl gases, be then using mass fraction in resolving hydrochloric acid device after resolving hydrochloric acid
97.5% sulfuric acid is dried, and the HCl gases after drying are delivered in the synthetic tower of chlorosulfonic acid process units.
Step 2) is in sulfuric acid production plant, the furnace gas generated after sulphur is burned, and conversion production obtains containing SO3Gas
Mixture, wherein contain SO3Admixture of gas in, SO3Content is 9.8%, SO2Content is 1.5%.Containing SO3Gas mixing
The temperature of object is 420-430 DEG C.Then contain SO using this3Admixture of gas to it is preceding a batch production chlorosulfonic acid generate through drying
Tail gas is preheated afterwards, after preheating, contains SO3Admixture of gas temperature control at 170-180 DEG C, then by containing after cooling
SO3Admixture of gas be delivered in the synthetic tower of chlorosulfonic acid process units.
SO of the step 3) by dry HCl gases and after cooling down3Gas synthesizes chlorosulfonic acid gas, synthetic tower in synthetic tower
Temperature is controlled at 100-110 DEG C.
The chlorosulfonic acid gas of step 4) synthesis is delivered to after cold point of tower carries out cooling and chlorosulfonic acid liquid is made.And it will be not anti-
The HCl gases answered described contain SO with unreacted3Admixture of gas be delivered to stand-by still and recycled, wherein auxiliary
Tower temperature degree controls 40-50 DEG C, further prepares chlorosulfonic acid gas.
Step 5) passes through circulated sprinkling in pickling tower by tail gas caused by chlorosulfonic acid is produced using 97.8% sulfuric acid
Absorb the SO in tail gas3Gas.
Step 6) absorbs the HCl gases in the tail gas using water circulated sprinkling in water scrubber, dense to be prepared
The hydrochloric acid that degree is 28%.
Step 7) dries the sulfuric acid of remaining waste gas utilization 97.5% to remove moisture removal；Then it is prepared into using step 3)
That arrives contains SO3Admixture of gas preheated, the tail gas after drying is preheated to temperature between 300-310 DEG C；Then again
It is heated to 400-410 DEG C using electric furnace, then this is heated to 400-410 DEG C of tail gas be delivered to converter, after heating
SO in tail gas2Gas is converted into SO3Gas, what inverted device converted contains SO3Tail gas temperature be 455 DEG C -465 DEG C.
What the inverted device of step 8) converted contains SO3Tail gas cool down by economizer, be cooled to 180-190 DEG C, drop
Wen Hou utilizes 98% sulfuric acid absorption, wherein the temperature on absorption tower is controlled at 55-65 DEG C in absorption tower.
Comparative example
Step 1) utilizes sulfuric acid production plant, and sulphur is burned to the SO generated2Furnace gas conversion production obtains containing SO3Gas
Mixture, then pass through sulfuric acid cyclic absorption wherein SO3, by SO in sulfuric acid3Concentration is improved to 20%, subsequently niacin is utilized to evaporate
Device is evaporated, and obtains high-purity SO3Gas, wherein SO3The purity of gas is 99.3%.
Step 2) generates HCl gases in resolving hydrochloric acid device, by resolving hydrochloric acid, and it is 97.8% then to utilize mass fraction
Sulfuric acid be dried, and the HCl gases after drying are delivered in the synthetic tower of chlorosulfonic acid process units.
Step 3) is by the SO of dry HCl gases and high-purity3Gas synthesizes chlorosulfonic acid gas, synthetic tower in synthetic tower
Temperature is controlled at 100-110 DEG C.
The chlorosulfonic acid gas of step 4) synthesis is delivered to after cold point of tower carries out cooling and chlorosulfonic acid liquid is made.And it will be not anti-
The HCl gases and SO answered3Gas be delivered to stand-by still and recycled, wherein stand-by still temperature controls 40-50 DEG C.
Step 5) will produce tail gas caused by chlorosulfonic acid and be inhaled by circulated sprinkling using 98% sulfuric acid in pickling tower
SO in ending gas3Gas.
Step 6) absorbs the HCl gases in the tail gas using water circulated sprinkling in water scrubber, dense to be prepared
Degree is 28% hydrochloric acid.
Step 7) is discharged after absorbing remaining waste gas utilization lye.
Comparative example 2
Step 1) will generate HCl gases, be then using mass fraction in resolving hydrochloric acid device after resolving hydrochloric acid
98.3% sulfuric acid is dried, and the HCl gases after drying are delivered in the synthetic tower of chlorosulfonic acid process units.
Step 2) is in sulfuric acid production plant, the furnace gas generated after sulphur is burned, and conversion production obtains containing SO3Gas
Mixture, wherein contain SO3Admixture of gas in, SO3Content is 10.3%, SO2Content is 1.1%.Containing SO3Gas it is mixed
The temperature for closing object is 450-460 DEG C.Then contain SO using this3Admixture of gas to it is preceding a batch production chlorosulfonic acid generate warp
Tail gas exchanges heat after drying, after preheating, contains SO3The temperature of admixture of gas be down to 150-160 DEG C, then will be after cooling
Containing SO3Admixture of gas be delivered in the synthetic tower of chlorosulfonic acid process units.
SO of the step 3) by dry HCl gases and after cooling down3Gas synthesizes chlorosulfonic acid gas, synthetic tower in synthetic tower
Temperature is controlled at 120-130 DEG C.
The chlorosulfonic acid gas of step 4) synthesis is delivered to after cold point of tower carries out cooling and chlorosulfonic acid liquid is made.And it will be not anti-
The HCl gases answered contain SO with described3Admixture of gas be delivered to stand-by still and recycled, wherein stand-by still temperature control
50-60 DEG C processed.
Step 5) will be produced after waste gas utilization lye caused by chlorosulfonic acid absorbs and be discharged.
Measure of merit
The content for the chlorosulfonic acid that embodiment 1-2 and comparative example 1-2 is prepared is measured, and to heat energy recovery and tail gas
Treatment effect is evaluated, as shown in table 1 below.
Table 1
Wherein, the test method of chlorosulfonic acid content is examined using chemical titration in 4.3.2 in GB/T 13549-2016
It surveys.
From the measure of merit of embodiment 1-2 and comparative example 1-2 it is found that the chlorine sulphur produced with the present processes and device
Acid content meets the requirement of chlorosulfonic acid Grade A.And the hydrochloric acid and sulfuric acid that exhaust gas treating method through the invention is prepared
The waste of resource can will not be caused with direct reuse in the chlorosulfonic acid production process of the present invention.
By embodiment 1-2 compared with comparative example 1-2, the thermal energy and tail gas of the embodiment of the present invention are attained by comprehensive profit
With not generating absorption relief liquor, and technological operation is simple, obtained SO3It can directly use into chlorosulfonic acid production process, and
And the tail gas of the present invention absorbs discharge without lye, can comprehensively utilize production hydrochloric acid and sulfuric acid.
The foregoing is merely the specific implementation modes of the present invention, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (16)
1. the exhaust gas treating method in a kind of chlorosulfonic acid preparation process, which is characterized in that include the following steps：
Acid pickling step：The SO in the tail gas is absorbed using absorbent3Gas；
Water-washing step：The HCl gases in the tail gas are absorbed using water, obtain hydrochloric acid；
Drying steps：Utilize the SO in tail gas described in desiccant dryness2Gas.
2. the exhaust gas treating method in chlorosulfonic acid preparation process according to claim 1, which is characterized in that the washing step
Suddenly a concentration of 28-34% of the hydrochloric acid obtained, preferably 28-32%.
3. the exhaust gas treating method in chlorosulfonic acid preparation process according to claim 1 or 2, which is characterized in that the acid
The temperature of step is washed at 70 DEG C or less；The absorbent includes sulfuric acid, it is preferable that a concentration of 93%-100% of the sulfuric acid,
Preferably 97.5%-98.5%.
4. the exhaust gas treating method in chlorosulfonic acid preparation process according to claim 1 or 2, which is characterized in that described dry
The temperature of dry step is at 70 DEG C or less；The drier includes sulfuric acid, it is preferable that a concentration of 93-100% of the sulfuric acid, it is excellent
It is selected as 97.5-98.5%.
5. according to the exhaust gas treating method in claim 1-4 any one of them chlorosulfonic acid preparation process, which is characterized in that institute
Stating drying steps further includes later：
Step of converting：Under the effect of the catalyst, by the SO in the tail gas after drying2Gas is converted into SO3Gas obtains containing SO3
Tail gas.
6. the exhaust gas treating method in chlorosulfonic acid preparation process according to claim 5, which is characterized in that the conversion step
Rapid temperature controls between 380-450 DEG C, preferably between 400-420 DEG C.
7. the exhaust gas treating method in chlorosulfonic acid preparation process according to claim 5 or 6, which is characterized in that described
After drying steps, before the step of converting, contain SO using what is obtained in chlorosulfonic acid preparation process3Admixture of gas to dry
Tail gas after dry is preheated, wherein described to contain SO3Admixture of gas temperature between 400-500 DEG C, preferably in 420-
Between 480 DEG C；
After preheating, contain SO3Admixture of gas temperature between 150-200 DEG C；The temperature of tail gas after preheating is in 250-350
Between DEG C.
8. the exhaust gas treating method in chlorosulfonic acid preparation process according to claim 7, which is characterized in that further include：
Contain SO using described3Tail gas exchange heat to the tail gas after the preheating of next group；Preferably, the temperature of the tail gas after heat exchange
Degree is between 340-430 DEG C, preferably between 370-400 DEG C.
9. a kind of preparation method of chlorosulfonic acid, which is characterized in that include the following steps：
HCl gas preparation processes：HCl gases will be generated after resolving hydrochloric acid；
SO3Gas preparation process：The furnace gas generated after sulphur is burned obtains containing SO using catalyst conversion production3Gas it is mixed
Close object；
Chlorosulfonic acid preparation process：The HCl gases are contained into SO with described3Admixture of gas mixed, obtain chlorosulfonic acid gas
Body；
Vent gas treatment step：Tail gas is handled according to claim 1-8 any one of them exhaust gas treating methods.
10. the preparation method of chlorosulfonic acid according to claim 9, which is characterized in that the chlorosulfonic acid preparation process is also wrapped
It includes：
Cooling step：The chlorosulfonic acid gas is cooled down；
Recycling step：The unreacted HCl gases are contained into SO with described3Admixture of gas recycling.
11. the preparation method of chlorosulfonic acid according to claim 9 or 10, which is characterized in that the SO3Gas preparation process
It is obtained to contain SO3Admixture of gas in, SO3Content is 8-11%, SO2Content is 0.5-2%；
Preferably, described to contain SO3Admixture of gas temperature between 400-500 DEG C, preferably between 420-480 DEG C.
12. a kind of implementation is according to the exhaust gas treating method in claim 1-8 any one of them chlorosulfonic acid preparation process
System, which is characterized in that including：
Pickling tower absorbs the SO in the tail gas using absorbent3Gas；
Water scrubber absorbs the HCl gases in the tail gas using water, obtains hydrochloric acid；
Drying tower utilizes the SO in tail gas described in desiccant dryness2Gas.
13. system according to claim 12, which is characterized in that the system also includes：
Converter is used for the SO in the tail gas after drying2Gas is converted into SO3Gas.
14. system according to claim 12 or 13, which is characterized in that the system also includes：Preheater, heat exchanger,
The combination on one or more of heater, economizer and absorption tower.
15. according to claim 12-14 any one of them systems, which is characterized in that the equipment for preparing the chlorosulfonic acid includes：
Resolving hydrochloric acid device is used to that HCl gases will to be generated after resolving hydrochloric acid；
Sulfuric acid production plant, the furnace gas generated after being used to burn in sulphur obtain containing SO using catalyst conversion production3Gas
Body mixture；
Chlorosulfonic acid process units is used to the HCl gases containing SO with described3Admixture of gas mixed, obtain chlorine sulphur
Acid gas.
16. system according to claim 15, which is characterized in that the chlorosulfonic acid process units includes：Synthetic tower, cold point
Tower and stand-by still, wherein
The synthetic tower is used to the HCl gases containing SO with described3Admixture of gas mixed, to obtain chlorosulfonic acid gas
Body；
The cold point of tower is for cooling down to obtained chlorosulfonic acid gas；
The stand-by still is used to the unreacted HCl gases containing SO with described3Admixture of gas recycling.
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