CN106621796A - Method and device for simultaneously removing carbonyl sulfide and carbon disulfide - Google Patents
Method and device for simultaneously removing carbonyl sulfide and carbon disulfide Download PDFInfo
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- CN106621796A CN106621796A CN201610928220.XA CN201610928220A CN106621796A CN 106621796 A CN106621796 A CN 106621796A CN 201610928220 A CN201610928220 A CN 201610928220A CN 106621796 A CN106621796 A CN 106621796A
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- fixed bed
- bed reaction
- reaction tower
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- heat
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 46
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000007921 spray Substances 0.000 claims abstract description 43
- 238000001816 cooling Methods 0.000 claims abstract description 39
- 238000011069 regeneration method Methods 0.000 claims abstract description 33
- 230000008929 regeneration Effects 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003546 flue gas Substances 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 23
- 239000002826 coolant Substances 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002918 waste heat Substances 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 15
- 230000023556 desulfurization Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- -1 Ferric nitrate modified activated-carbon Chemical class 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/808—Hydrolytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a method and a device for simultaneously removing carbonyl sulfide and carbon disulfide. The device which is a desulfurization device comprises a heat exchange system, an assistant catalysis system, a continuous operation system, a catalyst regeneration system and the like. The heat exchange system comprises a cooling tower and fixed-bed reaction towers, the assistant catalysis system comprises a stripping tower, a spray tower and a communication pipe, the continuous operation system comprises the two fixed-bed reaction towers, and the catalyst regeneration system comprises the heat exchange system and a regeneration spray system. The method and the device have the advantages that the method is high in desulfurization efficiency, heat from high-temperature flue gas can be effectively utilized, dilute sulfuric acid which is a product can be recycled, and accordingly the catalytic reaction efficiency can be improved; the double reaction towers are respectively positioned at a catalytic reaction stage and a catalyst regeneration stage and can be switched over by the aid of electromagnetic valves in a timed manner, and accordingly continuous operation of the systems can be guaranteed; elemental sulfur on the surfaces of deactivated catalysts can be transferred into liquid phases in regeneration procedures and is convenient to extract in follow-up procedures, and the device is high in integration level and automation degree.
Description
Technical field
The present invention relates to a kind of while removing cos, the method and device of carbon disulfide, belong to Air Pollution Control neck
Domain.
Background technology
As main organic sulfur, COS, CS2In being widely present in industrial smoke, such as yellow phosphoric tail gas, blast furnace tail gas etc..
Atmospheric environment is discharged into during industrial production and use, serious pollution and harm can be caused to environment and human body, industry
Micro CS in production2With COS to the toxic effect of catalyst so as to which catalytic effect and service life are affected by serious,
CS2Also H can be generated by slow hydrolysis with COS2S, corrodes production equipment, not only brings to industrial production very big
Economic loss, and equipment investment and product cost are increased, while COS and CS2Discharge be also the waste to Sulphur ressource.
Catalyzed hydrolytic methods remove COS and CS2Principle be：COS and CS2Change into vapor reaction on a catalyst
H2S, then H2S is removed in follow-up workshop section, and the reaction temperature of catalyzing hydrolysis is generally below 200 DEG C, and energy consumption is relatively low, secondary
Reaction is less, and containing the vapor needed for hydrolytic process in most of unstripped gas.At the same time, low-temperature catalyzed hydrolysis COS and
CS2Process can avoid the generation of the side reactions such as unstripped gas cracking, methanation, so the method becomes removing COS and CS at present2Grind
Study carefully one of focus in field.
Chinese patent CN 102886203A disclose the invention of " a kind of method of flue gas desulfurizing and hydrargyrum-removing ".The invention will contain
The water of chlorion is sprayed in circulating fluidized bed dry desulfuration demercuration dust arrester, then flue gas is purified.The method have compared with
High desulfuration efficiency, but the sulfur-containing compound of removing is SO2, and without catalyst step for regeneration.Chinese patent CN
103432861A discloses the invention of " sintering desulfuration white-smoke-removing system and its technological process ".The invention is according to desulfurization, eliminating water, drop
The order of temperature is purified to white cigarette.The method is with higher desulfuration efficiency and relatively low energy consumption, but the Containing Sulfur of removing
Compound is SO2, and without catalyst step for regeneration.Chinese patent CN 103657368A disclose a kind of " simultaneous SO_2 and NO removal demercuration
The invention of dry-method fume gas purification method and device ".The invention removes SO by the way of absorption2, reduction mode remove NOx,
The mode of oxidation removes Hg.The method has higher desulfurization denitration demercuration efficiency, but the sulfur-containing compound of removing is SO2,
And without catalyst step for regeneration.Remove cos, the method and device of carbon disulfide while involved in the present invention to have efficiently
Desulfuration efficiency, and high degree of automation, integrated level height, continuously-running, heat utilization ratio be high, sulfur recovery is convenient.
At present, report is had not seen with regard to strengthening removing cos, the method and device of carbon disulfide simultaneously with dilute sulfuric acid.
The content of the invention
It is an object of the invention to provide a kind of while removing cos, the method for carbon disulfide, the method not only has
Efficient desulfuration efficiency, and high degree of automation, integrated level height, continuously-running, heat utilization ratio height, sulfur recovery are conveniently, energy
The problem of effectively solving organic sulfur purification, comprises the following steps that：
（1）High-temperature flue gas after pre- dust removal process first pass through waste heat boiler and are cooled to 150 ~ 200 DEG C, then are entered by cooling tower
Row heat exchange, makes flue-gas temperature be down to 60 ~ 100 DEG C, and coolant is increased to 60 ~ 100 DEG C.
（2）Gas after cooling by the effect of stripper, brings the dilute sulfuric acid in stripper into fixed bed anti-again
Ying Tazhong.
（3）Step（1）It is middle to absorb in heat and the coolant inflow fixed bed reaction tower heat exchange jacket after intensification, will react
The temperature of catalyst brings up to 60 ~ 100 DEG C in tower.
（4）There is catalytic hydrolysis reaction in fixed bed reaction tower in the gas of entrainment dilute sulfuric acid（Produce H2S、SO2Deng product
Thing）.
（5）The SO of generation2Spray column being entered with air-flow and producing sulfuric acid, sulfurous acid, sulfuric acid and sulfurous acid are returned through communicating pipe
Stripper is flow to, purified gas is discharged from outlet.
（6）Coolant reenters cooling tower recycling after heat release in fixed bed reaction tower chuck.
（7）Regeneration water flows into fixed bed reaction tower and rinses decaying catalyst, by the sulfate and simple substance of catalyst surface
Sulphur is taken out of into sulphur recovery operation, the flash baking under the heat effect of chuck of the catalyst after washing, forms regeneration
Catalyst.
Dilute sulfuric acid molar concentration is 0.01 ~ 0.1mol/L in stripper of the present invention and spray column.
Coolant of the present invention is the mixed liquor of second alcohol and water, and ethanol is 0.5 ~ 20 with the mol ratio of water:1.
Catalyst in fixed bed reaction tower of the present invention is hydrolyst, for example：Modified active carbon catalyst, change
Property houghite catalyst, modified alumina catalyst, modified molecular sieve catalyst, modified metal-oxide catalyst etc..
Another object of the present invention is to provide a kind of while removing cos, the device of carbon disulfide, including waste heat pot
Stove 1, cooling tower 2, stripper 3, fixed bed reaction tower I 4, fixed bed reaction tower II 5, spray column 6, heat exchange pump I 7, heat exchange pump II
8th, regeneration pump 9, spray pump 10, communicating pipe 11, agitator 12, heat exchange jacket 13；Waste heat boiler 1 is connected with cooling tower 2, cooling tower
2 connect with stripper 3；Stripper 3 is connected respectively by three-way magnetic valve with fixed bed reaction tower I 4 and fixed bed reaction tower II 5
It is logical；Fixed bed reaction tower I 4 and fixed bed reaction tower II 5 are connected by three-way magnetic valve with spray column 6；Stripper 3 and spray column
By connecting communicating pipe 11, the lower end of spray column 6 is connected by spray pump 10 with the top of spray column 6 for 6 lower end；Cooling tower 2,
Fixed bed reaction tower I 4, the inwall of fixed bed reaction tower II 5 are equipped with heat exchange jacket 13；Regeneration water tank passes through regeneration pump 9 and consolidates
Fixed bed reaction tower I 4 is connected with the top of fixed bed reaction tower II 5, fixed bed reaction tower I 4 and the bottom of fixed bed reaction tower II 5 with
Sulfur recovery facility is connected；The outlet of heat exchange pump II 8 is connected with the top of the internal heat chuck of cooling tower 2, is changed inside cooling tower 2
The bottom of thermal jacket by heat exchange pump I 7 respectively with fixed bed reaction tower I 4 and the top of the internal heat chuck of fixed bed reaction tower II 5
Portion connects, and the bottom of fixed bed reaction tower I 4 and the internal heat chuck of fixed bed reaction tower II 5 is by three-way magnetic valve and heat exchange
The entrance connection of pump II 8.
The bottom of stripper of the present invention 3 and spray column 6 is respectively provided with agitator 12.
Fixed bed reaction tower I 4 of the present invention, the inside of fixed bed reaction tower II 5 arrange regeneration flusher, and bottom sets
Put reservoir.
The present invention principle be：Using hydrolyst, by micro water vapor in flue gas and O2, make COS, CS2Urge simultaneously
Change is hydrolyzed to H2S, the accessory substance SO produced under aerobic conditions2Continue to be oxidized to sulfuric acid in spray operation, the dilute sulfuric acid of generation with
Air-flow enters catalytic process steps, and so as to strengthen desulfuration efficiency, desulfurization reaction temperature is：60 ~ 100 DEG C, COS and CS2Removal efficiency is high
In 90%, key reaction is as follows：
The advantage and technique effect of the inventive method：
（1）The heat-exchange system being made up of cooling tower and fixed bed reaction tower, efficiently make use of the temperature of flue gas itself, be not required to volume
External heat source can make catalyst reach suitable reaction temperature；
（2）The co-catalysis system being made up of stripper, spray column and communicating pipe, can be by accessory substance SO2Recycle, generation it is dilute
Sulfuric acid can play enhanced effect to catalyzing hydrolysis process；
（3）The catalyst regeneration system being made up of heat-exchange system and regeneration spray system, the heat that heat-exchange system can be utilized to provide
Amount carries out flash baking to catalyst, improves the utilization ratio of heat, the sulphur energy contained in the waste liquid produced after regeneration
Access and reuse；
（4）The dilute sulfuric acid concentration that the agitator of spray column and stripper bottom is used to adjust in reservoir and reservoir between is put down
Weighing apparatus.
（5）The continuous operational system being made up of two fixed bed reaction towers, can be using same set of heat-exchanger rig and regeneration
Device is catalyzed and regenerative process, can exchange-column shift characteristic, allow reaction system continuously to work, and automaticity
High, integrated level is high.
Description of the drawings
Fig. 1 is the structural representation of device of the present invention；
Fig. 2 is present invention process flow chart.
In figure：1- waste heat boilers；2- cooling towers；3- strippers；4- fixed bed reactions tower I；5- fixed bed reactions tower II；6-
Spray column；7- heat exchange pumps I；8- heat exchange pumps II；9- regeneration pumps；10- spray pumps；11- communicating pipes；12- agitators；13- heat exchange folders
Set.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, but the scope of the present invention is not limited to following institute
State content.
While removing cos, the method equipment therefor of carbon disulfide described in the embodiment of the present invention, including waste heat boiler 1,
Cooling tower 2, stripper 3, fixed bed reaction tower I 4, fixed bed reaction tower II 5, spray column 6, heat exchange pump I 7, heat exchange pump II 8, again
Raw pump 9, spray pump 10, communicating pipe 11, agitator 12, heat exchange jacket 13；Waste heat boiler 1 is connected with cooling tower 2, cooling tower 2 with
Stripper 3 is connected；Stripper 3 is connected respectively by three-way magnetic valve with fixed bed reaction tower I 4 and fixed bed reaction tower II 5；Gu
Fixed bed reaction tower I 4 and fixed bed reaction tower II 5 are connected by three-way magnetic valve with spray column 6；Under stripper 3 and spray column 6
By connecting communicating pipe 11, the lower end of spray column 6 is connected by spray pump 10 with the top of spray column 6 at end；Cooling tower 2, fixation
Bed reaction tower I 4, the inwall of fixed bed reaction tower II 5 are equipped with heat exchange jacket 13；Regeneration water tank is by regeneration pump 9 and fixed bed
Reaction tower I 4 is connected with the top of fixed bed reaction tower II 5, fixed bed reaction tower I 4 and the bottom of fixed bed reaction tower II 5 and sulphur
Retracting device is connected；The outlet of heat exchange pump II 8 is connected with the top of the internal heat chuck of cooling tower 2, the internal heat of cooling tower 2 folder
The bottom of set by heat exchange pump I 7 respectively with connect at the top of fixed bed reaction tower I 4 and the internal heat chuck of fixed bed reaction tower II 5
Logical, the bottom of fixed bed reaction tower I 4 and the internal heat chuck of fixed bed reaction tower II 5 is by three-way magnetic valve and heat exchange pump II 8
Entrance connection；The bottom of stripper 3 and spray column 6 is respectively provided with agitator 12；Fixed bed reaction tower I 4, fixed bed reaction tower II
Setting regeneration flusher in 5, bottom arranges reservoir.
Cooling tower 2 and fixed bed reaction tower I 4 and the composition heat-exchange system of fixed bed reaction tower II 5, cooling tower 2 absorbs flue gas
Heat and be delivered in coolant, coolant after intensification flows into fixed bed reaction tower I 4 and fixed bed reaction tower II 5 is simultaneously put
Heat, maintains catalyst in a suitable reaction temperature, and the coolant after heat release is returned to absorbs heat again in cooling tower 2, from
And carry out recuperated cycle.
11 groups of co-catalysis systems of stripper 3, spray column 6 and communicating pipe are into from fixed bed reaction tower I 4 and fixed bed reaction
The accessory substance SO that tower II 5 is produced2Dilute sulfuric acid is formed in spray column, dilute sulfuric acid again through being back to communicating pipe 11 in stripper 3,
Dilute sulfuric acid in stripper 3 is brought in fixed bed reaction tower I 4 and fixed bed reaction tower II 5 in the presence of stripper and increases
Strong catalyzing hydrolysis effect, so as to reach promoting catalysis.
Heat-exchange system and regeneration spray system composition regenerative system, regeneration enters the fixation in the regenerative process stage with water
Bed reaction tower II 5 and fixed bed reaction tower I 4, the sulfate and sulphur of catalyst surface are rinsed to bottom under spray effect
Reservoir, while catalyst is dried under the heating of heat-exchange system, the waste liquid in reservoir is carried for follow-up sulphur
Take operation.
Fixed bed reaction tower I 4 and the composition continuous operational system of fixed bed reaction tower II 5, when a fixed bed reaction tower I 4
In course of reaction state when, another fixed bed reaction tower II 5 under the control of magnetic valve be in the state of regenerative process 5, often
Can automatically switch the working condition residing for two towers every certain hour magnetic valve, so as to reach the function of continuous operation.
Embodiment 1
Remove cos, the method for carbon disulfide described in the present embodiment simultaneously to comprise the following steps：
（1）High-temperature flue gas after pre- dust removal process first pass through waste heat boiler 1 and are cooled to 150 DEG C, then are carried out by cooling tower 2
Heat exchange, makes flue-gas temperature be down to 60 DEG C, and coolant is increased to 60 DEG C.
（2）Molar concentration in stripper 3 is again 0.01mol/L by the effect of stripper 3 by the gas after cooling
Dilute sulfuric acid bring in fixed bed reaction tower I 4 and fixed bed reaction tower II 5.
（3）Step（1）The coolant of 60 DEG C after middle absorption heat and intensification flows into fixed bed reaction tower I 4 and fixed bed
In the heat exchange jacket of reaction tower II 5, the temperature of catalyst in fixed bed reaction tower I 4 and fixed bed reaction tower II 5 is brought up to into 60
℃。
（4）To there are catalyzing hydrolysis in the gas of entrainment dilute sulfuric acid anti-in fixed bed reaction tower I 4 and fixed bed reaction tower II 5
Should.
（5）The SO of generation2Spray column 6 being entered with air-flow and producing sulfuric acid, sulfurous acid, sulfuric acid and sulfurous acid are through communicating pipe 11
Stripper 3 is back to, purified gas is discharged from outlet.
（6）Coolant reenters cooling tower 2 after heat release in fixed bed reaction tower I 4 and the chuck of fixed bed reaction tower II 5
Recycle.
（7）Regeneration water flows into fixed bed reaction tower I 4 and fixed bed reaction tower II 5 rinses decaying catalyst, by catalyst
The sulfate and elemental sulfur on surface is taken out of into sulphur recovery operation, and the catalyst after washing is under the heat effect of chuck
Flash baking, forms regenerated catalyst.
The present embodiment used catalyst is through Ferric nitrate modified activated-carbon catalyst Fe/AC.
By the method and device to sulfur-containing smoke gas（CS2Concentration 40ppm, COS concentration 500ppm, O2Concentration 1%, air speed
80000h-1）Carry out desulfurization, 100% CS2Clearance and 100% COS clearances respectively reach 600min and 540min.
This shows that the method and device have good desulfurized effect.
Embodiment 2
Remove cos, the method for carbon disulfide described in the present embodiment simultaneously to comprise the following steps：
（1）High-temperature flue gas after pre- dust removal process first pass through waste heat boiler 1 and are cooled to 200 DEG C, then are carried out by cooling tower 2
Heat exchange, makes flue-gas temperature be down to 80 DEG C, and coolant is increased to 80 DEG C.
（2）Molar concentration in stripper 3 is again 0.06mol/L by the effect of stripper 3 by the gas after cooling
Dilute sulfuric acid bring in fixed bed reaction tower I 4 and fixed bed reaction tower II 5.
（3）Step（1）The coolant of 80 DEG C after middle absorption heat and intensification flows into fixed bed reaction tower I 4 and fixed bed
In the heat exchange jacket of reaction tower II 5, the temperature of catalyst in fixed bed reaction tower I 4 and fixed bed reaction tower II 5 is brought up to into 80
℃。
（4）To there are catalyzing hydrolysis in the gas of entrainment dilute sulfuric acid anti-in fixed bed reaction tower I 4 and fixed bed reaction tower II 5
Should.
（5）The SO of generation2Spray column 6 being entered with air-flow and producing sulfuric acid, sulfurous acid, sulfuric acid and sulfurous acid are through communicating pipe 11
Stripper 3 is back to, purified gas is discharged from outlet.
（6）Coolant reenters cooling tower 2 after heat release in fixed bed reaction tower I 4 and the chuck of fixed bed reaction tower II 5
Recycle.
（7）Regeneration water flows into fixed bed reaction tower I 4 and fixed bed reaction tower II 5 rinses decaying catalyst, by catalyst
The sulfate and elemental sulfur on surface is taken out of into sulphur recovery operation, and the catalyst after washing is under the heat effect of chuck
Flash baking, forms regenerated catalyst.
The present embodiment used catalyst is the houghite catalyst being prepared into by ferric nitrate, copper nitrate, aluminum nitrate
FeCuAlOx。
By the method and device to sulfur-containing smoke gas（CS2Concentration 40ppm, COS concentration 500ppm, O2Concentration 1%, air speed
80000h-1）Carry out desulfurization, 100% CS2Clearance and 100% COS clearances respectively reach 840min and 630min.
This shows that the method and device have good desulfurized effect.
Embodiment 3
Remove cos, the method for carbon disulfide described in the present embodiment simultaneously to comprise the following steps：
（1）High-temperature flue gas after pre- dust removal process first pass through waste heat boiler 1 and are cooled to 180 DEG C, then are carried out by cooling tower 2
Heat exchange, makes flue-gas temperature be down to 95 DEG C, and coolant is increased to 95 DEG C.
（2）Molar concentration in stripper 3 is again 0.1mol/L by the effect of stripper 3 by the gas after cooling
Dilute sulfuric acid bring in fixed bed reaction tower I 4 and fixed bed reaction tower II 5.
（3）Step（1）The coolant of 95 DEG C after middle absorption heat and intensification flows into fixed bed reaction tower I 4 and fixed bed
In the heat exchange jacket of reaction tower II 5, the temperature of catalyst in fixed bed reaction tower I 4 and fixed bed reaction tower II 5 is brought up to into 95
℃。
（4）To there are catalyzing hydrolysis in the gas of entrainment dilute sulfuric acid anti-in fixed bed reaction tower I 4 and fixed bed reaction tower II 5
Should.
（5）The SO of generation2Spray column 6 being entered with air-flow and producing sulfuric acid, sulfurous acid, sulfuric acid and sulfurous acid are through communicating pipe 11
Stripper 3 is back to, purified gas is discharged from outlet.
（6）Coolant reenters cooling tower 2 after heat release in fixed bed reaction tower I 4 and the chuck of fixed bed reaction tower II 5
Recycle.
（7）Regeneration water flows into fixed bed reaction tower I 4 and fixed bed reaction tower II 5 rinses decaying catalyst, by catalyst
The sulfate and elemental sulfur on surface is taken out of into sulphur recovery operation, and the catalyst after washing is under the heat effect of chuck
Flash baking, forms regenerated catalyst.
The present embodiment used catalyst is the activated alumina catalyst Fe/Al being modified through copper nitrate2O3。
By the method and device to sulfur-containing smoke gas（CS2Concentration 40ppm, COS concentration 500ppm, O2Concentration 1%, air speed
80000h-1）Carry out desulfurization, 100% CS2Clearance and 100% COS clearances respectively reach 720min and 570min.
This shows that the method and device have good desulfurized effect.
Claims (7)
1. a kind of at the same remove cos, the method for carbon disulfide, it is characterised in that comprise the following steps that：
（1）High-temperature flue gas after pre- dust removal process first pass through waste heat boiler and are cooled to 150 ~ 200 DEG C, then are entered by cooling tower
Row heat exchange, makes flue-gas temperature be down to 60 ~ 100 DEG C, and coolant is increased to 60 ~ 100 DEG C；
（2）Gas after cooling by the effect of stripper, brings the dilute sulfuric acid in stripper into fixed bed reaction tower again
In；
（3）Step（1）It is middle to absorb in heat and the coolant inflow fixed bed reaction tower heat exchange jacket after intensification, by reaction tower
The temperature of catalyst brings up to 60 ~ 100 DEG C；
（4）There is catalytic hydrolysis reaction in fixed bed reaction tower in the gas of entrainment dilute sulfuric acid；
（5）The SO of generation2Spray column being entered with air-flow and producing sulfuric acid, sulfurous acid, sulfuric acid and sulfurous acid are back to vapour through communicating pipe
Stripper, purified gas is discharged from outlet；
（6）Coolant reenters cooling tower recycling after heat release in fixed bed reaction tower chuck；
（7）Regeneration water flows into fixed bed reaction tower and rinses decaying catalyst, by the sulfate of catalyst surface and elemental sulfur band
Go out into sulphur recovery operation, the flash baking under the heat effect of chuck of the catalyst after washing, form regeneration catalyzing
Agent.
2. cos, the method for carbon disulfide are removed according to claim 1 simultaneously, it is characterised in that：Stripper and spray
Dilute sulfuric acid molar concentration is 0.01 ~ 0.1mol/L in tower.
3. cos, the method for carbon disulfide are removed according to claim 1 simultaneously, it is characterised in that：Coolant is ethanol
With the mixed liquor of water, ethanol is 0.5 ~ 20 with the mol ratio of water:1.
4. according to claim 1 at the same remove cos, the method for carbon disulfide, it is characterised in that：Fixed bed reaction
Catalyst in tower is hydrolyst.
5. a kind of at the same remove cos, the device of carbon disulfide, it is characterised in that：Including waste heat boiler（1）, cooling tower（2）、
Stripper（3）, fixed bed reaction tower I（4）, fixed bed reaction tower II（5）, spray column（6）, heat exchange pump I（7）, heat exchange pump II
（8）, regeneration pump（9）, spray pump（10）, communicating pipe（11）, agitator（12）, heat exchange jacket（13）；Waste heat boiler（1）With cooling
Tower（2）Connection, cooling tower（2）With stripper（3）Connection；Stripper（3）By three-way magnetic valve respectively with fixed bed reaction tower I
（4）With fixed bed reaction tower II（5）Connection；Fixed bed reaction tower I（4）With fixed bed reaction tower II（5）By three-way magnetic valve
With spray column（6）Connection；Stripper（3）And spray column（6）Lower end pass through communicating pipe（11）Connection, spray column（6）Lower end
By spray pump（10）With spray column（6）Top connection；Cooling tower（2）, fixed bed reaction tower I（4）, fixed bed reaction tower II
（5）Inwall be equipped with heat exchange jacket（13）；Regeneration water tank passes through regeneration pump（9）With fixed bed reaction tower I（4）It is anti-with fixed bed
Answer tower II（5）Top connection, fixed bed reaction tower I（4）With fixed bed reaction tower II（5）Bottom connects with sulfur recovery facility
It is logical；Heat exchange pump II（8）Outlet and cooling tower（2）The top connection of internal heat chuck, cooling tower（2）Internal heat chuck
Bottom is by the pump I that exchanges heat（7）Respectively with fixed bed reaction tower I（4）With fixed bed reaction tower II（5）The top of internal heat chuck
Connection, fixed bed reaction tower I（4）With fixed bed reaction tower II（5）The bottom of internal heat chuck passes through three-way magnetic valve and changes
Heat pump II（8）Entrance connection.
6. cos, the device of carbon disulfide are removed according to claim 5 simultaneously, it is characterised in that：Stripper（3）And spray
Drench tower（6）Bottom be respectively provided with agitator（12）.
7. cos, the device of carbon disulfide are removed according to claim 5 simultaneously, it is characterised in that：Fixed bed reaction tower I
（4）, fixed bed reaction tower II（5）Inside arrange regeneration flusher, bottom arrange reservoir.
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| CN107726867A (en) * | 2017-09-28 | 2018-02-23 | 安徽省金鸿再生资源科技有限公司 | A kind of vacuum drying oven discharging opening material quickly cooling dust pelletizing system |
| CN109200707A (en) * | 2017-07-10 | 2019-01-15 | 邯郸学院 | A kind of chemical industry smelting furnace device for recovering tail gas |
| CN112239208A (en) * | 2020-12-09 | 2021-01-19 | 吉林三源化工有限公司 | Carbon disulfide production system |
| CN112387088A (en) * | 2020-09-18 | 2021-02-23 | 昆明理工大学 | Low-temperature plasma synergistic Cu/gamma-Al2O3Method for degrading carbonyl sulfide by catalyst |
| CN112403431A (en) * | 2020-10-27 | 2021-02-26 | 中国科学院过程工程研究所 | Wave-shaped supporting plate, tower equipment and application |
| CN112657331A (en) * | 2020-12-31 | 2021-04-16 | 成都达奇环境科技有限公司 | Flue gas desulfurization method and flue gas desulfurization equipment |
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| CN114515508A (en) * | 2020-11-19 | 2022-05-20 | 山东师范大学 | Method for removing carbonyl sulfide in flue gas by using hydrogen peroxide |
| CN114534471A (en) * | 2020-11-26 | 2022-05-27 | 中国石油天然气股份有限公司 | Treatment method of tail gas generated by regenerating mercaptan-removing alkali liquor |
| CN115400533A (en) * | 2022-08-23 | 2022-11-29 | 天津绿菱气体有限公司 | Method and device for recycling carbonyl sulfide tail gas |
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| CN114515508A (en) * | 2020-11-19 | 2022-05-20 | 山东师范大学 | Method for removing carbonyl sulfide in flue gas by using hydrogen peroxide |
| CN114534471A (en) * | 2020-11-26 | 2022-05-27 | 中国石油天然气股份有限公司 | Treatment method of tail gas generated by regenerating mercaptan-removing alkali liquor |
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| CN112657331A (en) * | 2020-12-31 | 2021-04-16 | 成都达奇环境科技有限公司 | Flue gas desulfurization method and flue gas desulfurization equipment |
| CN113117470A (en) * | 2021-05-12 | 2021-07-16 | 昆明理工大学 | Method for tail gas desulfurization and sulfur recycling in low-temperature methanol washing process |
| CN115400533A (en) * | 2022-08-23 | 2022-11-29 | 天津绿菱气体有限公司 | Method and device for recycling carbonyl sulfide tail gas |
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