CN206823499U - A kind of processing system of Claus device exhausts - Google Patents
A kind of processing system of Claus device exhausts Download PDFInfo
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- CN206823499U CN206823499U CN201720461975.3U CN201720461975U CN206823499U CN 206823499 U CN206823499 U CN 206823499U CN 201720461975 U CN201720461975 U CN 201720461975U CN 206823499 U CN206823499 U CN 206823499U
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Abstract
This disclosure relates to a kind of processing system of Claus device exhausts, the system includes combustion furnace, desulfurizing tower, bipolar membrane electrodialysis device and desorber；The gas access of the exhanst gas outlet of the combustion furnace and the desulfurizing tower is in fluid communication, the doctor solution outlet and the liquid inlet of the bipolar membrane electrodialysis device of the desulfurizing tower are in fluid communication, and the outlet of electrodialysis acid solution and the liquid inlet of the desorber of the bipolar membrane electrodialysis device are in fluid communication.Using the Claus device exhausts processing method of disclosure system can be handled Claus device exhausts to reach discharge standard, and operating cost is low.
Description
Technical field
A kind of this disclosure relates to processing system of Claus device exhausts.
Background technology
Claus (or being Crouse) technique is indispensable unit in petrochemical industry, mainly for the treatment of oil plus
Caused H during work2S gases.Processing H in 18832The Claus techniques of S gases are arisen at the historic moment, and it is by Carl Friedrich
Claus is invented, and core is H2S and SO2Sulphur is converted into by redox reaction, overall reaction is shown below：
2H2S(g)+SO2(g)→3Sx(s)+2H2O。
H in Claus technological basis unstripped gas2S concentration is different, can use direct current Claus methods (H2S concentration is higher than 50%), directly
Meet oxidation Claus methods (H215%) S concentration is less than and shunted Claus methods (H2S concentration is therebetween).Claus techniques are passed through
The development of last 100 yearses, oneself obtains elementary sulfur through turning into synthesis ammonia plant, methanol feedstock factory, natural gas and petroleum refiners etc.
Important component.Up to the present, Claus devices are covered, wherein 70% is used for refinery's sulphur recovery more the 600 had.2004
Year, the whole world is by Claus technique productions sulphur amounts up to 4.6 × 107T, increase by 3.5 × 10 in than 20026t.Sulphur is not only to produce
The raw material of sulfuric acid, and be widely used in oil plant, coke-oven plant, power station and chemical fertilizer factory etc., it is highly important chemical resource.
Traditional Claus recovery technology of sulfur flow is as shown in Figure 1 (it is Claus sulfur recovery facilities that dotted line frame is interior in Fig. 1).
The sour gas come from upstream device first passes around acid gas preheater, 145 DEG C is heated to, wherein 2/3 gas enters combustion furnace, with master
The preheated air that blower fan comes, is sufficiently mixed after-combustion at burner, by the control to air capacity, ensures only 1/2
H2S gases burning generation SO2.Temperature is about between 900-1300 DEG C in burner hearth, at this temperature, SO2With unburned H2S
Gas reaction generates elemental sulfur.Combustion gas mixes in combustion chamber with other 1/3 sour gas, still there is part elemental sulfur generation,
Sulphur enters sulphur liquid seal trough in liquid form；Mixed Process Gas enters waste heat boiler, by-product 0.5MPa (g) low-pressure steams,
The Process Gas for going out waste heat boiler is heated to 245 DEG C, into one-level converter (claus reaction device), in the presence of catalyst
H2S gases and SO2Gas continues to react, and generates elemental sulfur；210 DEG C are heated to about after Process Gas refrigerated separation, is converted into two level
Device is reacted, and reacted Process Gas enters B-grade condensation cooler, is condensed and is isolated Molten sulphur, goes out B-grade condensation cooling
The Claus device exhausts (or going out tail gas for Claus devices) of device send incinerator to fire after tail gas gathering device traps a small amount of sulphur
Burning processing, caused SO2Gas discharging, while by-product middle pressure steam.
Subject matter existing for traditional Claus sulfur recovery facilities is that Claus device exhausts contain SO2、H2S、COS、CS2
With Sx etc., the caused SO after burning disposal2Gas concentration is larger, if directly discharging, serious dirt will certainly be caused to environment
Dye.Improvement of the people to Claus techniques at present focuses primarily upon the improvement to Claus device exhausts, such as super Claus techniques,
SCOT techniques and RAR techniques etc., also there is the improvement with reference to Claus sulphur recoveries and treating tail gas technique, such as super excellent Claus works
Skill, low temperature Claus techniques.
Traditional Claus techniques improve merely H to super Claus process reforms in the past2S and SO2The reaction process in converter
Thinking, tail gas is handled, the elementary sulfur loss in incineration section and converter is reduced, so as to improve sulfur recovery rate, technique stream
Journey is shown in Fig. 2 (it is Claus sulfur recovery facilities that dotted line frame is interior in Fig. 2).Specifically increase H in traditional Claus techniques afterbody2S's
Selective oxidation reaction device, make unreacted H2S directly forms elemental sulfur under catalyst action and reclaimed.The technique is by the U.S.
Uop Inc. develops the seventies in last century, referred to as selectox techniques, and the core of the technology is the suitable selective catalysis of exploitation
Oxidant.H2S selective oxidation is not reversible reaction, and SO can be completely converted under catalytic oxidant effect2, so to entering
H at mouthful2S and SO2Proportion requirement it is not strict.
Super Claus techniques add a hydrogenation converter between converter and selective oxidation reaction device sometimes, make
SO2It is reduced to H2S, and COS and CS2Generation H is hydrolyzed Deng sulfur-containing compound2S, so as to farthest reclaim sulphur.Reaction such as following formula
It is shown：
SO2+H2→H2S+H2O (1)
COS+H2O→H2S+CO2 (2)
CS2+H2O→H2S+CO2。 (3)
Super excellent Claus is improved super Claus techniques, and the sulfur recovery rate of super excellent Claus devices is 99.4% or higher,
Its flow is as shown in Figure 3 (it is Claus sulfur recovery facilities that dotted line frame is interior in Fig. 3).Feature is the two level in super excellent Claus techniques
Hydrogenating reduction catalyst is added in converter, makes SO2It is reduced to H2S or S, reaction equation are shown below：
SO2+H2→S+H2O (1)
SO2+H2→H2S+H2O (2)
SO2+CO→S+CO2。 (3)
Super excellent claus process is wide suitable for sour gas concentration range, H in sour gas2S contents can be 23%~93%
Between, new device is can be not only used for, is also applied for existing Cross unit technological transformation, moreover it is possible to and oxygen-rich oxide sulfur recovery work
Skill is used in combination.The continuous gas phase catalysis of Process Gas in plant running, centre need not carry out condensation dehydration, be asked without " three wastes " processing
Topic.
Low-temperature Claus technique is also known as sub- dew point sulfur recovery technology, refers to the Ke Lao carried out at a temperature of less than sulphur dew point
This reaction.Sulphur dew point is influenceed by sulphur partial pressure in reactor, and in most of one-level Claus reactors, dew point is 170 DEG C,
Reactor minimum temperature must control 180~200 DEG C, to prevent liquefied sulphur from influenceing catalyst in reactor performance.Sub- dew point
Recovery technology of sulfur breaks through dew point to temperature limiting, extends use condition, reaction is carried out at a temperature of less than dew point,
The liquid sulfur of generation is adsorbed on low temperature catalyst.After cold bed absorption (CBA) technique, MCRC techniques and Clinsulf techniques are all
Come the sub- dew point recovery technology of sulfur developed, the technique can improve sulfur recovery rate to 99.2% or so.
SCOT techniques are researched and developed by shell international petroleum group.First set SCOT commercial plants were gone into operation in 1973.
In various tail gas treatment process, the technology investment and consumption indicators highest, but to the strong adaptability of claus sulphur recovery units,
Degree of purification is high, and sulfur recovery rate is up to 99.8%.SCOT technological processes are divided into three parts.(1) hydrogenating reduction part.Use fuel gas
Time chemical equivalent reaction occurs and produces H2Mix, sent out on hydrogenation catalyst with reducing gas, reducing gas and Process Gas such as CO
Raw hydrogenation reaction, makes elementary sulfur, the SO in Process Gas2Hydrogenation turns into H2S, COS and CS in Process Gas2It is hydrolyzed into H2S.(2) it is anxious
Cold part.Leave the Process Gas of hydrogenation reactor and heat reclaimed by waste heat boiler, and in chilling tower with low temperature ammonia water containing sulfur
Counter current contacting, a large amount of steam condensations, Process Gas temperature drop to absorption temperature in Process Gas.(3) absorption and regeneration part.With routine
Amine processing unit is identical, and the sour gas of regeneration overhead is back in the acid feed channel of claus sulphur recovery units.Its flow is such as
(it is Claus sulfur recovery facilities that dotted line frame is interior in Fig. 4) shown in Fig. 4.
RAR techniques are developed by the international power technology company (KTI) of Italy, and its general principle is identical with SCOT techniques, sulphur
The rate of recovery is more than 99.8%.RAR techniques include reducing and absorbing two steps.Reduction phase sulfur-containing compound such as SO2, COS and CS2
Deng by hydrogenation and hydrolysis generation H2S, absorption stage are that isopropanolamine or methyl diethanolamine (MDEA) absorb H2S, absorbing liquid
It can be come into operation again after desorption, and H2S enters circulation Claus converters.
Claus tail gas treatment process after improvement is while total sulfur recovery is improved, but there is also following main
Problem：
(1) equipment is perishable：There is larger amount of water to generate after Claus vent gas treatments, in reaction product, and in sour gas
H2S is equimolar, is to exist in the form of water vapour in high temperature, and condensate production is just had in the case where temperature is slightly lower
It is raw, with H2S and SO2Acid is combined to form, causes the corrosion of equipment and pipeline；
(2) pipeline easily blocks：Reaction product elemental sulfur fusing point is 112 DEG C, and boiling point is 444.6 DEG C, in order that sulphur can be
Flowed in pipeline, generally require heat tracing and sulphur is maintained into liquid, caused sulphur steam can be also entered in tail gas, slightly lower in temperature
In the case of crystallize, form powdery sulphur and be attached on tube wall, cause line clogging, system pressure difference increase；
(3) SO is arranged outside2Concentration is difficult to meet new standard：Claus tail gas treatment process after improvement can meet《Air
Pollutant comprehensive discharge standard》(GB16279-1996) provide, the SO in Sour gas disposal device flue gas2Highest allows to discharge
Concentration≤960mg/m3, but be difficult to meet what country promulgated for 2015《Petroleum refining industry pollutant emission standard》
(GB31570-2015) provide, the SO in Sour gas disposal device flue gas2Highest allows concentration of emission≤400mg/m3；
(4) operating cost is high：Claus tail gas treatment process after improvement, pass through SO in hydrogenating reduction tail gas2For H2S gas
Body, H2S, which is absorbed through MDEA, returns to Claus converters after desorber desorption continues to react, and absorbent MDEA consumptions are big and H2S gas
Body desorption consumes a large amount of steam, causes system operation expense higher.
Utility model content
The purpose of the disclosure is to provide a kind of processing system of Claus device exhausts, is filled using the Claus of disclosure system
Putting exhaust gas treating method can be handled Claus device exhausts to reach discharge standard, and operating cost is low.
To achieve these goals, the disclosure provides a kind of processing system of Claus device exhausts, and the system includes burning
Stove, desulfurizing tower, bipolar membrane electrodialysis device and desorber；The combustion furnace is provided with the entrance of Claus device exhausts, containing aerobic
The gas access of gas and exhanst gas outlet, the desulfurizing tower are provided with gas access, alkali wash water entrance, doctor solution outlet and flue gas and gone out
Mouthful, the bipolar membrane electrodialysis device is provided with liquid inlet, electrodialysis lye export and the outlet of electrodialysis acid solution, the desorption
Tower is provided with liquid inlet, gas vent and liquid outlet；The gas of the exhanst gas outlet of the combustion furnace and the desulfurizing tower enters
Mouth is in fluid communication, and the doctor solution outlet and the liquid inlet of the bipolar membrane electrodialysis device of the desulfurizing tower are in fluid communication, institute
The outlet of electrodialysis acid solution and the liquid inlet of the desorber for stating bipolar membrane electrodialysis device are in fluid communication.
Optionally, the exhanst gas outlet of the combustion furnace is connected by the gas access fluid of waste heat boiler and the desulfurizing tower
It is logical；And/or the doctor solution outlet of the desulfurizing tower passes sequentially through accurate filter and heat exchanger and filled with the bipolar membrane electrodialysis
The liquid inlet put is in fluid communication；And/or the electrodialysis lye export of the bipolar membrane electrodialysis device and the desulfurizing tower
Liquid inlet is in fluid communication.
Optionally, the system also includes drying tower, the entrance stream of the gas vent of the desorber and the drying tower
Body connects.
Optionally, the combustion furnace, which is additionally provided with, helps fuel gas inlet.
Optionally, the bipolar membrane electrodialysis device includes a negative electrode and an anode and positioned at negative electrode and anode
Between the membrane stack formed is alternately arranged by cation-exchange membrane and Bipolar Membrane, wherein, the cavity block of cation-exchange membrane and Bipolar Membrane
Side forms alkali room, and the anode membrane and cation-exchange membrane of Bipolar Membrane form sour room；The bipolar membrane electrodialysis device comprise at least by
The film pair that one cation-exchange membrane and a Bipolar Membrane are formed.
Optionally, the bipolar membrane electrodialysis device includes a negative electrode and an anode and positioned at negative electrode and anode
Between the membrane stack formed is alternately arranged by anion-exchange membrane and Bipolar Membrane, wherein, the cavity block of anion-exchange membrane and Bipolar Membrane
Side forms alkali room, and the anode membrane side of Bipolar Membrane and anion-exchange membrane form sour room；The bipolar membrane electrodialysis device comprises at least
A film pair being made up of an anion-exchange membrane and a Bipolar Membrane.
Optionally, the bipolar membrane electrodialysis device includes a negative electrode and an anode and positioned at negative electrode and anode
Between the membrane stack formed is alternately arranged by cation-exchange membrane, anion-exchange membrane and Bipolar Membrane, wherein, the cavity block side of Bipolar Membrane
Alkali room is formed with cation-exchange membrane, and cation-exchange membrane and anion-exchange membrane form salt room, anion-exchange membrane and bipolar
The anode membrane side of film forms sour room；The bipolar membrane electrodialysis device is comprised at least by a cation-exchange membrane, an anion
The film pair that exchange membrane and a Bipolar Membrane are formed.
Optionally, the desulfurizing tower includes tower body, positioned at the gas access of tower body bottom, the cigarette at the top of the tower body
Gas is exported and the doctor solution positioned at the tower body bottom exports, and spraying layer and sieve aperture are from top to bottom additionally provided with the tower body
Plate, at least one atomizer for being used to be sent into alkali wash water is provided with the spraying layer；Along short transverse, the spraying layer and
Sieve tray is between the gas access and exhanst gas outlet.
The disclosure also provides a kind of processing method of Claus device exhausts, and this method includes：A, by Claus device exhausts
It is sent into combustion furnace and is burnt with the gas containing oxygen, obtains the combustion product gases containing sulfur dioxide；B, by institute in step a
Obtain and contacted in combustion product gases feeding desulfurizing tower with alkali wash water and sulfur dioxide is carried out alkali cleaning processing with alkali wash water, obtain doctor solution
And desulfurization fume；C, gained doctor solution in step b is sent into bipolar membrane electrodialysis device and handled, obtain electrodialysis alkali lye
With the electrodialysis acid solution containing sulfurous acid；D, gained electrodialysis acid solution in step c is sent into desorber to be desorbed, contained
The stripping gas and stripping liquid of sulfur dioxide.
Optionally, methods described also includes：In stepb, the combustion product gases are sent into waste heat boiler and exchanged heat
After be re-fed into the desulfurizing tower and carry out the alkali cleaning processing；And/or methods described also includes：In step c, by gained desulfurization
Liquid is sequentially sent to accurate filter and filtered and be sent into heat exchanger carry out being re-fed into the Bipolar Membrane electricity after heat exchange cooling
Handled in electrodialysis apparatus；And/or methods described also includes：Gained electrodialysis alkali lye in step c is returned as alkali wash water
The alkali cleaning processing is carried out into the desulfurizing tower；And/or methods described also includes：Gained in step d is contained into sulfur dioxide
Stripping gas be sent into drying tower in be dried, stripping gas after being dried；Stripping gas is used to prepare liquid after gained is dried
Sulfur dioxide and/or sulfuric acid.
Optionally, Claus device exhausts described in step a contain hydrogen sulfide, sulfur dioxide, sulphur carbonoxide, carbon disulfide
And sulphur simple substance, oxygen content is 1~50 body % in the gas containing oxygen.
Optionally, the Claus device exhausts and the gas containing oxygen meet below equation：[1/2M(H)+2M(C)+
2M(S)]：M (O)=1：(1-1.08)；Wherein, hydrogen atom in gases of the M (H) for the Claus device exhausts and containing oxygen
Material amount, M (S) is the amount of the material of sulphur atom in the Claus device exhausts and gas containing oxygen, and M (C) is institute
The amount of the material of carbon atom in Claus device exhausts and gas containing oxygen is stated, M (O) is the Claus device exhausts and contained
There is the amount of the material of oxygen atom in the gas of oxygen.
Optionally, in step a, combustion-supporting pneumatic transmission is entered in the combustion furnace with the Claus device exhausts and containing aerobic
The gas of gas carries out the burning together；Wherein, the combustion-supporting gas bag includes hydrogen and/or methane.
Optionally, the bipolar membrane electrodialysis device includes a negative electrode and an anode and positioned at negative electrode and anode
Between the membrane stack formed is alternately arranged by cation-exchange membrane and Bipolar Membrane, wherein, the cavity block of cation-exchange membrane and Bipolar Membrane
Side forms alkali room, and the anode membrane and cation-exchange membrane of Bipolar Membrane form sour room；The bipolar membrane electrodialysis device comprise at least by
The film pair that one cation-exchange membrane and a Bipolar Membrane are formed；Gained doctor solution in step b is sent into Bipolar Membrane electric osmose
Sour room in analysis apparatus is handled, and alkali lye is obtained in alkali room, and the acid solution containing salt is obtained in the sour room；Or
The bipolar membrane electrodialysis device includes a negative electrode and an anode and between negative electrode and anode by the moon
Amberplex and Bipolar Membrane are alternately arranged the membrane stack of composition, wherein, the cavity block side of anion-exchange membrane and Bipolar Membrane forms alkali
Room, the anode membrane side of Bipolar Membrane and anion-exchange membrane form sour room；The bipolar membrane electrodialysis device is comprised at least by Yi Zhangyin
The film pair that amberplex and a Bipolar Membrane are formed；Gained doctor solution in step b is sent into bipolar membrane electrodialysis device
In alkali room handled, the alkali lye containing salt is obtained in alkali room, acid solution is obtained in the sour room；Or
The bipolar membrane electrodialysis device includes a negative electrode and an anode and between negative electrode and anode by sun
Amberplex, anion-exchange membrane and Bipolar Membrane are alternately arranged the membrane stack of composition, wherein, the cavity block side of Bipolar Membrane and cation
Exchange membrane forms alkali room, and cation-exchange membrane and anion-exchange membrane form the anode membrane of salt room, anion-exchange membrane and Bipolar Membrane
Side forms sour room；The bipolar membrane electrodialysis device comprise at least by a cation-exchange membrane, an anion-exchange membrane and
The film pair that one Bipolar Membrane is formed；The salt room that gained doctor solution is sent into bipolar membrane electrodialysis device in step b is carried out
Processing, electrodialysis alkali lye is obtained in alkali room, electrodialysis acid solution is obtained in the sour room, is desalinated in the salt room
Liquid.
Optionally, the desulfurizing tower includes tower body, positioned at the gas access of tower body bottom, the cigarette at the top of the tower body
Gas is exported and the doctor solution positioned at the tower body bottom exports, and spraying layer and sieve aperture are from top to bottom additionally provided with the tower body
Plate, at least one atomizer for being used to be sent into alkali wash water is provided with the spraying layer；Along short transverse, the spraying layer and
Sieve tray is between the gas access and exhanst gas outlet.
Optionally, the alkali wash water of the desulfurizing tower is included selected from sodium hydroxide solution, sodium carbonate liquor, sodium sulfite solution
At least one of with sodium bicarbonate solution, the weight fraction of the alkali wash water is 1~50 weight %, liquid gas in the desulfurizing tower
Volume ratio is 0.5-3.0 liters/rice3。
Optionally, the electrodialytic condition includes：Temperature is 20-35 DEG C, and pressure is 0.001-0.4 MPas, and film is to electricity
Press as 0.5-4 volts.
Claus device exhausts are burnt successively using the Claus device exhausts processing method of disclosure system, alkali cleaning
Processing, electrodialysis and desorption processing, can make Claus device exhausts reach discharge standard, and operating cost is low, may be used also in addition
To be recycled to the element sulphur in Claus device exhausts.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing further understanding of the disclosure, and a part for constitution instruction, with following tool
Body embodiment is used to explain the disclosure together, but does not form the limitation to the disclosure.In the accompanying drawings：
Fig. 1 is a kind of existing schematic flow sheet of embodiment of traditional Claus recovery technology of sulfur；
Fig. 2 is a kind of existing schematic flow sheet of embodiment of super Claus techniques；
Fig. 3 is a kind of existing super excellent schematic flow sheet of embodiment of Claus techniques；
Fig. 4 is a kind of schematic flow sheet of embodiment of existing SCOT techniques；
Fig. 5 includes the schematic flow sheet of the first embodiment of disclosure Claus device exhaust processing methods, also wraps
Include the structural representation of the first embodiment of disclosure Claus device exhaust processing systems；
Fig. 6 is the structural representation of the first embodiment of disclosure bipolar membrane electrodialysis device；
Fig. 7 includes the schematic flow sheet of disclosure Claus device exhausts second of embodiment of processing method, also wraps
Include the structural representation of disclosure Claus device exhausts second of embodiment of processing system；
Fig. 8 is the structural representation of disclosure bipolar membrane electrodialysis second of embodiment of device；
Fig. 9 includes the schematic flow sheet of the third embodiment of disclosure Claus device exhaust processing methods, also wraps
Include the structural representation of the third embodiment of disclosure Claus device exhaust processing systems；
Figure 10 is the structural representation of the third embodiment of disclosure bipolar membrane electrodialysis device；
Figure 11 includes the schematic flow sheet of disclosure Claus device exhausts the 4th kind of embodiment of processing method,
Include the structural representation of disclosure Claus device exhausts the 4th kind of embodiment of processing system；
Figure 12 is the structural representation of the 4th kind of embodiment of disclosure bipolar membrane electrodialysis device；
Figure 13 is a kind of structural representation of embodiment of disclosure desulfurizing tower.
Description of reference numerals
The one-level converter of 1000 combustion furnace, 1001 waste heat boiler 1002
1003 secondary reformers 1004 cool down the incinerator of condenser 1005
The sulphur tank of 1006 selective oxidation reaction device, 1007 deep freezer 1008
The waste heat boiler of 1009 hydrogenation catalyst reactor, 1010 hydrogenation reactor 1011
1012H2The rich amine solution desorber of 1013 incinerator of S absorption towers 1014
A Claus device exhausts B contains the combustion-supporting gas of gas C of oxygen
After D desulfurization fumes E is dried imbibition is mediated outside stripping gas F
The waste heat boiler of 1 combustion furnace 2
3 desulfurizing tower 3A tower body 3B spraying layers
3C sieve tray 3D atomizers
The bipolar membrane electrodialysis device of 4 accurate filter, 5 heat exchanger 6
The heat exchanger of 7 desorber, 8 drying tower 9
10 electrode liquid zones
The cation-exchange membrane of 101 first negative electrode, 102 first Bipolar Membrane 103 first
The sour room of 104 first anode, 20 first alkali room 30 first
The anion-exchange membrane of 201 second negative electrode, 202 second Bipolar Membrane 203 first
The sour room of 204 second plate, 21 second alkali room 31 second
The Bipolar Membrane of 301 the 3rd 302 second cation-exchange membrane 303 of negative electrode the 3rd
The sour room of 304 the 3rd alkali room 32 of third anode 22 the 3rd
The three cation exchange membrane of 401 the 4th the 4th Bipolar Membrane of negative electrode 402 403
The alkali room of 404 the 4th anode 23 of trianion exchange membrane 405 the 4th
The diluting compartment of 33 the 4th sour room 43
Embodiment
The embodiment of the disclosure is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explained the disclosure, is not limited to the disclosure.
The problem of processing cost is high, is had based on the processing of existing Claus device exhausts, as shown in Fig. 5,7,9 or 11, this public affairs
Open and a kind of processing method of Claus device exhausts is provided, this method includes：A, by Claus device exhausts A and gas containing oxygen
Body B, which is sent into combustion furnace 1, to be burnt, and obtains the combustion product gases containing sulfur dioxide；B, gained combustion product gases in step a are sent
Enter and contacted in desulfurizing tower 3 with alkali wash water and sulfur dioxide is carried out alkali cleaning processing with alkali wash water, obtain doctor solution and desulfurization fume
D；C, gained doctor solution in step b is sent into bipolar membrane electrodialysis device 6 and carries out electrodialysis, obtained electrodialysis alkali lye and contain
The electrodialysis acid solution of sulfurous acid；D, gained electrodialysis acid solution in step c is sent into desorber 7 to be desorbed, obtained containing dioxy
Change the stripping gas and stripping liquid of sulphur.The Claus device exhausts processing method of the disclosure is fired Claus device exhausts successively
Burning, alkali cleaning processing, electrodialysis and desorption processing, can make Claus device exhausts reach discharge standard, and operating cost is low,
It can in addition contain be recycled to the element sulphur in Claus device exhausts.
According to the disclosure, the temperature of combustion product gases is high, and available energy is big, and in order to prevent desulfurizing tower temperature rise excessive,
Desulfurizing tower operation is influenceed, as shown in Fig. 5,7,9 or 11, methods described can also include：In stepb, by the combustion product gases
It is sent into waste heat boiler 2 after being exchanged heat to be re-fed into the desulfurizing tower 3 and carries out the alkali cleaning processing, the burning cigarette by heat exchange
The temperature of gas is typically below 200 DEG C, preferably below 100 DEG C.Waste heat boiler be it is well-known to those skilled in the art, can be with
Used by Waste Heat Recovery with producing hot water or steam to supply miscellaneous equipment.
According to the disclosure, granular impurity may be contained in doctor solution, to protect follow-up electrodialysis plant, as Fig. 5,
7th, shown in 9 or 11, methods described can also include：In step c, gained doctor solution is sequentially sent to accurate filter 4 and carried out
Filtering and it is sent into heat exchanger 5 and be re-fed into the bipolar membrane electrodialysis device 6 after heat exchange cooling carrying out the electric osmose
Analysis.Doctor solution after cooling of filtering and exchange heat, its solid particle are greatly reduced, and reduce the wind of film filter blocking
Danger, while temperature reduces.In addition, as needed, the partial desulfurization liquid before secondary filter can return to desulfurizing tower 3, secondary filter
Partial desulfurization liquid afterwards can also return to desulfurizing tower 3.The accurate filter is well-known to those skilled in the art, such as can
Think selected from least one of inorganic membrane filter, metal film filter and organic membrane filter device, the organic membrane filter device
Preferably high-temperature resistant filter.It is different according to filtering accuracy, the membrane aperture of the accurate filter may range from 1 nanometer-
10000 nanometers.Heat exchanger is also well-known to those skilled in the art, and the disclosure repeats no more, its temperature of the doctor solution after heat exchange
Degree is preferably less than 35 DEG C, more preferably less than 30 DEG C.
According to the disclosure, in order to reduce the usage amount of alkali wash water, as shown in Fig. 5,7,9 or 11, methods described can also wrap
Include：Gained electrodialysis alkali lye in step c is back in the desulfurizing tower 3 as alkali wash water and carries out the alkali cleaning processing.Electric osmose
Analysis alkali lye is similar to the composition of alkali wash water and impurity is less, suitably return using alkali cleaning.
Also have according to the disclosure, in the stripping gas containing sulfur dioxide compared with juicy, be not suitable for directly compression storage or system
Standby sulfuric acid, as shown in Fig. 5,7,9 or 11, methods described can also include：By stripping gas of the gained containing sulfur dioxide in step d
It is sent into drying tower 8 and is dried, stripping gas E after being dried；Stripping gas E is used to prepare liquid titanium dioxide after gained is dried
Sulphur and/or sulfuric acid.The method that sulfuric acid and liquid sulfur dioxide are prepared using gaseous sulfur dioxide is that those skilled in the art institute is ripe
Know, the process for preparing sulfuric acid can be that the mode of one turn of one suction, double-absorption, three-conversion three-absorption or non-stationary transformantion is carried out, gas
State sulfur dioxide prepares liquid sulfur dioxide and can carried out by the way of compression cools down.
According to the disclosure, Claus device exhausts are well-known to those skilled in the art described in step a, are such as Fig. 1-4
The tail gas that traditional Claus recovery technology of sulfur of shown dashed box part is discharged.For from composition, the Claus devices tail
Gas typically contains hydrogen sulfide and sulfur dioxide, can also contain sulphur carbonoxide, carbon disulfide and sulphur simple substance (such as liquid sulfur or sulphur
Steam), it can further contain nitrogen gas and water, hydrogen, carbon monoxide and carbon disulfide, according to the sulfur-bearing handled by Claus devices
Gas is different, and each component content of Claus device exhausts can also change, but can use at the device of the disclosure
Reason.
According to the disclosure, the gas containing oxygen described in step a is used to make the hydrogen sulfide and list in Claus device exhausts
The burnings such as matter sulphur turn into sulfur dioxide, and the content of its oxygen can be 1~50 body %, preferably 5~40 body %, and more preferably 10
~30 body %, can be the mixing of the mixture of air, air and nitrogen, the mixture of air and flue gas and air and flue gas
Thing etc..Further, since part sulphite can be oxidized referred to as sulfate, it is impossible to sulfur dioxide, shadow are desorbed in desorber
Later use is rung, control sulfate is generally required and accounts for less than the 8% of sulfate and sulphite total content, thus it is, it is necessary to strict
The total content of oxygen in Claus device exhausts and gas containing oxygen is controlled, for example, the Claus device exhausts and containing
The composition of the gas of oxygen meets below equation：[1/2M(H)+2M(C)+2M(S)]：M (O)=1：(1-1.08)；Wherein, M (H)
The amount of the material of hydrogen atom in gas for the Claus device exhausts and containing oxygen, M (S) are the Claus device exhausts
With the amount of the material of sulphur atom in the gas containing oxygen, M (C) is in the Claus device exhausts and gas containing oxygen
The amount of the material of carbon atom, M (O) are the amount of the material of oxygen atom in the Claus device exhausts and gas containing oxygen.It is excellent
Selection of land, [1/2M (H)+2M (C)+2M (S)]：M (O)=1：(1-1.05), it is further preferred that [1/2M (H)+2M (C)+2M
(S)]：M (O)=1：(1-1.03).
According to the disclosure, burning is a kind of chain reaction, because combustible content is relatively low in Claus device exhausts, in order to
Prevent combustion process from stopping, in step a, combustion-supporting gas C can be sent into the combustion furnace 1 and the Claus device exhausts
The burning is carried out together with the gas containing oxygen；Wherein, the combustion-supporting gas can include hydrogen and/or methane, Yi Jiqi
Its imflammable gas, preferably hydrogen.The usage amount disclosure of combustion-supporting gas is not particularly limited, as long as being able to maintain that burning i.e.
Can, the combustion product of combustion-supporting gas is generally water, carbon dioxide and carbon monoxide, preferably water, to reduce the consumption of alkali wash water.
According to the disclosure, bipolar membrane electrodialysis device is well-known to those skilled in the art, generally comprises negative electrode, anode
And the film pair between negative electrode, anode, separated out, can be used for doctor solution by electrode solution between negative electrode, anode and film pair
In zwitterion by bronsted lowry acids and bases bronsted lowry and and/or salt in the form of separate, concrete structure can be that two compartments and/or three compartments are double
Pole EDBM device, the film of the electrodialysis plant can be Bipolar Membrane-anode membrane-Bipolar Membrane repeat unit shape to combination
Formula or Bipolar Membrane-cavity block-Bipolar Membrane repeat unit or anode membrane-Bipolar Membrane-anode membrane repeat unit, bipolar membrane electrodialysis
The organizational form of membrane stack can be one section of one-level or multistage multistage.The electrodialytic condition is well known to those skilled in the art
, such as can include：Temperature is 20-35 DEG C, and pressure is 0.001-0.4 MPas, and film is 0.5-4 volts to voltage, the electricity
The concentration of alkali (such as sodium hydroxide) can be 0.05~10 weight % in dialysis alkali lye, the electrodialysis acid solution sulfite
Concentration can be 0.05~8 weight %.The structure and electrodialytic flow of specific bipolar membrane electrodialysis device are referring to following four kinds
Embodiment.
The first embodiment, as shown in fig. 6, the bipolar membrane electrodialysis device 6 is two compartment Bipolar Membrane electric osmoses
Analysis apparatus, including the first negative electrode 101 and the first anode 104 and between the first negative electrode 101 and the first anode 104 extremely
Few one group of first film pair, first film to including at least two first Bipolar Membranes 102 and positioned at adjacent first Bipolar Membrane 102 it
Between the first cation-exchange membrane 103, first cation-exchange membrane 103 it is its immediate be located at first negative electrode 101
Form the first alkali room 20 between first Bipolar Membrane 102 of side, first cation-exchange membrane 103 it is its immediate be located at institute
State and form the first sour room 30 between the first Bipolar Membrane 102 of the side of the first anode 104；It is as shown in figure 5, gained in step b is de-
The first sour room 30 that sulphur liquid is sent into bipolar membrane electrodialysis device 6 carries out the first electrodialysis, and first is obtained in the first alkali room 20
Electrodialysis alkali lye, the first electrodialysis acid solution containing salt is obtained in first sour room 30.Due to doctor solution is sent into first
Sour room 30 carries out electrodialysis, therefore the first electrodialysis acid solution of partial cation meeting exists in a salt form.Using alkali wash water as hydrogen-oxygen
Exemplified by changing sodium solution, the first alkali room 20 obtains NaOH solution and is back to the absorption tail gas of desulfurizing tower 3, and the first sour room 30 obtains H2SO3It is molten
Liquid and a small amount of Na2SO4Solution enters desorber 7, desorbs SO2Drying tower 8 is removed, desorber 7 goes out stripping liquid and cooled through heat exchanger 9
To Na during 20-35 DEG C of return alkali room 202SO4Concentration is 1.0 weight % or following, and the desorber 7 mediates imbibition F out
Na during sewage disposal2SO4Concentration is more than 1.0 weight %.
Second of embodiment, as shown in figure 8, the bipolar membrane electrodialysis device 6 is two compartment Bipolar Membrane electric osmoses
Analysis apparatus, including the second negative electrode 201 and second plate 204 and between the second negative electrode 201 and second plate 204 extremely
Few one group of second film pair, second film to including at least two second Bipolar Membranes 202 and positioned at adjacent second Bipolar Membrane 202 it
Between the first anion-exchange membrane 203, first anion-exchange membrane 203 it is its immediate be located at second negative electrode 201
Form the second alkali room 21 between second Bipolar Membrane 202 of side, first anion-exchange membrane 203 it is its immediate be located at institute
State and form the second sour room 31 between the second Bipolar Membrane 202 of the side of second plate 204；It is as shown in fig. 7, gained in step b is de-
The second alkali room 21 that sulphur liquid is sent into bipolar membrane electrodialysis device 6 carries out the second electrodialysis, is contained in the second alkali room 21
Second electrodialysis alkali lye of salt, obtains the second electrodialysis acid solution in second sour room 31.It is molten by sodium hydroxide of alkali wash water
Exemplified by liquid, the second alkali room 21 obtains NaOH solution and is back to the absorption tail gas of desulfurizing tower 3, and the second sour room 31 obtains H2SO3Solution and few
Measure H2SO4Solution enters desorber 7, desorbs SO2Drying tower 8 is removed, desorber 7 goes out stripping liquid and is cooled to 20-35 through heat exchanger 9
DEG C return the second sour room 31 when H2SO4Concentration is 1.0 weight % or following, and the desorber 7 mediates imbibition F decontaminated waters out
H during processing2SO4Concentration is more than 1.0 weight %.
The third embodiment, as shown in Figure 10, the bipolar membrane electrodialysis device 6 are two compartment Bipolar Membrane electric osmoses
Analysis apparatus, including the 3rd negative electrode 301 and third anode 304 and between the 3rd negative electrode 301 and third anode 304 extremely
Few one group of tertiary membrane pair, the tertiary membrane to including at least two second cation-exchange membranes 302 and positioned at the adjacent second sun from
The 3rd Bipolar Membrane 303 between proton exchange 302, the 3rd Bipolar Membrane 303 it is its immediate be located at the 3rd negative electrode 301
Between second cation-exchange membrane 302 of side formed the 3rd sour room 32, the 3rd Bipolar Membrane 303 it is its immediate be located at institute
State and the 3rd alkali room 22 is formed between the second cation-exchange membrane 302 of the side of third anode 304；As shown in figure 9, by step b
The 3rd alkali room 22 and the 3rd sour room 32 that gained doctor solution is sent into bipolar membrane electrodialysis device 6 simultaneously carry out the 3rd electrodialysis,
To ensure the pressure balance of the 3rd alkali room 22 and the 3rd sour room 32, the 3rd electrodialysis alkali containing salt is obtained in the 3rd alkali room 22
Liquid, the 3rd electrodialysis acid solution is obtained in the 3rd sour room 32.So that alkali wash water is sodium hydroxide solution as an example, the 3rd alkali room 22
Obtain NaOH and Na2SO3Mixed solution and a small amount of Na2SO4Solution is back to desulfurizing tower 3 and absorbs tail gas, and the 3rd sour room 32 obtains
H2SO3Solution and a small amount of H2SO4Solution enters desorber 7, desorbs SO2Drying tower 8 is removed, desorber 7 goes out stripping liquid and returns to desulfurization
H during tower 32SO4Concentration is 1.0 weight % or following, and the desorber 7 goes out to mediate H during imbibition F decontamination water process2SO4
Concentration is more than 1.0 weight %.
4th kind of embodiment, as shown in figure 12, the bipolar membrane electrodialysis device 6 are three compartment Bipolar Membrane electric osmoses
Analysis apparatus, including the 4th negative electrode 401 and the 4th anode 405 and between the 4th negative electrode 401 and the 4th anode 405 extremely
Few one group of the 4th film pair, the 4th film is to including at least two the 4th Bipolar Membranes 402 and positioned at adjacent 4th Bipolar Membrane
Three cation exchange membrane 403 and trianion exchange membrane 404 between 402；It is described positioned at adjacent 4th Bipolar Membrane 402 it
Between three cation exchange membrane 403 close to the side of the 4th negative electrode 401, it is described between adjacent 4th Bipolar Membrane 402
Trianion exchange membrane 404 close to the side of the 4th anode 405；4th Bipolar Membrane 402 is its immediate to be located at
The 4th sour room 33 is formed between the trianion exchange membrane 404 of the side of 4th negative electrode 401, the three cation exchanges
Between film 403 and trianion exchange membrane 404 formed diluting compartment 43, the 4th Bipolar Membrane 402 it is its immediate be located at institute
State and the 4th alkali room 23 is formed between the three cation exchange membrane 403 of the side of the 4th anode 405；As shown in figure 11, by step b
The diluting compartment 43 that gained doctor solution is sent into bipolar membrane electrodialysis device 6 carries out the 4th electrodialysis, is obtained in the 4th alkali room 23
4th electrodialysis alkali lye, the 4th electrodialysis acid solution is obtained in the 4th sour room 33, desalinated in the diluting compartment 43
Liquid.So that alkali wash water is sodium hydroxide solution as an example, the doctor solution is passed through the 4th salt room of three compartment bipolar membrane electrodialysis devices
43 carry out electrodialysis, and the 4th alkali room 23 obtains NaOH solution and is back to the absorption tail gas of desulfurizing tower 3, and the 4th salt room 43 obtains desalination solution
The 4th alkali room 23 is returned to, the 4th sour room 33 obtains H2SO3Solution and a small amount of H2SO4Solution enters desorber 7, desorbs SO2Go to do
Dry tower 8, desorber 7 go out H when stripping liquid returns to four sour rooms 332SO4Concentration is 1.0 weight % or following, the desorber 7
H during imbibition F decontamination water process is mediated out2SO4Concentration is more than 1.0 weight %.
According to the disclosure, desulfurizing tower is well-known to those skilled in the art, for by the sulfur dioxide in combustion product gases
Removed by alkali wash water, discharged so as to which desulfurization fume be up to state standards.For example, as shown in figure 13, the desulfurizing tower 3
Tower body 3A, the exhanst gas outlet positioned at the gas access of tower body 3A bottoms, at the top of the tower body 3A can be included and positioned at institute
The doctor solution outlet of tower body 3A bottoms is stated, spraying layer 3B and sieve tray 3C is from top to bottom additionally provided with the tower body 3A, it is described
It is preferably inorganic more that at least one atomizer 3D, the atomizer 3D for being used to be sent into alkali wash water is provided with spraying layer 3B
Hole agglomerated material；Along short transverse, the spraying layer 3B and sieve tray 3C are between the gas access and exhanst gas outlet, institute
The doctor solution obtained can be pumped out desulfurizing tower by water pump and carry out carrying out returning use in electrodialysis or the atomizer for returning to desulfurizing tower.
Alkali wash water is sprayed by atomizer 3D and carries out counter current contacting with combustion product gases, while sieve tray 3C can be uniformly distributed alkali wash water
And combustion product gases, increase gas-liquid mass transfer area, so as to improve alkali cleaning efficiency.
According to the disclosure, alkali cleaning processing is well-known to those skilled in the art, and it is entered using alkali wash water and sulfur dioxide
The principle of row reaction is with by the sulfur dioxide removal in combustion product gases, for example, the alkali wash water can include being selected from sodium hydroxide
At least one of solution, sodium carbonate liquor, sodium sulfite solution and sodium bicarbonate solution, or other art technologies
Aqueous slkali known to personnel.The weight fraction of the alkali wash water can be 1~50 weight %, preferably 5~40 weight %, more
Preferably 10~30 weight %, according to the difference of content of sulfur dioxide in combustion product gases, the condition of alkali cleaning processing can be different, example
As liquid air volume ratio can be 0.5-3.0 liters/rice in the desulfurizing tower 33, alkali cleaning processing the temperature and pressure disclosure do not have
It is specifically limited, such as alkali wash water can be normal temperature, pressure is pumping pressure.
As shown in Fig. 5,7,9 or 11, the disclosure also provides a kind of processing system of Claus device exhausts, and the system includes
Combustion furnace 1, desulfurizing tower 3, bipolar membrane electrodialysis device 6 and desorber 7；The combustion furnace 1 is provided with entering for Claus device exhausts
Mouthful, the gas access containing oxygen and exhanst gas outlet, the desulfurizing tower 3 is provided with gas access, alkali wash water entrance, doctor solution go out
Mouth and exhanst gas outlet, the bipolar membrane electrodialysis device 6 are provided with liquid inlet, electrodialysis lye export and electrodialysis acid solution and gone out
Mouthful, the desorber 7 is provided with liquid inlet, gas vent and liquid outlet；The exhanst gas outlet of the combustion furnace 1 takes off with described
The gas access of sulphur tower 3 is in fluid communication, the doctor solution outlet of the desulfurizing tower 3 and the liquid of the bipolar membrane electrodialysis device 6
Entrance is in fluid communication, the electrodialysis acid solution outlet of the bipolar membrane electrodialysis device 6 and the liquid inlet fluid of the desorber 7
Connection.Using the system of the disclosure, Claus device exhausts can be burnt successively, at alkali cleaning processing, electrodialysis and desorption
Reason, can make Claus device exhausts reach discharge standard, and operating cost is low, it can in addition contain in Claus device exhausts
Element sulphur recycled.
According to the disclosure, the temperature of combustion product gases is high, and available energy is big, and in order to prevent desulfurizing tower temperature rise excessive,
Influence desulfurizing tower operation, as shown in Fig. 5,7,9 or 11, the exhanst gas outlet of the combustion furnace 1 can by waste heat boiler 2 with it is described
The gas access of desulfurizing tower 3 is in fluid communication.Waste heat boiler be it is well-known to those skilled in the art, can by Waste Heat Recovery with
Production hot water or steam use to supply miscellaneous equipment.
According to the disclosure, granular impurity may be contained in doctor solution, to protect follow-up electrodialysis plant, as Fig. 5,
7th, shown in 9 or 11, the outlet of the doctor solution of the desulfurizing tower 3 can pass sequentially through accurate filter 4 and heat exchanger 5 with it is described bipolar
The liquid inlet of EDBM device 6 is in fluid communication.Doctor solution after cooling of filtering and exchange heat, its solid particle is significantly
Reduce, reduce the risk of film filter blocking, while temperature reduces.The accurate filter is that those skilled in the art institute is ripe
Know, for example, can be selected from least one of inorganic membrane filter, metal film filter and organic membrane filter device, it is described to have
Machine film filter is preferably high-temperature resistant filter, different according to filtering accuracy.The membrane aperture scope of the accurate filter can be with
For 1 nanometer -10000 nanometers.Heat exchanger is also well-known to those skilled in the art, and the disclosure repeats no more, de- after heat exchange
Its temperature of sulphur liquid is preferably less than 35 DEG C, more preferably less than 30 DEG C.
According to the disclosure, in order to reduce the usage amount of alkali wash water, as shown in Fig. 5,7,9 or 11, the bipolar membrane electrodialysis
The electrodialysis lye export of device 6 can be in fluid communication with the liquid inlet of the desulfurizing tower 3.Electrodialysis alkali lye and alkali wash water
It is less to form similar and impurity, suitably return using alkali cleaning.
Also have according to the disclosure, in the stripping gas containing sulfur dioxide compared with juicy, be not suitable for directly compression storage or system
Standby sulfuric acid, as shown in Fig. 5,7,9 or 11, the system also includes drying tower 8, and the gas vent of the desorber 7 is done with described
The entrance of dry tower 8 is in fluid communication.
According to the disclosure, burning is a kind of chain reaction, because combustible content is relatively low in Claus device exhausts, in order to
Prevent combustion process from stopping, the combustion furnace 1, which is additionally provided with, helps fuel gas inlet, wherein, the combustion-supporting gas can include hydrogen and/
Or methane, and other imflammable gas, preferably hydrogen.The usage amount disclosure of combustion-supporting gas is not particularly limited, as long as energy
Enough to maintain burning, the combustion product of combustion-supporting gas is generally water, carbon dioxide and carbon monoxide, preferably water, to reduce alkali
The consumption of washing lotion.
According to the disclosure, bipolar membrane electrodialysis device is well-known to those skilled in the art, generally comprises negative electrode, anode
And the film pair between negative electrode, anode, separated out, can be used for doctor solution by electrode solution between negative electrode, anode and film pair
In zwitterion by bronsted lowry acids and bases bronsted lowry and and/or salt in the form of separate, concrete structure can be two compartments and/or three compartments it is bipolar
EDBM device, the film of the electrodialysis plant can be Bipolar Membrane-anode membrane-Bipolar Membrane repeat unit to combination
Or Bipolar Membrane-cavity block-Bipolar Membrane repeat unit or anode membrane-Bipolar Membrane-anode membrane repeat unit, bipolar membrane electrodialysis film
The organizational form of heap can be one section of one-level or multistage multistage.The concentration of the electrodialysis acid solution sulfite can be 0.05~
8 weight %.The structure of specific bipolar membrane electrodialysis device is referring to following four kinds of embodiments.
The first embodiment, as seen in figs. 5-6, the bipolar membrane electrodialysis device 6 are two compartment Bipolar Membranes electricity
Electrodialysis apparatus, including the first negative electrode 101 and the first anode 104 and between the first negative electrode 101 and the first anode 104
At least one set of first film pair, first film is to including at least two first Bipolar Membranes 102 and positioned at adjacent first Bipolar Membrane 102
Between the first cation-exchange membrane 103, first cation-exchange membrane 103 it is its immediate be located at first negative electrode
The first alkali room 20, its immediate position of first cation-exchange membrane 103 are formed between first Bipolar Membrane 102 of 101 sides
The first sour room 30 is formed between the first Bipolar Membrane 102 of the side of the first anode 104；First sour room 30 is set
The liquid inlet of bipolar membrane electrodialysis device 6 is stated, first alkali room 20 is provided with the electric osmose of the bipolar membrane electrodialysis device 6
Lye export is analysed, first sour room 30 is provided with the electrodialysis acid solution outlet.
Second of embodiment, as Figure 7-8, the bipolar membrane electrodialysis device 6 are two compartment Bipolar Membranes electricity
Electrodialysis apparatus, including the second negative electrode 201 and second plate 204 and between the second negative electrode 201 and second plate 204
At least one set of second film pair, second film is to including at least two second Bipolar Membranes 202 and positioned at adjacent second Bipolar Membrane 202
Between the first anion-exchange membrane 203, first anion-exchange membrane 203 it is its immediate be located at second negative electrode
The second alkali room 21, its immediate position of first anion-exchange membrane 203 are formed between second Bipolar Membrane 202 of 201 sides
The second sour room 31 is formed between the second Bipolar Membrane 202 of the side of second plate 204；Second alkali room 21 is set
Liquid inlet and the electrodialysis lye export of bipolar membrane electrodialysis device 6 are stated, second sour room 31 is provided with the electrodialysis
Acid solution exports.
The third embodiment, as shown in figs. 9-10, the bipolar membrane electrodialysis device 6 are two compartment Bipolar Membranes electricity
Electrodialysis apparatus, including the 3rd negative electrode 301 and third anode 304 and between the 3rd negative electrode 301 and third anode 304
At least one set of tertiary membrane pair, the tertiary membrane is to including at least two second cation-exchange membranes 302 and positioned at the adjacent second sun
The 3rd Bipolar Membrane 303 between amberplex 302, the 3rd Bipolar Membrane 303 it is its immediate be located at the 3rd negative electrode
The 3rd sour room 32, its immediate position of the 3rd Bipolar Membrane 303 are formed between second cation-exchange membrane 302 of 301 sides
The 3rd alkali room 22 is formed between the second cation-exchange membrane 302 of the side of third anode 304；The He of 3rd alkali room 22
3rd sour room 32 is provided with the liquid inlet of the bipolar membrane electrodialysis device 6, and the 3rd alkali room 22 is provided with described double
The electrodialysis lye export of pole EDBM device 6, the 3rd sour room 32 are provided with the electrodialysis acid solution outlet.
4th kind of embodiment, as depicted in figs. 11-12, the bipolar membrane electrodialysis device 6 are three compartment Bipolar Membranes
Electrodialysis plant, including the 4th negative electrode 401 and the 4th anode 405 and between the 4th negative electrode 401 and the 4th anode 405
The film pair of at least one set the 4th, the 4th film is to including at least two the 4th Bipolar Membranes 402 and bipolar positioned at the adjacent 4th
Three cation exchange membrane 403 and trianion exchange membrane 404 between film 402；It is described to be located at adjacent 4th Bipolar Membrane 402
Between three cation exchange membrane 403 close to the side of the 4th negative electrode 401, it is described positioned at adjacent 4th Bipolar Membrane 402 it
Between trianion exchange membrane 404 close to the side of the 4th anode 405；Its immediate position of 4th Bipolar Membrane 402
The 4th sour room 33 is formed between the trianion exchange membrane 404 of the side of the 4th negative electrode 401, the three cation is handed over
Formation diluting compartment 43 between film 403 and trianion exchange membrane 404 is changed, the 4th Bipolar Membrane 402 is its immediate to be located at
The 4th alkali room 23 is formed between the three cation exchange membrane 403 of the side of 4th anode 405；The diluting compartment 43 is provided with
The liquid inlet of the bipolar membrane electrodialysis device 6 and desalination solution outlet, the 4th alkali room 23 are provided with the Bipolar Membrane electricity
The electrodialysis lye export of electrodialysis apparatus 6, the 4th sour room 33 are provided with the electrodialysis acid solution outlet.
According to the disclosure, desulfurizing tower is well-known to those skilled in the art, for by the sulfur dioxide in combustion product gases
Removed by alkali wash water, discharged so as to which desulfurization fume be up to state standards.For example, as shown in figure 13, the desulfurizing tower 3
Exhanst gas outlet including tower body 3A, positioned at the gas access of tower body 3A bottoms, at the top of the tower body 3A and positioned at the tower
The doctor solution of body 3A bottoms is exported, and spraying layer 3B and sieve tray 3C, the spray are from top to bottom additionally provided with the tower body 3A
It is preferably inorganic porous burning that at least one atomizer 3D, the atomizer 3D for being used to be sent into alkali wash water is provided with layer 3B
Tie material；Along short transverse, the spraying layer 3B and sieve tray 3C are between the gas access and exhanst gas outlet.Gained
Doctor solution can be pumped out desulfurizing tower by water pump and carry out carrying out returning use in electrodialysis or the atomizer for returning to desulfurizing tower.Pass through
Atomizer 3D sprays alkali wash water and carries out counter current contacting with combustion product gases, while sieve tray 3C can be uniformly distributed alkali wash water and combustion
Flue gas is burnt, increases gas-liquid mass transfer area, so as to improve alkali cleaning efficiency.
The disclosure is further illustrated below by embodiment, but the disclosure is not therefore and by any limit
System.
Claus device exhausts are handled using method of disclosure.As shown in Fig. 5,7,9 or 11, Claus device exhausts are through burning
Stove 1 is burnt, and the sulphur-containing substance in tail gas is completely converted into SO2Gas, combustion product gases are through the sodium hydroxide solution in desulfurizing tower 3
By SO2After gas absorbs, desulfurization fume qualified discharge, doctor solution (contains Na2SO3/NaHSO3) filter and change through accurate filter 4
Sulphite is converted into NaOH and H by the hot heat exchange of device 5 by bipolar membrane electrodialysis device 62SO3Solution, NaOH solution return to desulfurization
Tower recycles, H2SO3Solution goes desorber 7 to desorb, the SO desorbed2Gas removes liquid SO processed after the drying of drying tower 82Production
Product or H processed2SO4。
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited.
Embodiment
As shown in fig. 7, the step of the present embodiment, is as follows：
(1) tail gas burns in combustion furnace
The Claus device exhausts A of index shown in table 1 is entered into combustion furnace 1, it is combustion-supporting in combustion furnace 1 through combustion-supporting gas C (hydrogen)
Burnt with the gas B (air) containing oxygen, reaction temperature is about more than 1000 DEG C, the sulphur-containing substance conversion in tail gas A
For SO2Gas, heat exchanges heat through waste heat boiler 2 caused by course of reaction, for producing low pressure or middle pressure steam.
(2)SO2Absorb
Combustion product gases (main component N after heat exchange2And SO2) entering desulfurizing tower 3, combustion product gases are through alkali wash water
Qualified discharge after (NaOH solution) absorbs, doctor solution main component is sulphite (Na2SO3/NaHSO3), the main work of desulfurizing tower
Skill index is as shown in table 2.
(3) electrodialysis
Desulfurizing tower 3 goes out doctor solution and enters Bipolar Membrane electric osmose after the filtering of metal film accurate filter 4 and heat exchanger 5 exchange heat
Analysis apparatus, is handled through bipolar membrane electrodialysis device, and main technique index is shown in Table 3.Electrodialysis alkali lye (NaOH solution) regeneration returns
Recycled to desulfurizing tower 3, obtained H2SO3Solution goes desorber 7 to be desorbed.
(4)SO2Desorb and liquid SO processed2
Bipolar membrane electrodialysis device 6 is made sulfurous acid solution (abbreviation rich solution) and (not shown into lean/rich liquid heat exchanger through pump
Go out, the sulfurous acid solution abbreviation lean solution that desorber comes out).Temperature from top enters desorber 7 after being increased to 80~90 DEG C.Solving
Inhale in tower 7, rich solution is flowed downward, and SO is desorbed by the vapor constantly stripping that bottom of towe rises2, concrete technology index is shown in Table 4.Solution
Inhale the bottom of towe of tower 7 and be provided with and boil mouth again, sulfurous acid is heated using steam.The SO desorbed2Together with vapor in cooler (not
Show) in be cooled to 40 DEG C, then through gas-liquid separator (not shown) remove foam, subsequently into drying tower 8.With 98%
H2SO4Wherein moisture is removed, obtains more than 99.9% SO2Dry gas, 0.5~0.6Mpa is pressed onto through compressor, temperature reaches 140
DEG C then exchanged heat by condenser (not shown) and water to 40 DEG C, gas SO2Become liquid SO2, it is pressed onto SO2Storage tank export trade.
The lean solution of the bottom of desorber 7 is pumped into lean/rich liquid heat exchanger (not shown), and lean solution recycles into desulfurizing tower 3.Due to considering
Liquid SO2Market conditions or compressor troubleshooting, in order to not influence the use of processing system, the present embodiment system is also
Build simultaneously and a set of prepare dense H2SO4Device.
(5)SO2Desorb and concentrated sulfuric acid product processed
2.5% sulfurous acid solution is delivered in desorber 7 with pump caused by bipolar membrane electrodialysis device 6, is being desorbed
It is mixed with tower 7 with air, the sulfur dioxide desorption in sulfurous acid is come out.The sulfur dioxide gas content desorbed is
6.5% (V/V) left and right, through in drying tower 8 93% sulfuric acid absorption moisture therein.Sulfur dioxide gas enters conversion section,
Converter uses III I, IV II flows using conventional 3+1 flows, heat exchanger, and main technique index is shown in Table 5.Sulphur Dioxide
It is slowly into sulfur trioxide, while is a reversible reaction again, therefore catalyst is made to improve by vanadic anhydride
Reaction speed, desulfurization is entered by the tail gas after double-absorption to improve conversion ratio using the content for absorbing reduction product twice
Qualified discharge after the desulfurization of tower 3 absorbs.The sulfuric acid of generation is as international sale.
Specific material balance table, engineering consumption and operating cost are as shown in table 6-10.
Comparative example
Claus sulfur recovery facilities tail gas is through SCOT PROCESS FOR TREATMENTs, and the operational factor of SCOT PROCESS FOR TREATMENT Claus tail gas is such as
Shown in table 11, the operating cost of SCOT PROCESS FOR TREATMENT Claus tail gas is as shown in table 12.
It was found from the data analysis of table 11, after SCOT PROCESS FOR TREATMENT Claus tail gas, SO in outer waste air2Average content is about
700mg/m3Though temporarily country can be met at present《Discharge standard of air pollutants》(GB16279-1996) provide, but with
The reinforcement of national environmental protection policy, especially State Ministry of Environmental Protection promulgates petroleum refining enterprise for 2015《Petroleum refining industry
Pollutant emission standard》(GB31570-2015) SO in outer exhaust is required2Content is less than 400mg/m3, and existing enterprise 2017
New standard is had to carry out from July 1, in, it is evident that existing SCOT techniques have been difficult to meet the new environmental requirement of country.
It was found from the data analysis of table 12, after SCOT PROCESS FOR TREATMENT Claus tail gas, nearly 37,000,000 yuan of annual operating cost, wherein
It is 2345.3 ten thousand yuan to consume expense caused by steam, and 63%, the SCOT plant running expenses for occupying overall running cost are substantially higher.
It can be seen that from above-described embodiment and comparative example and prepare liquid sulfur dioxide according to Claus device exhausts, use
The exhaust gas treating method expense of disclosure system is about 9,630,000；The concentrated sulfuric acid is prepared according to Claus device exhausts, using this public affairs
The exhaust gas treating method expense of open system is about 13,980,000, is far below 37,000,000 yuan using SCOT techniques.
The preferred embodiment of the disclosure is described in detail above in association with accompanying drawing, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical scheme of the disclosure
Monotropic type, these simple variants belong to the protection domain of the disclosure.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the disclosure to it is various can
The combination of energy no longer separately illustrates.
In addition, it can also be combined between a variety of embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought, it should equally be considered as disclosure disclosure of that.
The Claus device exhaust A indexs of table 1
The desulfurizing tower main technique index of table 2
(used electrodialysis plant is pair as shown in FIG. 7 and 8 to the bipolar membrane electrodialysis device main technique index of table 3
Pole EDBM device, is alternately arranged by Bipolar Membrane and cavity block and formed)
| Sequence number | Project | Operation index |
| 1 | Bipolar Membrane enters doctor solution salinity, Wt% | 8 |
| 2 | Bipolar Membrane goes out mixed liquor NaOH concentration, Wt% | 2 |
| 3 | Bipolar Membrane goes out H2SO3Concentration, Wt% | 2.5 |
The desorber of table 4 and liquid SO2Preparation facilities main technique index
| Sequence number | Project | Operation index |
| 1 | Temperature in desorber | 100~105 DEG C |
| 2 | Drying tower moisture content of outlet | 0.1g/Nm3 |
| 3 | Condensator outlet temperature | ≤40℃ |
| 4 | SO2Storage pressure | ≤0.6Mpa |
| 5 | Liquid SO2Concentration | >=99.9% |
| 6 | SO2Desorption efficiency | >=90% |
The desorber of table 5 and concentrated sulfuric acid preparation facilities main technique index
| Sequence number | Project | Operation index |
| 1 | Temperature in desorber | 50~60 DEG C |
| 2 | Drying tower acid concentration | 92.5%~93.5% |
| 3 | Conversion ratio | >=99.7% |
| 4 | Desulfurizing tower absorptivity | ＞ 99.98% |
| 5 | Desorber exit gas SO2Concentration | 6.0%~6.5% |
| 6 | SO2Desorption efficiency | >=85% |
The material balance table of table 6
Note：Surge tank (not shown in accompanying drawing) connects heat exchanger 5 and bipolar membrane electrodialysis device 6.
The Claus tail gas liquid SO of table 72Total public work consumption
The total public work consumption of the Claus tail gas concentrated sulfuric acids of table 8
The Claus tail gas liquid SO of table 92Operating cost
| Sequence number | Project | Unit | Consumption | Price/member | Annual operating cost/member |
| 1 | Consume 0.5MPa steam | t/h | 4 | 154 | 5174400 |
| 2 | Consume industry water | t/h | 53 | 3 | 1335600 |
| 3 | Consume recirculated water | t/h | 200 | 0.25 | 420000 |
| 4 | Consume 30%NaOH | t/h | 0.118 | 800 | 792960 |
| 5 | Consume 98% sulfuric acid | t/h | 0.29 | 80 | 194880 |
| 6 | Consume instrument air | Nm3/h | 50 | 0.1 | 42000 |
| 7 | Gas | t/h | 0.11 | 1759 | 1625316 |
| 8 | Power consumption | kwh | 1326.75 | 0.65 | 7244055 |
| 9 | Produce liquid sulfur dioxide | t/h | -0.571 | 1500 | -7194600 |
| It is total | / | / | / | 9634611 |
The Claus tail gas concentrated sulfuric acid operating costs of table 10
| Sequence number | Project | Unit | Consumption | Price/member | Annual operating cost/member |
| 1 | Consume 0.5MPa steam | t/h | 1 | 154 | 1293600 |
| 2 | Consume industry water | t/h | 53 | 3 | 1335600 |
| 3 | Consume recirculated water | t/h | 100 | 0.25 | 210000 |
| 4 | Consume 30%NaOH | t/h | 0.118 | 800 | 792960 |
| 5 | Consume instrument air | Nm3/h | 50 | 0.1 | 42000 |
| 6 | Gas | t/h | 0.11 | 1759 | 1625316 |
| 7 | Power consumption | kwh | 1726.75 | 0.65 | 9428055 |
| 8 | Produce the concentrated sulfuric acid | t/h | -0.892 | 100 | -749280 |
| It is total | / | / | / | 13978251 |
Explanation：Operate above expense and do not calculate depreciation of fixed assets and maintenance cost and labor wage.
The operational factor of the SCOT PROCESS FOR TREATMENT Claus tail gas of table 11
| Sequence number | Project name | Unit | Numerical value |
| 1 | Claus exhaust temperatures | ℃ | 140 |
| 2 | Burn furnace temperature | ℃ | 1000 |
| 3 | Claus tail gas tolerance | t/h | 30 |
| 4 | Air input | t/h | 30.41 |
| 5 | Outer capacity | t/h | 39.28 |
| 6 | Outer exhaust SO2Content | mg/m3 | 700 |
The operating cost of the SCOT PROCESS FOR TREATMENT Claus tail gas of table 12
Claims (9)
1. a kind of processing system of Claus device exhausts, it is characterised in that the system includes combustion furnace (1), desulfurizing tower (3), double
Pole EDBM device (6) and desorber (7)；
The combustion furnace (1) is provided with entrance, the gas access containing oxygen and the exhanst gas outlet of Claus device exhausts, described
Desulfurizing tower (3) is provided with gas access, alkali wash water entrance, doctor solution outlet and exhanst gas outlet, the bipolar membrane electrodialysis device
(6) be provided with liquid inlet, electrodialysis lye export and electrodialysis acid solution outlet, the desorber (7) be provided with liquid inlet,
Gas vent and liquid outlet；
The exhanst gas outlet of the combustion furnace (1) is in fluid communication with the gas access of the desulfurizing tower (3), the desulfurizing tower (3)
Doctor solution exports to be in fluid communication with the liquid inlet of the bipolar membrane electrodialysis device (6), the bipolar membrane electrodialysis device (6)
The outlet of electrodialysis acid solution be in fluid communication with the liquid inlet of the desorber (7).
2. system according to claim 1, it is characterised in that the exhanst gas outlet of the combustion furnace (1) passes through waste heat boiler
(2) gas access with the desulfurizing tower (3) is in fluid communication；And/or
The doctor solution outlet of the desulfurizing tower (3) passes sequentially through accurate filter (4) and heat exchanger (5) and the Bipolar Membrane electric osmose
The liquid inlet of analysis apparatus (6) is in fluid communication；And/or
The electrodialysis lye export of the bipolar membrane electrodialysis device (6) is in fluid communication with the liquid inlet of the desulfurizing tower (3).
3. system according to claim 1, it is characterised in that the system also includes drying tower (8), the desorber
(7) entrance of gas vent and the drying tower (8) is in fluid communication.
4. system according to claim 1, it is characterised in that the combustion furnace (1), which is additionally provided with, helps fuel gas inlet.
5. system according to claim 1, it is characterised in that the bipolar membrane electrodialysis device (6) includes the first negative electrode
And the first anode (104) and the film of at least one set first between the first negative electrode (101) and the first anode (104) (101)
Right, first film is to first including at least two first Bipolar Membranes (102) and between adjacent first Bipolar Membrane (102)
Cation-exchange membrane (103), first cation-exchange membrane (103) it is its immediate be located at first negative electrode (101) one
The first alkali room (20), its immediate position of first cation-exchange membrane (103) are formed between the first Bipolar Membrane (102) of side
The first sour room (30) is formed between first Bipolar Membrane (102) of the first anode (104) side；First sour room (30)
The liquid inlet of the bipolar membrane electrodialysis device (6) is provided with, first alkali room (20) is provided with the Bipolar Membrane electric osmose
The electrodialysis lye export of analysis apparatus (6), first sour room (30) are provided with the electrodialysis acid solution outlet.
6. system according to claim 1, it is characterised in that the bipolar membrane electrodialysis device (6) includes the second negative electrode
And second plate (204) and the film of at least one set second between the second negative electrode (201) and second plate (204) (201)
Right, second film is to first including at least two second Bipolar Membranes (202) and between adjacent second Bipolar Membrane (202)
Anion-exchange membrane (203), first anion-exchange membrane (203) it is its immediate be located at second negative electrode (201) one
The second alkali room (21), its immediate position of first anion-exchange membrane (203) are formed between the second Bipolar Membrane (202) of side
The second sour room (31) is formed between second Bipolar Membrane (202) of the second plate (204) side；Second alkali room (21)
Liquid inlet and the electrodialysis lye export of the bipolar membrane electrodialysis device (6) are provided with, second sour room (31) is set
There is the electrodialysis acid solution to export.
7. system according to claim 1, it is characterised in that the bipolar membrane electrodialysis device (6) includes the 3rd negative electrode
And third anode (304) and at least one set of tertiary membrane between the 3rd negative electrode (301) and third anode (304) (301)
Right, the tertiary membrane is to including at least two second cation-exchange membranes (302) and positioned at adjacent second cation-exchange membrane
(302) the 3rd Bipolar Membrane (303) between, the 3rd Bipolar Membrane (303) it is its immediate be located at the 3rd negative electrode (301)
The 3rd sour room (32) is formed between the second cation-exchange membrane (302) of side, the 3rd Bipolar Membrane (303) is its immediate
The 3rd alkali room (22) is formed between second cation-exchange membrane (302) of the third anode (304) side；Described 3rd
Alkali room (22) and the 3rd sour room (32) are provided with the liquid inlet of the bipolar membrane electrodialysis device (6), the 3rd alkali room
(22) the electrodialysis lye export of the bipolar membrane electrodialysis device (6) is provided with, the 3rd sour room (32) is provided with described
Electrodialysis acid solution exports.
8. system according to claim 1, it is characterised in that the bipolar membrane electrodialysis device (6) includes the 4th negative electrode
And the 4th anode (405) and the film of at least one set the 4th between the 4th negative electrode (401) and the 4th anode (405) (401)
Right, the 4th film is to including at least two the 4th Bipolar Membranes (402) and between adjacent 4th Bipolar Membrane (402)
Three cation exchange membrane (403) and trianion exchange membrane (404)；It is described between adjacent 4th Bipolar Membrane (402)
Three cation exchange membrane (403) close to the 4th negative electrode (401) side, it is described to be located at adjacent 4th Bipolar Membrane (402)
Between trianion exchange membrane (404) close to the 4th anode (405) side；4th Bipolar Membrane (402) and its
Close between the trianion exchange membrane (404) of the 4th negative electrode (401) side formed the 4th sour room (33), institute
State and diluting compartment (43) is formed between three cation exchange membrane (403) and trianion exchange membrane (404), the described 4th is bipolar
Its immediate formation the 4th between the three cation exchange membrane (403) of the 4th anode (405) side of film (402)
Alkali room (23)；The diluting compartment (43) is provided with the liquid inlet and desalination solution outlet of the bipolar membrane electrodialysis device (6), institute
State the electrodialysis lye export that the 4th alkali room (23) is provided with the bipolar membrane electrodialysis device (6), the 4th sour room (33)
It is provided with the electrodialysis acid solution outlet.
9. system according to claim 1, it is characterised in that the desulfurizing tower (3) includes tower body (3A), positioned at tower body
The gas access of (3A) bottom, the exhanst gas outlet at the top of the tower body (3A) and the desulfurization positioned at the tower body (3A) bottom
Liquid exports, and is from top to bottom additionally provided with spraying layer (3B) and sieve tray (3C) in the tower body (3A), in the spraying layer (3B)
It is provided with least one atomizer (3D) for being used to be sent into alkali wash water；Along short transverse, the spraying layer (3B) and sieve tray
(3C) is between the gas access and exhanst gas outlet.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201720461975.3U CN206823499U (en) | 2017-04-28 | 2017-04-28 | A kind of processing system of Claus device exhausts |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786397A (en) * | 2017-04-28 | 2018-11-13 | 湖南中天元环境工程有限公司 | A kind of processing method and system of Claus device exhausts |
| US11530131B1 (en) | 2021-11-16 | 2022-12-20 | Saudi Arabian Oil Company | Methods and systems of sub-dew point sulfur recovery with interstage membrane units |
-
2017
- 2017-04-28 CN CN201720461975.3U patent/CN206823499U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786397A (en) * | 2017-04-28 | 2018-11-13 | 湖南中天元环境工程有限公司 | A kind of processing method and system of Claus device exhausts |
| US11530131B1 (en) | 2021-11-16 | 2022-12-20 | Saudi Arabian Oil Company | Methods and systems of sub-dew point sulfur recovery with interstage membrane units |
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