CN110282606A - The wet processing system and technique of aqueous sulphur cream and desulfurization waste liquor - Google Patents
The wet processing system and technique of aqueous sulphur cream and desulfurization waste liquor Download PDFInfo
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- CN110282606A CN110282606A CN201910603929.6A CN201910603929A CN110282606A CN 110282606 A CN110282606 A CN 110282606A CN 201910603929 A CN201910603929 A CN 201910603929A CN 110282606 A CN110282606 A CN 110282606A
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- 238000000034 method Methods 0.000 title claims abstract description 243
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000005864 Sulphur Substances 0.000 title claims abstract description 76
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 72
- 239000002699 waste material Substances 0.000 title claims abstract description 71
- 230000023556 desulfurization Effects 0.000 title claims abstract description 69
- 238000012545 processing Methods 0.000 title claims abstract description 66
- 239000006071 cream Substances 0.000 title claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 277
- 230000008569 process Effects 0.000 claims abstract description 120
- 238000004140 cleaning Methods 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000746 purification Methods 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims description 306
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002918 waste heat Substances 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 30
- 239000003595 mist Substances 0.000 claims description 24
- 238000007872 degassing Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000008246 gaseous mixture Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000012717 electrostatic precipitator Substances 0.000 claims description 8
- 239000002737 fuel gas Substances 0.000 claims description 8
- 230000008676 import Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 28
- 238000001816 cooling Methods 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 13
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 150000003839 salts Chemical group 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 7
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007255 decyanation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000035611 feeding Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010237 hybrid technique Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses the wet processing systems and technique of a kind of aqueous sulphur cream and desulfurization waste liquor.Wet processing system of the present invention includes: a molten sulphur device, a burner, a purification device, a Benitration reactor, a combination type reactor, a sulfuric acid vapor condenser, a sulfuric acid blending tank and an exhaust gas processing device.The various concentration desulfurization waste liquor generated after coke-oven plant's cleaning and desulfurization and the conversion of aqueous sulphur cream are produced as the sulfuric acid of high added value by the present invention, and equipment is few, and process is short, and heat exchange is simple, and pressure drop is small, and low energy consumption, and the waste acid quantity for needing to discharge is few.
Description
Technical field
The present invention relates to the wet processing systems and technique of a kind of aqueous sulphur cream and desulfurization waste liquor.
Background technique
Currently, numerous coal chemical enterprises use the ammonia process Wet-type oxidation sweetening technique removing coke with HPF, PDS etc. for catalyst
Hydrogen sulfide and hydrogen cyanide in producer gas.This method have desulfuration efficiency is high, process flow is short, small investment, stable operation, operation at
This low advantage, but the desulfurization waste liquor of by-product, sulphur mud form secondary pollution again, and difficulty of governance is very big.
In addition, above-mentioned sulfur removal technology generates the secondary salts waste liquid such as ammonium thiocyanate and ATS (Ammonium thiosulphate) during desulfuration and decyanation.
When secondary salt concentration buildup is higher in system, coal gas desulfurization decyanation efficiency, aggravation equipment corrosion can be seriously affected.It is currently used
Secondary salt process for treating waste liquor has: waste liquid is blended into coke making and coal blending, send coke oven to burn and decomposes；Extract ammonium thiocyanate and ATS (Ammonium thiosulphate) pair
Salt.
Production practices show secondary salt waste liquid being blended into coke making and coal blending, send coke oven to burn decomposition technique, since waste liquid is being blended into
During coke making and coal blending, the pernicious gases volatile emission such as ammonia in waste liquid is dissolved in into atmosphere, environmental pollution is caused and makes it
Using being restricted；And take and extract ammonium thiocyanate and ATS (Ammonium thiosulphate) secondary salt technique, then due to secondary salt product market capacity is small,
Secondary salt product sales difficulty, especially ATS (Ammonium thiosulphate) market form new coking solid waste, subsequent environmental protection are brought to ask without demand
Topic.
Since there are problem above, it is restricted currently used desulfuration waste liquid treatment process in practical applications, leads
The control of secondary salt concentration is higher in the most desulfurizers of cause, affects the normal performance and coking Environmental Protection Level of desulfurizer performance
Raising.Low-quality sulfur majority is used simultaneously with selling at a low price or freely giving user, and Sulphur ressource fails to obtain effective and reasonable
It utilizes, generates due surcharge.
Although having in the prior art using the direct incineration method relieving haperacidity of sulphur foam, vacuum potassium carbonate method desulfurization-matched condensation system
The recycling and utilization of Sulphur ressource may be implemented in acid, the techniques such as Claus sulfur recovery, but all there is process flow complexity, investment
Greatly, the problem of production run is at high cost etc. and defect.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome the desulfurization generated after coke-oven plant's cleaning and desulfurization in the prior art
Waste liquid and aqueous sulphur cream are difficult, generate secondary pollution, process flow is complicated, investment is big, production run is at high cost etc.
Problem and defect provide the wet processing system and technique of a kind of aqueous sulphur cream and desulfurization waste liquor, and the process equipment is few, process
Short, heat exchange is simple, and pressure drop is small, and low energy consumption, and the waste acid quantity for needing to discharge is few.
The present invention is to solve above-mentioned technical problem by following technical proposals:
The present invention provides the wet processing systems of a kind of aqueous sulphur cream and desulfurization waste liquor comprising: a molten sulphur device, one
Burner, a purification device, a Benitration reactor, a combination type reactor, a sulfuric acid vapor condenser, a sulfuric acid blending tank
With an exhaust gas processing device；
For melting aqueous sulphur cream, the molten sulphur device is connected the molten sulphur device with the burner；
The burner be used for by desulfurization waste liquor and through melting aqueous sulphur cream burning generate contain SO2Process gas, institute
The gas vent for stating burner is connected with the gas feed of the purification device；
The purification device contains SO for removing2Process gas in solid impurity and acid mist, the gas of the purification device
Body outlet is connected with the import of the Benitration reactor；
The Benitration reactor contains SO for being catalytically decomposed2Process gas in oxynitrides, the Benitration reactor
Outlet be connected with the import of the combination type reactor；
The combination type reactor will be for that will contain SO2Process gas catalysis oxidation generate contain SO3Process gas, the combination
The outlet of formula reactor is connected with the sulfuric acid vapor condenser；
The sulfuric acid vapor condenser will be for that will contain SO3Process gas condense to form sulfuric acid, the sulfuric acid vapor condenser
Exhaust port be connected with the exhaust gas processing device, the leakage fluid dram of the sulfuric acid vapor condenser and the sulfuric acid blending tank
It is connected.
In the following, being described further to sour wet processing system of the invention:
The desulfurization waste liquor generated after coke-oven plant's cleaning and desulfurization and aqueous sulphur cream are sent into burner and burned by the present invention, burn
Generate SO2, send after purified processing, denitration into combination type reactor, SO2It is converted into gaseous state SO under the effect of the catalyst3,
Then gaseous state SO3It send to sulfuric acid vapor condenser and condenses to form sulfuric acid.
Preferably, the upstream of the burner is also connected with an enrichment facility, for desulfurization waste liquor to be concentrated.Institute
The enrichment facility that enrichment facility can be this field routine is stated, the present invention is preferably concentration tower.
Preferably, the exhaust port of the molten sulphur device is connected with the exhaust gas processing device.
Preferably, the burner is a combustion furnace.
Preferably, the burner is also connected with a waste-heat recoverer, for recycle generated in burner containing SO2
Process gas heat.The waste-heat recoverer is connect with the burner using direct coupled structure, i.e., in the described burner
What is generated contains SO2Process gas be directly entered the import of the waste-heat recoverer, using direct heat transfer technology, heat recovery efficiency
Height overcomes the defect of equipment easy fouling and blocking.
More preferably, it is additionally provided with a process gas heat exchanger between the waste-heat recoverer and the purification device, is used for into one
Step recycling contains SO2Process gas in heat.What is generated in the burner contains SO2Process gas recycled through waste-heat recoverer
Enter the process gas heat exchanger after heat, the purification device is entered after the process gas heat exchanger further cools down.
Preferably, the purification device includes sequentially connected technique gas wash tower, an electrostatic precipitator and a process gas
Air-introduced machine.More preferably, the process gas air-introduced machine is connected with the process gas heat exchanger.What is generated in the burner contains
SO2Process gas dust and objectionable impurities (such as halogen, arsenic etc.) are removed in technique gas wash tower, by technique air purge
It washs tower purified gas and enters electrostatic precipitator removing acid mist, the gas after removing acid mist is after the pressurization of process gas air-introduced machine in institute
It states in process gas heat exchanger and contains SO with from the waste-heat recoverer2Process gas exchange heat, from the waste heat recycle
Device contains SO2The heat of process gas be recovered, while purified process gas is heated.
Preferably, the technique gas wash tower is equipped with a cleaning solution circulation loop, on the cleaning solution circulation loop successively
Equipped with a detergent circulator, a filter and a cleaning solution cooler, the cleaning solution circulation loop is used for the technique
Cleaning solution in gas wash tower is pressurized, is filtered and is cooled down, and realizes the circulation of cleaning solution.
On the one hand the outlet of the filter is connected with the cleaning solution cooler, be on the other hand connected with a degassing tower,
Cleaning solution in the technique gas wash tower enters the filter after detergent circulator pressurization and filters, after filtering
Cleaning solution a part enter the cleaning solution cooler it is cooling after return in the technique gas wash tower, another part enters institute
It is discharged after stating degassing tower degassing as spent acid.
Preferably, the gas vent of the degassing tower is connected with the exhaust gas processing device.
The downstream of the cleaning solution cooler is also connected with process water supply pipeline, and the process water supply pipeline is used for
Fresh process water is supplemented into the technique gas wash tower, technique gas wash tower outlet temperature is can control, adjusts process gas
Water sulphur ratio controls water sulfur balance, is convenient for the relieving haperacidity of downstream wet process, produces high value added product to greatest extent, while improving product
The flexibility of matched design.In addition, can control the discharge amount of waste water by supplement Fresh process water, waste water can be greatly reduced
Treating capacity.
Preferably, being additionally provided with a gaseous mixture branch, the gaseous mixture between the purification device and the Benitration reactor
Branch road is equipped with an air preheater and a mixing arrangement, the mixing arrangement be used for by ammonia and through the air preheater it is pre-
The air of heat mixes to obtain gaseous mixture, and the gaseous mixture contains SO with through the purification device is purified2Process gas mixing it is laggard
Enter the Benitration reactor.
Preferably, the Benitration reactor is SCR denitration reaction device.
Preferably, the combination type reactor is successively arranged the first bed, the first sect heat-exchanger, second from top to bottom
Layer, the second sect heat-exchanger, third bed and technique Gas Cooler.First bed~third bed is filled with catalyst, is urging
Under agent effect, SO2Catalysis oxidation is converted into SO3。SO2Catalytic oxidation process be an exothermic reaction, therefore leave described
The process gas temperature of one bed is increased, and second bed is entered after the first sect heat-exchanger lowered temperature reclamation heat
The reaction was continued, and the process gas from second bed enters after the second sect heat-exchanger lowered temperature reclamation heat described in
Third bed, the process gas from the third bed enter the technique Gas Cooler and are cooled down.The combination type reactor
Compact-sized, save the cost optimizes space layout, convenient for manufacture maintenance, and is conducive to the recycling of thermal energy gradient, science is closed
Reason.
Preferably, the wet processing system of the aqueous sulphur cream and desulfurization waste liquor further includes a drum, the drum and institute
It states waste-heat recoverer to connect to form one first residual heat collection circuit, the drum connect to form one with the technique Gas Cooler
Two residual heat collection circuits, the drum are also successively connect with second sect heat-exchanger, first sect heat-exchanger, make to come
The cold end for sequentially entering second sect heat-exchanger and first sect heat-exchanger from the steam of drum is overheated, from
And recycle the heat that acid process solid/liquid/gas reactions generate in combination type reactor.
Preferably, the bottom of the sulfuric acid vapor condenser, which is equipped with one, contains SO for inputting3Process gas process gas into
For exporting the leakage fluid dram and an air outlet of sulfuric acid, the top of the sulfuric acid vapor condenser is equipped with an air by port, one
Air inlet.Air enters the top of the sulfuric acid vapor condenser tube box after cooling blower pressure-raising from the air inlet,
In sulfuric acid vapor condenser and containing SO3Process gas heat exchange after be discharged through the air outlet；Containing SO3Process gas from institute
It states after process gas air inlet enters the sulfuric acid vapor condenser and flows from bottom to top, reduced with temperature after air heat-exchange, gradually
Form drop after condensation, the bottom of the sulfuric acid vapor condenser is dropped in by gravity, is discharged through leakage fluid dram.
Preferably, the air outlet is connected with the burner, after sulfuric acid vapor condenser heat exchange
To hot-air be input in the burner, used as combustion air.
Preferably, the air outlet is also connected with the process gas air-introduced machine, changed through the sulfuric acid vapor condenser
The hot-air obtained after heat is input in the process gas air-introduced machine.
Preferably, the air outlet is also connected with the degassing tower, after sulfuric acid vapor condenser heat exchange
To hot-air be input in the degassing tower, for being de-gassed to filtered cleaning solution.
Preferably, the air outlet is also connected with the enrichment facility, exchanged heat using the sulfuric acid vapor condenser
Desulfurization waste liquor is concentrated in the hot-air obtained afterwards, carries out air lift concentration using the hot-air in device region, does not need volume
Outer consumption steam.
Preferably, the sulfuric acid vapor condenser is also connected with an acid mist eliminator, the acid mist eliminator is for trapping
Remove the sulfuric acid aerosol of entrainment；The offgas outlet of the acid mist eliminator is connected with the exhaust gas processing device, the acid mist
The liquid outlet of trap is connected with the sulfuric acid blending tank.
Preferably, the exhaust gas processing device is tail gas washing tower, tail gas carries cleaning solution secretly in order to prevent, and the tail gas is washed
The top for washing tower is equipped with a demister.
The demister blocks in order to prevent, and the top of the demister is additionally provided with a spray port, and periodically spray is de-
Salt water is rinsed demister.
The tail gas washing tower is additionally provided with a tail gas washing liquid circulation loop, and the tail gas washing liquid circulation loop is equipped with
One tail gas washing liquid circulating pump, for tail gas washing liquid after tail gas washing liquid circulating pump pressurization, a part is back to the tail
In gas wash tower, the circulation of tail gas washing liquid is realized, another part is exported as byproduct.
Preferably, the downstream of the exhaust gas processing device is additionally provided with a demister.
Preferably, the outlet of the sulfuric acid blending tank is additionally provided with a sulfuric acid cooler and a sulfuric acid storage tank, the sulfuric acid is cold
But on the one hand device is connected with the leakage fluid dram of the sulfuric acid vapor condenser, is on the other hand connected with the sulfuric acid storage tank.Through sulfuric acid
Sulfuric acid temperature under steam condenser condenses and separates is higher, to avoid corrosion of the high-temperature sulfuric acid to pipeline and sulfuric acid storage tank, by sulphur
Acid cooler sulfuric acid a part after cooling is back at the outlet nozzle of sulfuric acid vapor condenser, is gone out with sulfuric acid vapor condenser
The hot sulfuric acid mixing chilling cooling of mouth；Another part is input in sulfuric acid storage tank as output of products.
The present invention also provides the wet processing process of a kind of aqueous sulphur cream and desulfurization waste liquor, use and contain as described above
The wet processing system of water sulphur cream and desulfurization waste liquor carries out comprising following steps:
(1) desulfurization waste liquor and the aqueous sulphur cream melted through molten sulphur device enter burner progress combustion reaction, and generation contains
SO2Process gas；
(2) contain SO2Process gas purified device purification after enter Benitration reactor denitration, reacted subsequently into combined type
Device carries out catalytic oxidation, obtains containing SO3Process gas；
(3) contain SO3Process gas condensed in sulfuric acid vapor condenser and form sulfuric acid, the tail gas warp of sulfuric acid vapor condenser
It is discharged after exhaust gas processing device processing.
Present invention process object can be the desulfurization waste liquor and aqueous sulphur cream that generate after coke-oven plant's cleaning and desulfurization, in desulfurization waste liquor
The mass percent concentration of ammonium salt is generally 20~25%, and water content is 80~90wt%；Specifically, containing ammonium thiocyanate 120
~150g/L, 60~100g/L of ATS (Ammonium thiosulphate), 10~25g/L of ammonium sulfate.Sulfur content is 3~6wt% in aqueous sulphur cream, aqueous
Amount is 93~96wt%.
Present invention process be suitable for various concentration desulfurization waste liquor, if the concentration of desulfurization waste liquor to be processed less than 40%,
It can burn again after concentrated device progress concentration.Preferably, in step (1), the matter of ammonium salt in the desulfurization waste liquor
Measuring percent concentration is 40~45%.Desulfurization waste liquor concentration is increased to 40%~45% to handle again, help to obtain compared with
High SO2Conversion ratio can also reduce burner gas consumption, and the whole energy consumption of useless wet processing system can be effectively reduced, subtract
The size of small burner reduces investment.
Preferably, being also passed through fuel gas and air, the flow of fuel gas and air in the burner in step (1)
It can be adjusted according to the oxygen content in ignition temperature and process gas than those skilled in the art.The fuel gas is preferably coke oven
Coal gas.It is passed through air in burner, suitable oxygen amount can be filled into, reduces burner size, save the cost.
Preferably, the temperature of the combustion reaction is 1050~1100 DEG C (such as 1150 DEG C) in step (1).
Preferably, described contain SO2Process gas in SO2Concentration of volume percent be 5%~8%, preferably 5%~
6%.
Preferably, when the burner is also connected with a waste-heat recoverer, it is described to contain SO2Process gas pass through described in
Temperature is down to 550 DEG C~650 DEG C, preferably 550 DEG C~570 DEG C after waste-heat recoverer.
Preferably, catalyst is KSC-13 and/or KSV-13 in the combination type reactor, which is wet process catalysis
Agent, it is aqueous for making relieving haperacidity conversion process.
When the combination type reactor is successively arranged the first bed, the first sect heat-exchanger, the second bed, from top to bottom
When two sect heat-exchangers, third bed and technique Gas Cooler, preferably, the process gas inlet temperature of first bed is
400~410 DEG C, the process gas inlet temperature of second bed is 380~410 DEG C, the process gas import of the third bed
Temperature is 380~390 DEG C.Further, process gas enters the first bed of the combination type reactor with 400~410 DEG C, instead
Should after temperature improve to 560~580 DEG C, after in the first sect heat-exchanger be cooled to 380~410 DEG C of second beds of feedings, reaction
Temperature is improved to 430~450 DEG C afterwards, after in the second sect heat-exchanger be cooled to 380~390 DEG C of feeding third beds, after reaction
Temperature be 395~405 DEG C, after 250~300 DEG C (such as 280 DEG C) are cooled in technique Gas Cooler, through technique Gas Cooler
Process gas temperature after cooling is 15~25 DEG C higher than sulphuric acid dew point temperature, to prevent the sulfuric acid vapor condensation deposition in downstream process
Equipment is caused to corrode.
When the wet processing system of the aqueous sulphur cream and desulfurization waste liquor further includes a drum, the drum and the waste heat
Recover connects to form one first residual heat collection circuit, and the drum connect to form one second waste heat with the technique Gas Cooler
Collecting loop, when the drum is also successively connect with second sect heat-exchanger, first sect heat-exchanger, the drum
Pressure be 4.8MPag~5.6MPag.By setting drum pressure in certain value, make to contact with high-concentration sulfur trioxide gas
Tube wall temperature on dew-point temperature, avoiding device occur dew point corrosion.
Preferably, Xiang Suoshu sulfuric acid vapor condenser is passed through air and contains SO in step (3)3Process gas exchange heat,
After exchanging heat, contain SO3The temperature of process gas be down to 90~110 DEG C, preferably 90~95 DEG C, reduced with process gas temperature, sulphur
Acid vapor forms drop after gradually condensing.Through with contain SO3Process gas heat exchange after, the temperature of air rises to 200~220 DEG C, excellent
It is selected as 200~210 DEG C.
More preferably, in step (3), the hot-air after sulfuric acid vapor condenser heat exchange is input to the burner
In, it is used as combustion air.
More preferably, in step (3), the hot-air after sulfuric acid vapor condenser heat exchange is input to the degassing tower
In, for being de-gassed to filtered cleaning solution.
More preferably, in step (3), the hot-air after sulfuric acid vapor condenser heat exchange is input in enrichment facility,
For desulfurization waste liquor to be concentrated.
Preferably, the exhaust gas processing device is tail gas washing tower, Xiang Suoshu tail gas washing tower sprays into desalted water, can be effective
Avoid the escaping of ammonia.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
The present invention is that the various concentration desulfurization waste liquor that will be generated after coke-oven plant's cleaning and desulfurization and the conversion of aqueous sulphur cream are produced as
The problems such as method of the sulfuric acid of high added value, the energy consumption for overcoming existing dry method relieving haperacidity technology is high, long flow path.Both processing had been solved
Difficult problem, while very big economic benefit is generated, realize economic benefit and the double growths of environmental benefit.
Detailed description of the invention
Fig. 1 is the wet processing system burning of the aqueous sulphur cream and desulfurization waste liquor of embodiment 1 and the schematic diagram of purification section；
Fig. 2 is the aqueous sulphur cream of embodiment 1 and wet processing system reaction, relieving haperacidity and the vent gas treatment workshop section of desulfurization waste liquor
Schematic diagram.
Description of symbols:
1- melts sulphur device,
2- burner, 201- waste-heat recoverer,
3- technique gas wash tower, 301- detergent circulator, 302- filter, 303- cleaning solution cooler, 304- degassing
Tower, 305- process water feed pipeline,
4- electrostatic precipitator,
5- process gas air-introduced machine,
6- process gas heat exchanger,
7- Benitration reactor, 701- air preheater, 702- mixing arrangement,
8- combination type reactor, the first bed of 801-, the first sect heat-exchanger of 802-, the second bed of 803-, 804- second
Sect heat-exchanger, 805- third bed, 806- technique Gas Cooler,
9- drum,
10- sulfuric acid vapor condenser, 1001- cooling blower,
11- sulfuric acid blending tank, 1101- sulfuric acid cooler, 1102- sulfuric acid storage tank,
12- enrichment facility,
13- acid mist eliminator,
14- exhaust gas processing device, 1401- demister, 1402- tail gas washing liquid circulating pump, 1403- demister, 1404- tail
Gas blower, 1405- exhaust tube,
S1- saturated water,
S2- steam water interface,
S3- hot-air,
S4- hybrid technique gas,
S5- degassing tower tail gas.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1
As shown in Fig. 1~2, the wet processing system of a kind of aqueous sulphur cream and desulfurization waste liquor is present embodiments provided, is wrapped
Include: a molten sulphur device 1, a burner 2, a purification device, a Benitration reactor 7, a combination type reactor 8, a sulfuric acid steam
Vapour condenser 10, a sulfuric acid blending tank 11 and an exhaust gas processing device 14.
For melting aqueous sulphur cream, molten sulphur device 1 is connected molten sulphur device 1 with burner 2；The tail gas row of molten sulphur device 1
Mouth is put to be connected with exhaust gas processing device 14.
Burner 2 be used for by desulfurization waste liquor and through melting aqueous sulphur cream burning generate contain SO2Process gas, burning dress
Set 2 and be also connected with a waste-heat recoverer 201, for recycle generated in burner 2 containing SO2Process gas heat.Waste heat
Recover 201 is connect with burner 2 using direct coupled structure, i.e., what is generated in burner 2 contains SO2Process gas be directly entered
The import of waste-heat recoverer 201, using direct heat transfer technology, heat recovery efficiency is high, overcomes the easy fouling of equipment and what is blocked lacks
It falls into.
Specifically, burner 2 is a combustion furnace.
A process gas heat exchanger 6 is additionally provided between waste-heat recoverer 201 and purification device, what is generated in burner 2 contains
SO2Process gas through waste-heat recoverer 201 recycle heat after enter process gas heat exchanger 6, through process gas heat exchanger 6 further drop
Enter purification device after temperature.
Purification device includes sequentially connected technique gas wash tower 3, an electrostatic precipitator 4 and a process gas air-introduced machine 5, work
Skill gas air-introduced machine 5 is connected with process gas heat exchanger 6.What is generated in burner 2 contains SO2Process gas in technique gas wash tower 3
Middle removing dust with to the harmful impurity of catalyst (such as halogen, arsenic etc.), by the purified gas of technique gas wash tower 3
Body enters electrostatic precipitator 4 and removes acid mist, and the gas after removing acid mist enters process gas heat exchanger after the pressurization of process gas air-introduced machine 5
It heats up in 6.Through the pressurized process gas of process gas air-introduced machine 5 in process gas heat exchanger 6 and from waste-heat recoverer 201
Contain SO2Process gas exchange heat, from waste-heat recoverer 201 contain SO2The heat of process gas be recovered, purify simultaneously
Process gas afterwards is heated.
Technique gas wash tower 3 is equipped with a cleaning solution circulation loop, is successively arranged a cleaning solution on the cleaning solution circulation loop
Circulating pump 301, a filter 302 and a cleaning solution cooler 303, cleaning solution circulation loop is used for will be in technique gas wash tower 3
Cleaning solution be pressurized, filtered and cooled down, realize the circulation of cleaning solution.
On the one hand the outlet of filter 302 is connected with cleaning solution cooler 303, be on the other hand connected with a degassing tower 304,
The washed liquid circulating pump 301 of cleaning solution in technique gas wash tower 3 enters filter 302 after being pressurized and filters, washing after filtering
It washs after liquid a part enters the cooling of cleaning solution cooler 303 and returns in technique gas wash tower 3, another part enters degassing tower 304
It is discharged after degassing as spent acid.The gas vent of degassing tower 304 is connected with exhaust gas processing device 14.
The downstream of cleaning solution cooler 303 is also connected with process water supply pipeline 305, which feeds pipeline 305
For supplementing fresh process water into technique gas wash tower 3, it can control 3 outlet temperature of technique gas wash tower, adjust process gas
Water sulphur ratio, control water sulfur balance, be convenient for the relieving haperacidity of downstream wet process, produce high value added product to greatest extent, while improving production
The flexibility of product matched design.In addition, can control the discharge amount of waste water by supplement Fresh process water, waste water can be greatly reduced
Treating capacity.
Benitration reactor 7 is connected with the cold fluid outlet of process gas heat exchanger 6, and Benitration reactor 7 contains for being catalytically decomposed
SO2Process gas in oxynitrides.
A gaseous mixture branch is additionally provided between process gas heat exchanger 6 and Benitration reactor 7, which is equipped with one
Air preheater 701 and a mixing arrangement 702, mixing arrangement 702 are used for ammonia and the air preheated through air preheater 701
Gaseous mixture is mixed to obtain, the gaseous mixture and purified device are purified containing SO2Process gas mixing after obtained hybrid technique gas
S4 enters Benitration reactor 7.
Specifically, Benitration reactor 7 is SCR denitration reaction device.
The outlet of Benitration reactor 7 is connected with the import of combination type reactor 8, and combination type reactor 8 will be for that will contain SO2's
Process gas catalysis oxidation, which generates, contains SO3Process gas.
Combination type reactor 8 is successively arranged the first bed 801, the first sect heat-exchanger 802, the second bed from top to bottom
803, the second sect heat-exchanger 804, third bed 805 and technique Gas Cooler 806.First bed~third bed is filled with and urges
Agent, under the action of catalyst, SO2Catalysis oxidation is converted into SO3。SO2Catalytic oxidation process be an exothermic reaction, therefore
The process gas temperature for leaving the first bed 801 is increased, and second is entered after 802 lowered temperature reclamation heat of the first sect heat-exchanger
The reaction was continued for bed 803, and it is laggard that the process gas from the second bed 803 enters 804 lowered temperature reclamation heat of the second sect heat-exchanger
Enter third bed 805, the process gas from third bed 805 enters technique Gas Cooler 806 and cooled down.Combined type reaction
Device 8 is compact-sized, save the cost, optimizes space layout, convenient for manufacture maintenance, and is conducive to the recycling of thermal energy gradient, section
It is reasonable to learn.
The wet processing system of the aqueous sulphur cream of the present embodiment and desulfurization waste liquor further includes a drum 9, and drum 9 and waste heat recycle
The connection of device 201 forms one first residual heat collection circuit, recycles the heat in burner 2, i.e. the cold end of waste-heat recoverer 201 is adopted
With the saturated water S1 from drum 9, using the saturated water S1 from drum 9 in waste-heat recoverer 201 with contain SO2Process gas
It is vaporized after heat exchange, obtained steam water interface S2 is back to drum 9；Drum 9 connect formation one second with technique Gas Cooler 806
Residual heat collection circuit, the heat in process gas that recycling third bed 805 comes out, the i.e. cold end of technique Gas Cooler 806 use
Saturated water from drum 9, vapour after saturated water exchanges heat in technique Gas Cooler 806 with the process gas from third bed 805
Change, obtained steam water interface is back to drum 9.Drum 9 also successively with the second sect heat-exchanger 804, the first sect heat-exchanger
802 connections, are sent to combined type by the saturated vapor in the first residual heat collection circuit and the second residual heat collection circuit institute by-product and are reacted
In device 8, make the steam from drum 9 sequentially enter to the cold end of the second sect heat-exchanger 804 and the first sect heat-exchanger 802 into
Row overheat, to recycle the heat that acid process solid/liquid/gas reactions generate in combination type reactor 8.
The outlet of combination type reactor 8 is connected with sulfuric acid vapor condenser 10, and sulfuric acid vapor condenser 10 will be for that will contain SO3
Process gas condense to form sulfuric acid, the exhaust port of sulfuric acid vapor condenser 10 is connected with exhaust gas processing device 14, sulfuric acid steam
The leakage fluid dram of vapour condenser 10 is connected with sulfuric acid blending tank 11.
The bottom of sulfuric acid vapor condenser 10 is equipped with a process gas air inlet, a leakage fluid dram and an air outlet, sulfuric acid
The top of steam condenser 10 is equipped with an air inlet.Air enters sulphur from air inlet after 1001 pressure-raising of cooling blower
The top of 10 bobbin carriage of acid vapor condenser, in sulfuric acid vapor condenser 10 and containing SO3Process gas heat exchange after hot-air S3,
Hot-air S3 is discharged through air outlet；Containing SO3Process gas from process gas air inlet enter sulfuric acid vapor condenser 10 after by
Under flow up, reduced with temperature after air heat-exchange, gradually condense after form drop, be dropped in sulfuric acid vapor condenser by gravity
10 bottom, is discharged through leakage fluid dram.
Air outlet is connected with burner 2, the hot-air S3 input obtained after the heat exchange of sulfuric acid vapor condenser 10
Into burner 2, used as combustion air.
The upstream of burner 2 can also be connected with an enrichment facility 12, for desulfurization waste liquor to be concentrated.Specifically,
Enrichment facility 12 is concentration tower.
Air outlet is also connected with enrichment facility 12, the hot-air S3 obtained after being exchanged heat using sulfuric acid vapor condenser 10
Desulfurization waste liquor is concentrated, air lift concentration is carried out using the hot-air in device region, does not need additionally to consume steam.
Air outlet is also connected with degassing tower 304, and the hot-air S3 obtained after the heat exchange of sulfuric acid vapor condenser 10 is defeated
Enter into degassing tower 304, for being de-gassed to filtered cleaning solution, the degassing tower tail gas S5 after degassing enters vent gas treatment
The processing of device 14.
Sulfuric acid vapor condenser 10 is also connected with an acid mist eliminator 13, and acid mist eliminator 13 is used to trap removing entrainment
Sulfuric acid aerosol；The offgas outlet of acid mist eliminator 13 is connected with exhaust gas processing device 14, the liquid outlet of acid mist eliminator 13
It is connected with sulfuric acid blending tank 11.
Specifically, exhaust gas processing device 14 is tail gas washing tower, tail gas carries cleaning solution secretly in order to prevent, tail gas washing tower
Top is equipped with a demister 1401.Demister 1401 blocks in order to prevent, and the top of demister 1401 is additionally provided with a spray
Mouthful, it periodically sprays desalted water and demister 1401 is rinsed.
Tail gas washing tower is additionally provided with a tail gas washing liquid circulation loop, and tail gas washing liquid circulation loop is equipped with a tail gas and washes
Liquid circulating pump 1402 is washed, for tail gas washing liquid after the pressurization of tail gas washing liquid circulating pump 1402, a part is back to tail gas washing tower
In, realize the circulation of tail gas washing liquid, another part is exported as byproduct.
The downstream of exhaust gas processing device 14 is additionally provided with a demister 1403, passes through through treated the tail gas of exhaust gas processing device 14
Demister 1403 reaches discharge standard after removing acid mist, is discharged after the pressurization of exhaust fan 1404 by exhaust tube 1405.
The outlet of sulfuric acid blending tank 11 is additionally provided with a sulfuric acid cooler 1101 and a sulfuric acid storage tank 1102, sulfuric acid cooler
1101 one side are connected with the leakage fluid dram of sulfuric acid vapor condenser 10, are on the other hand connected with sulfuric acid storage tank 1102.It is steamed through sulfuric acid
Sulfuric acid temperature under vapour condenser 10 condenses and separates is higher, to avoid corrosion of the high-temperature sulfuric acid to pipeline and sulfuric acid storage tank, by sulphur
The sulfuric acid a part after cooling of acid cooler 1101 is back at the outlet nozzle of sulfuric acid vapor condenser 10, cold with sulfuric acid vapor
The hot sulfuric acid mixing chilling cooling that condenser 10 exports；Another part is input in sulfuric acid storage tank 1102 as output of products.
Embodiment 2
The wet processing process for present embodiments providing a kind of aqueous sulphur cream and desulfurization waste liquor, uses containing for embodiment 1
The wet processing system of water sulphur cream and desulfurization waste liquor carries out.
The present embodiment object to be processed is the desulfurization waste liquor and aqueous sulphur cream that generate after coke-oven plant's cleaning and desulfurization.Wherein,
Desulfurization waste liquor discharge capacity is 90m3/ day.Desulfurization waste liquor amine salt control≤240g/L, wherein ammonium thiocyanate 140g/L, ATS (Ammonium thiosulphate)
80g/L, ammonium sulfate 20g/L, water content 86wt%.
The discharge capacity of aqueous sulphur cream is 15.6t/h, sulfur content 5wt%, water content 95wt%.
The present invention does not limit the minimum concentration of desulfurization waste liquor to be processed, if but wherein ammonium salt (refers to ammonium thiocyanate, thiosulfuric acid
Ammonium and ammonium sulfate) mass percent concentration less than 40%, need to use enrichment facility desulfurization waste liquor concentration is increased to 40%~
45% is handled again, help to obtain higher SO2Conversion ratio can also reduce burner gas consumption, can be effectively reduced
The whole energy consumption of useless wet processing system, reduces the size of burner, reduces investment.
(1) desulfurization waste liquor/aqueous sulphur cream burns purification
At battery limit (BL), the desulfurization waste liquor through melting the aqueous sulphur cream that sulphur device melts and the concentration of concentrated device enters burner
Combustion reaction occurs for 2 burning zone, wherein the hot-air gas concentration of the concentrated device of desulfurization waste liquor.
By pyroprocess gas heat content after the recycling burning of waste-heat recoverer 201, saturated vapor is pressed in recycling preparation.Burning dress
It sets 2 to be directly connected to the waste-heat recoverer 201 in downstream, the heat technologic gas after burning is by being directly entered waste heat in burner 2
The bobbin carriage of recover 201.
It is also passed through fuel gas and air in burner 2, by adjusting the supply of fuel gas and air, protects ignition temperature
Hold SO in the process gas after making burning at 1150 DEG C or so2Concentration of volume percent control 6%.With coke in the present embodiment
Producer gas is fuel gas.
The hot-air S3 obtained after the heat exchange of sulfuric acid vapor condenser 10 is shunted, a part enters in burner 2,
A part is filled into the upstream of process gas air-introduced machine 5, while reasonable recovery system heat, by filling into suitable oxygen amount, is subtracted
Small burner size reduces investment.
What is generated contains SO2Technique pneumatic transmission to technique gas wash tower 3 and electrostatic precipitator 4 purified, in technique gas washing
Dust and objectionable impurities therein are removed in tower 3, are pressurized after electrostatic precipitator 4 removes acid-mist-removing through process gas air-introduced machine 5, later
It heats up into process gas heat exchanger 6.
303 downstream connection of cleaning solution cooler on 3 cleaning solution circulation loop of technique gas wash tower has technique water supply tube
Road 305, process water supply pipeline 305 can control technique gas washing for supplementing fresh process water into technique gas wash tower 3
3 outlet temperature of tower adjusts the water sulphur ratio of process gas, controls water sulfur balance, is convenient for the relieving haperacidity of downstream wet process, production is high to greatest extent
Value-added product, while improving the flexibility of product matched design.In addition, can control waste water by supplement Fresh process water
The treating capacity of waste water can be greatly reduced in discharge amount.
(2) SCR denitration converts
Ammonia (NH from battery limit (BL)3) after the hot-air that is preheated through air preheater 701 of mixing gaseous mixture, the gaseous mixture with
Purified process gas enters SCR denitration reaction device.Nitrogen oxides is in NH3Under the action of be reduced into harmless N2, this reaction is not
Significant heat release, the process gas after reaction can be directly entered downstream catalytic oxidation.
(3)SO2Catalysis oxidation is SO3
Process gas enters combination type reactor 8 after denitration, the combination type reactor 8 be 33 heat exchange structures, process gas according to
It is secondary that SO is occurred under special wet process sulfuric acid catalyst effect by catalyst bed and sect heat-exchanger2Wet process catalysis oxidation
It is converted into SO3。
The high-temperature technology gas of third bed 805 is cooled to 280 DEG C through technique Gas Cooler 806 out, which is higher than sulfuric acid
It is about 15-25 DEG C of dew-point temperature, rear to be sent into sulfuric acid vapor condenser 10.
The saturated vapor that waste-heat recoverer 201 and technique Gas Cooler 806 produce sequentially enters 804 He of the second sect heat-exchanger
First sect heat-exchanger 802 overheat.
(4)SO3Conversion and H2SO4Steam condensation
Under the high temperature conditions, part SO3Hydration reaction is generated into H2SO4Steam is reduced with temperature, the degree of hydration reaction
It will aggravation.
The heat technologic gas for leaving technique Gas Cooler 806 entersSulfuric acid vapor condenser 10, heat technologic gas exists
Temperature is further decreased in the sulfuric acid vapor condenser 10, sulfuric acid vapor is promoted to condense, 280 DEG C of following temperature of heat technologic gas enter
Sulfuric acid vapor condenser 10, flows from bottom to top, exchanges the temperature for reducing process gas with the heat of heat technologic gas by air
To 90 DEG C, being reduced with process gas temperature, sulfuric acid vapor is gradually condensed on the glass heat exchange pipe of sulfuric acid vapor condenser 10, after
Form drop, the bottom of sulfuric acid vapor condenser 10 is dropped in by gravity.Air by 1001 pressure-raising of cooling blower send toSulfuric acid vapor condenser 10, into the top of bobbin carriage, bobbin carriage divides left and right ends, and each section passes through internal partition point
It is segmented into multistage, it is eventually offThe hot air temperature of sulfuric acid vapor condenser 10 is 200 DEG C, the visual feelings of the hot-air
Condition is sent respectively recycles heat into enrichment facility 12, burner 2 and degassing tower 304.
(5) sulfuric acid cooling is quenched
ThroughSulfuric acid temperature under sulfuric acid vapor condenser 10 condenses and separates is higher, to avoid high-temperature sulfuric acid pair
Sulfuric acid cooler 1101 is arranged in the outlet of sulfuric acid blending tank 11, by sulfuric acid cooler 1101 in the corrosion of pipeline and sulfuric acid storage tank
Sulfuric acid a part after cooling is back toAt the outlet nozzle of sulfuric acid vapor condenser 10, mixed with hot sulfuric acid anxious
It is cold be cooled to 55 DEG C after enter sulfuric acid blending tank 11, another part is input in sulfuric acid storage tank 1102 as output of products.
(6) tail-gas deep is handled
Sulfuric acid vapor condenser 10 is also connected with an acid mist eliminator 13, the tail gas after trapping through acid mist eliminator 13,
Remain micro SO2Gas is sent by the tail gas washing tower of setting with detergent circulator 1402 to absorb oxysulfide
Cleaning solution (ammonium hydroxide) counter current contacting humidification；SO in tail gas2It being removed, clean tail gas is discharged from the top of tail gas washing tower,
Reach discharge standard after demister 1403 removes acid mist, exhaust tube 1405 is entered after the pressurization of exhaust fan 1404, it is final to arrange
Enter atmosphere.
Tail gas carries cleaning solution secretly in order to prevent, and washing tail gas top of tower is provided with demister 1401, and demister 1401 can be
Wire mesh demister and/or vane type demister；1401 ammonium salt blockage of demister in order to prevent, tail gas washing tower top is periodically with de-
Salt water rinses, and also can effectively avoid the escaping of ammonia using desalted water flushing.The washed liquid circulation of the cleaning solution of washing tail gas tower bottom
After 1402 pressurization of pump, it is back to tail gas washing tower and continues to wash tail gas, fraction cleaning solution is sent out battery limit (BL) as byproduct.
Above-mentioned reaction step discharges a large amount of reaction heat, and this programme carries out in such a way that boiler feedwater exchanges heat byproduct steam
Heat recovery, byproduct steam.I.e. by setting drum 9, drum 9 is connect with waste-heat recoverer 201 forms one first residual heat collection
The heat in burner 2 is recycled in circuit, i.e. the cold end of waste-heat recoverer 201 uses the saturated water S1 from drum 9, uses
Saturated water S1 from drum 9 is in waste-heat recoverer 201 and containing SO2Process gas heat exchange after vaporize, obtained steam-water mixing
Object S2 is back to drum 9；Drum 9 is connect with technique Gas Cooler 806 forms one second residual heat collection circuit, recycles third bed
Heat in 805 process gas come out, the i.e. cold end of technique Gas Cooler 806 use the saturated water from drum 9, and saturated water exists
It is vaporized in technique Gas Cooler 806 with after the heat exchange of the process gas of third bed 805, obtained steam water interface is back to vapour
Packet 9.It is sent by the saturated vapor in the first residual heat collection circuit and the second residual heat collection circuit institute by-product to combination type reactor 8
It is interior, by exchanging heat with process gas, the reaction heat of recycling catalysis reaction, while hot steam is pressed through in obtaining.
The pressure of drum 9 be 5.6MPag, make the tube wall temperature contacted with high-concentration sulfur trioxide gas dew-point temperature it
On, dew point corrosion occurs for avoiding device.
The hot air temperature of eventually off sulfuric acid vapor condenser 10 be 200 DEG C, the hot-air can optionally send respectively to
Heat is recycled in enrichment facility 12, burner 2 and degassing tower 304.
In the present embodiment, coke-stove gas consumption is 325Nm3/ h, sulfuric acid (concentration 93wt%) yield are 90 ton/days,
Wastewater discharge is 3 ton/days, and steam production (4.2Mpag, 410 DEG C) is 168 ton/days.
When normal operating, device exhaust emission behaviour is as follows:
SO2Content < 50mg/m3, acid mist < 5mg/m3。
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only
For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from
Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and
Modification each falls within protection scope of the present invention.
Claims (10)
1. a kind of wet processing system of aqueous sulphur cream and desulfurization waste liquor characterized by comprising a molten sulphur device, a burning
Device, a purification device, a Benitration reactor, a combination type reactor, a sulfuric acid vapor condenser, a sulfuric acid blending tank and one
Exhaust gas processing device；
For melting aqueous sulphur cream, the molten sulphur device is connected the molten sulphur device with the burner；
The burner be used for by desulfurization waste liquor and through melting aqueous sulphur cream burning generate contain SO2Process gas, the burning
The gas vent of device is connected with the gas feed of the purification device；
The purification device contains SO for removing2Process gas in solid impurity and acid mist, the gas vent of the purification device
It is connected with the import of the Benitration reactor；
The Benitration reactor contains SO for being catalytically decomposed2Process gas in oxynitrides, the outlet of the Benitration reactor
It is connected with the import of the combination type reactor；
The combination type reactor will be for that will contain SO2Process gas catalysis oxidation generate contain SO3Process gas, the combined type is anti-
The outlet of device is answered to be connected with the sulfuric acid vapor condenser；
The sulfuric acid vapor condenser will be for that will contain SO3Process gas condense to form sulfuric acid, the tail gas of the sulfuric acid vapor condenser
Discharge outlet is connected with the exhaust gas processing device, and the leakage fluid dram of the sulfuric acid vapor condenser is connected with the sulfuric acid blending tank.
2. the wet processing system of aqueous sulphur cream and desulfurization waste liquor as described in claim 1, which is characterized in that the burning dress
The upstream set is also connected with an enrichment facility, for desulfurization waste liquor to be concentrated；
And/or the exhaust port of the molten sulphur device is connected with the exhaust gas processing device；
And/or the burner is a combustion furnace；
And/or the Benitration reactor is SCR denitration reaction device；
And/or a gaseous mixture branch is additionally provided between the purification device and the Benitration reactor, the gaseous mixture branch road
Equipped with an air preheater and a mixing arrangement, the mixing arrangement is used for ammonia and the sky preheated through the air preheater
Gas mixes to obtain gaseous mixture, and the gaseous mixture contains SO with through the purification device is purified2Process gas mixing after enter it is described
Benitration reactor；
And/or the exhaust gas processing device is tail gas washing tower, the top of the tail gas washing tower is equipped with a demister, described
The top of demister is additionally provided with a spray port；The tail gas washing tower is additionally provided with a tail gas washing liquid circulation loop, the tail gas
Cleaning solution circulation loop is equipped with a tail gas washing liquid circulating pump；
And/or the downstream of the exhaust gas processing device is additionally provided with a demister；
And/or the outlet of the sulfuric acid blending tank is additionally provided with a sulfuric acid cooler and a sulfuric acid storage tank, the sulfuric acid cooler one
Aspect is connected with the leakage fluid dram of the sulfuric acid vapor condenser, is on the other hand connected with the sulfuric acid storage tank.
3. the wet processing system of aqueous sulphur cream and desulfurization waste liquor as described in claim 1, which is characterized in that the purification dress
It sets including sequentially connected technique gas wash tower, an electrostatic precipitator and a process gas air-introduced machine.
4. the wet processing system of aqueous sulphur cream and desulfurization waste liquor as claimed in claim 3, which is characterized in that the burning dress
Set and be also connected with a waste-heat recoverer, for recycle generated in burner containing SO2Process gas heat；
The waste-heat recoverer is connect with the burner using direct coupled structure；
It is additionally provided with a process gas heat exchanger between the waste-heat recoverer and the purification device, contains SO for further recycling2's
Heat in process gas；
The process gas air-introduced machine is connected with the process gas heat exchanger；
The technique gas wash tower is equipped with a cleaning solution circulation loop, is successively arranged a cleaning solution on the cleaning solution circulation loop
Circulating pump, a filter and a cleaning solution cooler, the cleaning solution circulation loop is used for will be in the technique gas wash tower
Cleaning solution is pressurized, is filtered and is cooled down, and realizes the circulation of cleaning solution；
The downstream of the cleaning solution cooler is also connected with process water supply pipeline；
The combination type reactor is successively arranged from top to bottom between the first bed, the first sect heat-exchanger, the second bed, second segment
Heat exchanger, third bed and technique Gas Cooler.
5. the wet processing system of aqueous sulphur cream and desulfurization waste liquor as claimed in claim 4, which is characterized in that the filter
Outlet on the one hand be connected with the cleaning solution cooler, be on the other hand connected with a degassing tower；
The gas vent of the degassing tower is connected with the exhaust gas processing device.
6. the wet processing system of aqueous sulphur cream and desulfurization waste liquor as claimed in claim 4, which is characterized in that the aqueous sulphur
The wet processing system of cream and desulfurization waste liquor further includes a drum, and the drum connect to form one first with the waste-heat recoverer
Residual heat collection circuit, the drum connect to form one second residual heat collection circuit with the technique Gas Cooler, and the drum is also
Successively it is connect with second sect heat-exchanger, first sect heat-exchanger.
7. the wet processing system of aqueous sulphur cream and desulfurization waste liquor as claimed in claim 5, which is characterized in that the sulfuric acid steams
The bottom of vapour condenser is equipped with one and contains SO for inputting3Process gas process gas air inlet, one for exporting the drain of sulfuric acid
The top of mouth and an air outlet, the sulfuric acid vapor condenser is equipped with an air inlet；
The air outlet is connected with the burner；
The air outlet is also connected with the process gas air-introduced machine；
The air outlet is also connected with the degassing tower；
The upstream of the burner is also connected with an enrichment facility, for desulfurization waste liquor to be concentrated, the air outlet
Mouth is also connected with the enrichment facility；
The sulfuric acid vapor condenser is also connected with an acid mist eliminator, and the acid mist eliminator is used to trap the sulphur of removing entrainment
Acid gas colloidal sol；
The offgas outlet of the acid mist eliminator is connected with the exhaust gas processing device, the liquid outlet of the acid mist eliminator with
The sulfuric acid blending tank is connected.
8. a kind of wet processing process of aqueous sulphur cream and desulfurization waste liquor, which is characterized in that it is used such as claim 1~7 times
The wet processing system of aqueous sulphur cream and desulfurization waste liquor described in one carries out comprising following steps:
(1) desulfurization waste liquor and the aqueous sulphur cream melted through molten sulphur device enter burner progress combustion reaction, generate and contain SO2's
Process gas；
(2) contain SO2Process gas purified device purification after enter Benitration reactor denitration, subsequently into combination type reactor into
Row catalytic oxidation, obtains containing SO3Process gas；
(3) contain SO3Process gas condensed in sulfuric acid vapor condenser and form sulfuric acid, the tail gas of sulfuric acid vapor condenser is through tail gas
It is discharged after processing unit processing.
9. the wet processing process of aqueous sulphur cream and desulfurization waste liquor as claimed in claim 8, which is characterized in that in step (1),
The mass percent concentration of ammonium salt is 40~45% in the desulfurization waste liquor；
In step (1), it is also passed through fuel gas and air in the burner,
In step (1), the temperature of the combustion reaction is 1050~1100 DEG C；
It is described to contain SO2Process gas in SO2Concentration of volume percent be 5%~8%；
It is described to contain SO when the burner is also connected with a waste-heat recoverer2Process gas after the waste-heat recoverer
Temperature is down to 550 DEG C~650 DEG C；
Catalyst is KSC-13 and/or KSV-13 in the combination type reactor；
When the combination type reactor is successively arranged the first bed, the first sect heat-exchanger, the second bed, second segment from top to bottom
Between heat exchanger, third bed and when technique Gas Cooler, the process gas inlet temperature of first bed is 400~410 DEG C, institute
The process gas inlet temperature for stating the second bed is 380~410 DEG C, and the process gas inlet temperature of the third bed is 380~390
℃；
When the wet processing system of the aqueous sulphur cream and desulfurization waste liquor further includes a drum, the drum and the waste heat are recycled
Device connects to form one first residual heat collection circuit, and the drum connect to form one second residual heat collection with the technique Gas Cooler
Circuit, when the drum is also successively connect with second sect heat-exchanger, first sect heat-exchanger, the pressure of the drum
Power is 4.8MPag~5.6MPag；
In step (3), Xiang Suoshu sulfuric acid vapor condenser is passed through air and contains SO3Process gas exchange heat, after exchanging heat, contain
SO3The temperature of process gas be down to 90~110 DEG C, the temperature of air rises to 200~220 DEG C；
When the exhaust gas processing device is tail gas washing tower, Xiang Suoshu tail gas washing tower sprays into desalted water.
10. the wet processing process of aqueous sulphur cream and desulfurization waste liquor as claimed in claim 9, which is characterized in that the fuel
Gas is coke-stove gas；
It is described to contain SO2Process gas in SO2Concentration of volume percent be 5%~6%；
It is described to contain SO when the burner is also connected with a waste-heat recoverer2Process gas after the waste-heat recoverer
Temperature is down to 550 DEG C~570 DEG C；
When the combination type reactor is successively arranged the first bed, the first sect heat-exchanger, the second bed, second segment from top to bottom
Between heat exchanger, third bed and when technique Gas Cooler, process gas enters the of the combination type reactor with 400~410 DEG C
One bed, temperature is improved to 560~580 DEG C after reaction, after the first sect heat-exchanger be cooled to 380~410 DEG C be sent into second
Bed, temperature is improved to 430~450 DEG C after reaction, after in the second sect heat-exchanger be cooled to 380~390 DEG C of feeding third beds
Layer, after reaction temperature be 395~405 DEG C, after 250~300 DEG C are cooled in technique Gas Cooler；
In step (3), Xiang Suoshu sulfuric acid vapor condenser is passed through air and contains SO3Process gas exchange heat, after exchanging heat, contain
SO3The temperature of process gas be down to 90~95 DEG C, the temperature of air rises to 200~210 DEG C；
In step (3), the hot-air after sulfuric acid vapor condenser heat exchange is input in the burner, as burning
Air uses；
When the upstream of the burner is also connected with an enrichment facility, in step (3), changed through the sulfuric acid vapor condenser
Hot-air after heat is input in enrichment facility, for desulfurization waste liquor to be concentrated.
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