CN110272027A - Waste Sulfuric Acid wet processing system and technique - Google Patents
Waste Sulfuric Acid wet processing system and technique Download PDFInfo
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- CN110272027A CN110272027A CN201910567369.3A CN201910567369A CN110272027A CN 110272027 A CN110272027 A CN 110272027A CN 201910567369 A CN201910567369 A CN 201910567369A CN 110272027 A CN110272027 A CN 110272027A
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- acid
- gas
- fuming
- heat
- sulfuric acid
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 110
- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000012545 processing Methods 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 206
- 230000008569 process Effects 0.000 claims abstract description 63
- 238000005336 cracking Methods 0.000 claims abstract description 54
- 239000000779 smoke Substances 0.000 claims abstract description 50
- 238000000746 purification Methods 0.000 claims abstract description 27
- 238000003860 storage Methods 0.000 claims abstract description 24
- 239000006096 absorbing agent Substances 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 166
- 239000002918 waste heat Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 230000008676 import Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000002737 fuel gas Substances 0.000 claims description 10
- 239000012717 electrostatic precipitator Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 230000003009 desulfurizing effect Effects 0.000 claims description 5
- 229960003512 nicotinic acid Drugs 0.000 claims description 5
- 235000001968 nicotinic acid Nutrition 0.000 claims description 5
- 239000011664 nicotinic acid Substances 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 4
- -1 cooler Substances 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 105
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000002895 organic esters Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 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
- C01B17/76—Preparation by contact processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
-
- 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
-
- 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
Abstract
The invention discloses a kind of Waste Sulfuric Acid wet processing system and techniques.The Waste Sulfuric Acid wet processing system includes: a cracker, a purification device, a combination type reactor, a smoke acid tower, a fuming acid storage tank, a tail gas absorber, a fuming acid circulating slot, a SO3Evaporator, a SO3Condenser and a SO3Storage tank.The present invention uses wet processing, by certain density Waste Sulfuric Acid by cracking, catalysis oxidation production oleum and sulfur trioxide, compared to more traditional spent acid dry method acid manufacturing processes more energy-saving and emission-reduction, low consumption high yield.Present invention process equipment is few, and process is short, and heat exchange is simple, and pressure drop is small, and low energy consumption.
Description
Technical field
The present invention relates to a kind of Waste Sulfuric Acid wet processing system and techniques.
Background technique
Numerous chemical processes are using the concentrated sulfuric acid as catalyst or dehydrating agent.In the process, sulfuric acid becomes spent acid, this
A little spent acid have the nitrification installation and acrylonitrile that explosive and pesticide are produced from the alkyl plant for improving octane number and
Methyl methacrylate device, these spent acid, containing organosilane ester and inorganic pollutant, property is unstable, is unable to direct emission, and
There is be difficult to the problem of being recycled.
Traditional spent acid acid-making process is a kind of dry process, which is usually used double-absorption process flow, packet
Include spent acid cracking, purification, the conversion of sulfur dioxide, the processes such as sulfur trioxide absorption, acquisition concentrated sulfuric acid product.The technique there is
The problems such as equipment is more, long flow path, and heat-exchange network is complicated, and pressure drop is big, and energy consumption is higher, and tail gas is not up to standard.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome, there are energy consumption height, processes for spent acid acid-making process in the prior art
Long defect provides a kind of Waste Sulfuric Acid wet processing system and technique.The present invention uses wet processing, by certain density sulfur waste
Acid is by cracking, catalysis oxidation production oleum and sulfur trioxide, more compared to more traditional spent acid dry method acid manufacturing processes
Energy-saving and emission-reduction, low consumption high yield.Present invention process equipment is few, and process is short, and heat exchange is simple, and pressure drop is small, and low energy consumption.
The present invention is to solve above-mentioned technical problem by following technical proposals:
The present invention provides a kind of Waste Sulfuric Acid wet processing systems comprising: a cracker, a purification device, one group
Box-like reactor, a smoke acid tower, a fuming acid storage tank, a tail gas absorber, a fuming acid circulating slot, a SO3Evaporator, one
SO3Condenser and a SO3Storage tank；
Cracking gas is made for cracking Waste Sulfuric Acid in the cracker, the gas vent of the cracker with
The gas feed of the purification device is connected；
The purification device is used to remove the solid impurity in cracking gas and dehumidifies to cracking gas and is pressurized, the purification device
Gas vent be connected with the import of the combination type reactor；
The combination type reactor is used for the SO in cracking gas2Catalysis oxidation generates SO3, the combination type reactor
Outlet is connected with the smoke acid tower；
The smoke acid tower is used to absorb the SO in the combination type reactor exit gas3High concentration fuming acid is made,
The gas vent of the smoke acid tower is connected with the tail gas absorber, the liquid outlet and the fuming acid of the smoke acid tower
Circulating slot is connected；
The fuming acid circulating slot is used for the high concentration fuming acid from the smoke acid tower and comes from the SO3Evaporation
The low concentration fuming acid of device mixes, and mixing fuming acid is made；Outlet one side and the SO of the fuming acid circulating slot3Evaporation
The liquid-inlet of device is connected, and is on the other hand connected with the fuming acid storage tank；
The SO3Evaporator is used to make the SO in the mixing fuming acid3Part is evaporated, and SO is made3It is sent out with the low concentration
Niacin；The SO3The liquid-inlet of evaporator is connected with the outlet of the fuming acid circulating slot, liquid outlet and the fuming acid
The import of circulating slot is connected, gas vent successively with the SO3Condenser and the SO3Storage tank is connected.
In the following, being described further to Waste Sulfuric Acid wet processing system of the invention:
Sulfuric acid through cracker Pintsch process, is cracked into SO by Waste Sulfuric Acid by the present invention2, send after then purifying to combined type
In reactor.SO2It is converted into gaseous state SO under the effect of the catalyst3, gaseous state SO3It send to smoke acid tower, high concentration smoke is made
Acid, high concentration fuming acid is in fuming acid circulating slot and from SO3The low concentration fuming acid of evaporator mixes to obtain mixing fuming acid,
Fuming acid a part is mixed as output of products, another part enters SO as circulation fuming acid3Evaporator.In SO3Evaporator
In, mixing fuming acid evaporates SO3, SO3It is exported after being condensed, remaining low concentration fuming acid is back to fuming acid circulating slot and height
Concentration fuming acid is mixed.
Preferably, the upstream of the cracker is also connected with an enrichment facility, for Waste Sulfuric Acid to be carried out concentrate.
Preferably, the cracker is a pyrolysis furnace.
Preferably, the cracker is also connected with a waste-heat recoverer, for recycling the high temperature generated in cracker
The heat of cracking gas.The waste-heat recoverer is connect with the cracker using direct coupled structure, i.e., produces in the described cracker
Raw Pintsch process gas is directly entered the import of the waste-heat recoverer, and using direct heat transfer technology, heat recovery efficiency is high, overcomes
The defect of equipment easy fouling and blocking.
More preferably, it is additionally provided with a process gas heat exchanger between the afterheat heat exchanger and the purification device, is used for into one
The heat of step recycling cracking gas.The cracking gas generated in the cracker enters the work after afterheat heat exchanger recycles heat
Skill gas heat exchanger enters the purification device after the process gas heat exchanger further cools down.
Preferably, the purification device include sequentially connected washing chilling tower, electrostatic precipitator, cooler, air blower and
Technique hot-air heater.The cracking gas generated in the cracker removes Cl in washing chilling tower-, the impurity such as dust and oil,
Water during this in cracking gas is saturated, water phase be for fuming acid processed it is excessive, go out from washing chilling tower bottom dilute
Acid enters diluted acid refinement treatment.Enter electrostatic precipitator removing acid mist by washing chilling tower purified gas, subsequently into
Cooler carries out cooling and dehumidifying, and water is further condensed out after subcooler, keeps combination type reactor water sulfur balance, leads to
Control water sulfur balance is crossed, whole process does not need additionally to supplement fresh water.It is miscellaneous that the condensate liquid generated in cooler is free from solid
Matter, a part can be used as downstream acid making system moisturizing.Gas after purified dehumidifying adds after blower through process gas
Enter the combination type reactor after hot device heating.
More preferably, the technique hot-air heater uses the process gas heat exchanger, the i.e. work after the blower
Skill gas exchanges heat in the process gas heat exchanger with the cracking gas from the afterheat heat exchanger, and the heat of cracking gas is returned
It receives, while process gas is heated.
Preferably, the import of the cooler is also connected with an air blower, the air blower is used for after cleaning
Air is filled into cracking gas, to adjust sulphur oxygen ratio.Purified cracking gas and the air filled into mix in the cooler
It is even, while carrying out cooling and dehumidifying.
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 and third bed.First bed~third bed is filled with catalyst, under the action of catalyst, SO2
Catalysis oxidation is converted into SO3。SO2Catalytic oxidation process be an exothermic reaction, therefore leave the process gas of first bed
Temperature is increased, and second bed is entered after the first sect heat-exchanger lowered temperature reclamation heat, and the reaction was continued, is come from
The process gas of second bed enters the third bed after entering the second sect heat-exchanger lowered temperature reclamation heat.The group
Box-like structure of reactor is compact, save the cost, optimizes space layout, convenient for manufacture maintenance, and is conducive to the recycling of thermal energy gradient
It utilizes, it is scientific and reasonable.
Preferably, the combination type reactor is also connected with a technique Gas Cooler, for recycling in combination type reactor
The heat of process gas, the outlet of the technique Gas Cooler are connected with the smoke acid tower.
Preferably, the Waste Sulfuric Acid wet processing system further includes a drum, the drum and the waste-heat recoverer connect
It connects to form one first residual heat collection circuit, the drum connect to form one second residual heat collection time with the technique Gas Cooler
Road, the drum are also successively connect with second sect heat-exchanger, first sect heat-exchanger, make the saturation from drum
Steam sequentially enters second sect heat-exchanger and the cold end of first sect heat-exchanger is overheated, thus recycling group
The heat that acid process solid/liquid/gas reactions generate in box-like reactor.
Preferably, the tail gas absorber is desulfurizing tower, tail gas can direct emission after carrying out deep purifying processing.
Preferably, the Waste Sulfuric Acid wet processing system further includes a SO3Evaporate preheater, the SO3Evaporate preheater
Cold fluid inlet is connected with the fuming acid circulating slot, cold fluid outlet and the SO3Evaporator is connected, hot fluid inlet and institute
State SO3Evaporator is connected, and hot fluid outlet ports are connected with the fuming acid circulating slot, the mixing oleum from fuming acid circulating slot
Acid with come from SO3Enter SO after the low concentration fuming acid heat exchange of evaporator3Evaporator.
Preferably, the smoke acid tower is additionally provided with a cooling water cooler, for cooling down the phegma in the smoke acid tower,
So that oleum is maintained alap temperature, reduces the vapour pressure of circulation oleum, effectively improve the suction of sulfur trioxide
Yield.
Preferably, the Waste Sulfuric Acid wet processing system further includes a head tank, the head tank is connected to the smoke
Sour circulating slot and the SO3Between evaporator.When the Waste Sulfuric Acid wet processing system includes SO3When evaporating preheater, the height
Position slot is connected to the fuming acid circulating slot and the SO3Between the cold fluid inlet for evaporating preheater.
Preferably, the Waste Sulfuric Acid wet processing system further includes a smoke acid cooler, the smoke acid cooler with
The outlet of the fuming acid circulating slot is connected.
The present invention also provides a kind of Waste Sulfuric Acid wet processing process, use Waste Sulfuric Acid wet-treating as described above system
System carries out comprising following steps:
(1) Waste Sulfuric Acid carries out cracking reaction by entering cracker after medium atomization, obtains cracking gas；
(2) enter combination type reactor after the purified device purification of the cracking gas and carry out catalytic oxidation, obtain containing SO3
Process gas；
(3) contain SO3Process gas enter smoke acid tower and obtain high concentration fuming acid, tail gas handles heel row through tail gas absorber
Out；
(4) the high concentration fuming acid is in fuming acid circulating slot and from SO3The low concentration fuming acid of evaporator mixes,
Fuming acid must be mixed, for described mixing fuming acid a part as output of products to fuming acid storage tank, another part enters SO3Evaporation
Device；In the SO3In evaporator, part SO in the mixing fuming acid3Low concentration fuming acid is obtained after being evaporated, and is evaporated
SO3Through SO3Enter SO after condenser condensation3Storage tank；The low concentration fuming acid enter the fuming acid circulating slot with it is described highly concentrated
Spend fuming acid mixing.
Preferably, in step (1), H in the Waste Sulfuric Acid2SO4Mass percent concentration >=80%, preferably 80%~
98%.Sulfur waste acid concentration is improved to 80% or more and is handled again, the entirety of Waste Sulfuric Acid wet processing system can be effectively reduced
Energy consumption reduces the size of cracker, reduces investment.Present invention process is suitable for the Waste Sulfuric Acid of various concentration, if to be processed
H in Waste Sulfuric Acid2SO4Mass percent concentration less than 80%, can be cracked again after concentrated processing.
Preferably, in step (1), the H for being 80%~98% containing mass percentage content in the Waste Sulfuric Acid2SO4, matter
Measure the sulfuric ester that degree is 1%~5% and the water that mass percentage content is 1%~15%.
Preferably, being also passed through fuel gas and air, the flow of fuel gas and air in the cracker in step (1)
Than that can be adjusted according to the oxygen content in the ignition temperature and cracking gas in cracker.The fuel gas is preferably H2S or
Sulphur.Using H2S or sulphur may advantageously facilitate H as fuel gas2SO4Reduction decomposition and supplement sulphur loss, lead in cracker
Enter air, suitable oxygen amount can be filled into, reduces cracker size, save the cost.It may include organic ester in the Waste Sulfuric Acid,
Heat needed for sulfur waste acid cleavage is mainly provided by fuel gas, and the organic ester in Waste Sulfuric Acid also provides partial heat.
Preferably, in step (1), the temperature of the cracking reaction is 1050~1200 DEG C, preferably 1050~1100 DEG C,
When one timing for the treatment of capacity of Waste Sulfuric Acid, the temperature of cracker can be made to maintain by the supply of adjusting fuel gas and air
Target temperature.
Preferably, SO in the cracking gas2Concentration of volume percent be 6%~10%, preferably 8%~10% (example
As 9.6%).
Preferably, the cracking gas is returned by the waste heat when the cracker is also connected with a waste-heat recoverer
Temperature is down to 450~650 DEG C after receiving device, is preferably down to 550~650 DEG C.
Preferably, cracking gas volume percent content of water after purification device purification is 2%~3%.Tool
Body, the cracking gas through it is described washing chilling tower after water volume percent content be 8%~15% (for example, 12%~
15%), the volume percent content of water is 4%~7% (such as 6%), the water after the cooler after the electrostatic precipitator
Volume percent content be 2%~3% (such as 6%).
Preferably, 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, from top to bottom
When two sect heat-exchangers and third bed, preferably, the process gas inlet temperature of first bed is 400~410 DEG C, it is described
The process gas inlet temperature of second bed is 380~410 DEG C, and the process gas inlet temperature of the third bed is 380~390
℃.Further, process gas with 400~410 DEG C enter the combination type reactor the first bed, after reaction 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 feeding, temperature is improved to 430 after reaction
~450 DEG C, after in the second sect heat-exchanger be cooled to 380~390 DEG C of feeding third beds, temperature is 395~405 after reaction
℃。
When the combination type reactor is also connected with a technique Gas Cooler, contain SO3Process gas through the process gas
Cooler is cooled to 240~250 DEG C, and the temperature is 15~25 DEG C higher than sulphuric acid dew point temperature, to prevent the sulfuric acid in downstream process
Steam condensation deposition causes equipment to corrode.
When the Waste Sulfuric Acid wet processing system further includes a drum, the drum connect to be formed with the waste-heat recoverer
One first residual heat collection circuit, the drum connect to form one second residual heat collection circuit with the technique Gas Cooler, described
When drum is also successively connect with second sect heat-exchanger, first sect heat-exchanger, the pressure of the drum is
4.8MPag~5.6MPag.By setting drum pressure in certain value, make the tube wall temperature contacted with high-concentration sulfur trioxide gas
On dew-point temperature, dew point corrosion occurs degree for avoiding device.
In the present invention, the high concentration fuming acid and the low concentration fuming acid are opposite concept, wherein described highly concentrated
Spend the SO that dissociates in fuming acid3The mass percent concentration mixing fuming acid it is high, dissociate SO in the low concentration fuming acid3
The mass percent concentration mixing fuming acid it is low.
Preferably, the SO that dissociates in the high concentration fuming acid3Mass percent concentration be 26%~30%.
Preferably, the SO that dissociates in the low concentration fuming acid3Mass percent concentration be 16~20%.
Preferably, the SO that dissociates in the mixing fuming acid3Mass percent concentration be 22~25%.
The positive effect of the present invention is that: the present invention is that the conversion of various concentration Waste Sulfuric Acid is produced as high added value
The problems such as oleum and sulfur trioxide, the energy consumption for overcoming existing dry method relieving haperacidity technology is high, long flow path.Both it is difficult to solve processing
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 Waste Sulfuric Acid wet processing system schematic diagram of inventive embodiments 1.
Description of symbols:
10- cracker
101- waste-heat recoverer
11- technique hot-air heater
12- washs chilling tower
13- electrostatic precipitator
14- cooler
15- air blower
16- combination type reactor
The first bed of 161-
The first sect heat-exchanger of 162-
The second bed of 163-
The second sect heat-exchanger of 164-
165- third bed
17- technique Gas Cooler
18- smoke acid tower
19- fuming acid storage tank
20- tail gas absorber
21- air blower
22- drum
23- fuming acid circulating slot
24- head tank
25-SO3Evaporator
26-SO3Condenser
27-SO3Storage tank
28-SO3Evaporate preheater
29- smoke acid cooler
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.
Embodiment 1
As shown in Figure 1, present embodiments providing a kind of Waste Sulfuric Acid wet processing system comprising: a cracker 10, one
Purification device, a combination type reactor 16, a smoke acid tower 18, a fuming acid storage tank 19, a tail gas absorber 20, a fuming acid
Circulating slot 23, a head tank 24, a SO3Evaporator 25, a SO3Condenser 26 and a SO3Storage tank 27.
For cracker 10 for cracking Waste Sulfuric Acid, cracker 10 is connected with a waste-heat recoverer 101, and waste heat returns
The gas vent for receiving device 101 is connected with the gas feed of purification device；Waste-heat recoverer 101 and cracker 10 use direct-connected knot
Structure connection, for recycling the heat of the Pintsch process gas generated in cracker 10.
Purification device is used to remove the solid impurity in cracking gas and dehumidifies to cracking gas and is pressurized, wherein purification device packet
Include sequentially connected washing chilling tower 12, electrostatic precipitator 13, cooler 14, air blower 15 and technique hot-air heater 11；Process gas
The gas vent of heater 11 is connected with the import of combination type reactor 16；Technique hot-air heater 11 is also used to further decrease remaining
The temperature of 101 exit gas of heat regenerator, the pressurized process gas of air blower 15 is in technique hot-air heater 11 and from waste heat
The cracking gas of heat exchanger 101 exchanges heat, and the heat of cracking gas is recovered, while process gas is heated.
Combination type reactor 16 is used for SO2Process gas catalysis oxidation generates SO3Process gas, combination type reactor 16 connect
There is a technique Gas Cooler 17, for recycling the heat of process gas in combination type reactor 16, the outlet of technique Gas Cooler 16
It is connected with smoke acid tower 18.
The import of cooler 14 is also connected with an air blower 21, and air blower 21 enters air flow, a part
In cracker 10, a part is filled into the upstream of cooler 14.
Smoke acid tower 18 is used to absorb the SO in 16 exit gas of combination type reactor3Fuming acid, smoke acid tower 18 is made
Gas vent be connected with tail gas absorber 20, the liquid outlet of smoke acid tower 18 is connected with fuming acid circulating slot 23.
The import of fuming acid circulating slot 23 is connected with the liquid outlet of smoke acid tower 18, the outlet object of fuming acid circulating slot 23
Flow point is two strands, one is connected with the import of head tank 24, and another stock is connected with fuming acid storage tank 19；The outlet of head tank 24 with
SO3The import of evaporator 25 is connected, SO3The gas vent of evaporator 25 successively with SO3Condenser 26, SO3Storage tank 27 is connected；SO3
The liquid outlet of evaporator 25 is connected with the import of fuming acid storage circulating slot 23.
In this implementation, cracker 10 is pyrolysis furnace.
Tail gas absorber 20 is desulfurizing tower, enters from the tail gas that 18 tower top of smoke acid tower comes from each layer bottom of desulfurizing tower, takes off
SO is adsorbed in sulphur agent2After saturation, desulfuration efficiency decline is switched to regeneration.
Combination type reactor 16 is successively arranged the first bed 161, the first sect heat-exchanger 162, the second bed from top to bottom
163, the second sect heat-exchanger 164 and third bed 165.
Waste Sulfuric Acid wet processing system further includes a drum 22, and drum 22 connect formation one first with waste-heat recoverer 101
Residual heat collection circuit, drum 22 connect with technique Gas Cooler 17 formed one second residual heat collection circuit, drum 22 also successively with
Second sect heat-exchanger 164, the connection of the first sect heat-exchanger 162, sequentially enter the saturated vapor from drum 22 to second
The cold end of sect heat-exchanger 164 and the first sect heat-exchanger 162 is overheated, to recycle acid work in combination type reactor 16
The heat that skill solid/liquid/gas reactions generate.
The present embodiment Waste Sulfuric Acid wet processing system further includes a SO3Evaporate preheater 28, SO3Evaporate the cold of preheater 28
Side-entrance is connected with head tank 24, cold side outlet port and SO3Evaporator 25 is connected, hot side import and SO3Evaporator 25 is connected, hot side
Outlet is connected with fuming acid circulating slot 23, and the oleum from head tank 24 enters SO3Evaporate preheater 28, with come from SO3It steams
Enter SO after sending out the low concentration fuming acid heat exchange of device 253Evaporator 25.
SO in the present embodiment, in 16 exit gas of combination type reactor3It is absorbed in smoke acid tower 18 and is made highly concentrated
Spend fuming acid, the high concentration fuming acid with come from SO3The low concentration fuming acid of evaporator 25 mixes in fuming acid circulating slot 23
Dilution, obtains the fuming acid of moderate concentration, and fuming acid a part of the moderate concentration is as output of products to fuming acid storage tank 19, and one
Part enters SO through head tank 243Evaporator 25.In SO3In evaporator 25, a part of SO3It is condensed after being evaporated, into SO3Storage
Slot 27, remaining fuming acid are back to fuming acid circulating slot 23 and send out as low concentration fuming acid and the high concentration from smoke acid tower 18
Niacin is mixed.
Smoke acid tower 18 is additionally provided with a cooling water cooler, using cooling medium (such as water) to 18 phegma of smoke acid tower into
Row cooling makes circulation oleum maintain alap temperature, reduces the vapour pressure of circulation oleum, effectively improve three
The absorptivity of sulfur oxide.
The present embodiment Waste Sulfuric Acid wet processing system further includes a smoke acid cooler 29, smoke acid cooler 29 and smoke
The outlet of sour circulating slot 23 is connected.
Embodiment 2
A kind of Waste Sulfuric Acid wet processing process is present embodiments provided, the Waste Sulfuric Acid wet-treating system of embodiment 1 is used
System carries out.The present embodiment Waste Sulfuric Acid to be processed is alkylation spent acid, the H for being 80% containing mass percent concentration2SO4, matter
Measure the sulfuric ester that percent concentration is 5% and the water that mass percent concentration is 15%.
The present invention does not limit the minimum concentration of Waste Sulfuric Acid to be processed, if but wherein H2SO4Mass percent concentration it is insufficient
80%, enrichment facility need to be used H2SO4Mass percent concentration improve to 80% or more and handled again (such as by more
Effect evaporation is concentrated), the whole energy that Waste Sulfuric Acid wet processing system can be effectively reduced in processing is carried out after Waste Sulfuric Acid is concentrated again
Consumption reduces the size of cracker, reduces investment.
(1) alkylation spent acid cracking
Spent acid is alkylated to enter by medium atomization (the present embodiment is using atomizing air to alkylation spent acid distribution atomization)
Cracker 10, cracker 10 and the waste-heat recoverer 101 in downstream are directly connected to, i.e., the thermal technology after burning in cracker 10
Skill gas passes through the bobbin carriage that waste-heat recoverer 101 is directly entered in cracker 10.Waste-heat recoverer 101 and technique Gas Cooler 17
The saturated vapor of production sequentially enters the second sect heat-exchanger 164 and the first sect heat-exchanger 162 overheat.
It is also passed through fuel gas and air in cracker 10, by adjusting the supply of fuel gas and air, makes cracking temperature
1050 DEG C or so are maintained at, SO in cracking gas is made2Concentration of volume percent control 9.6%.With H in the present embodiment2S is combustion
Expect gas, produces sulfur trioxide and oleum to greatest extent.
By air flow, a part enters in cracker 10 air blower 21, and a part is in the upstream of cooler 14
It fills into.
(2) gas purification
Alkylation spent acid is evaporated at high temperature and resolves into SO2、H2O and O2.Dust and oil after being alkylated spent acid cracking
Equal impurity remove dust therein into washing chilling tower 12.The percent by volume of water contains in gas after water washing cleaning
Amount is 15%, the further cooling and dehumidifying in cooler 14 after electrostatic precipitator 13 removes acid mist, through 14 cooling and dehumidifying of cooler
The volume percent content of water is 2% in gas afterwards, is pressurized afterwards by air blower 15.Through 14 water of subcooler by further cold
It coagulates, this partial condensation liquid is free from solid impurity, and a part can be used as downstream acid making system moisturizing and send out battery limit (BL).Pass through
Cooler 14 is set, can be effectively controlled water sulfur balance, whole process does not need additionally to supplement fresh water, and production is high to greatest extent
Value-added product, while improving the flexibility of product matched design.
(3) catalysis oxidation
The volume percent content of water is 2% in process gas after purified dehumidifying, through pressurized process gas in technique
Enter combination type reactor 16 after being heated to 400 DEG C in hot-air heater 11, process gas passes sequentially through the of combination type reactor 16
One bed 161, the first sect heat-exchanger 162, the second bed 163, the second sect heat-exchanger 164 and third bed 165, special
Wet process sulfuric acid catalyst KSC-13/KSV-13 effect under, occur SO2Wet process catalysis oxidation is converted into SO3.Part hot-air exists
It is filled into heat technologic gas before cooler 14, to adjust sulphur oxygen ratio and adjust bed intake air temperature.
The high-temperature technology gas of third bed 165 is cooled to 240 DEG C through technique Gas Cooler 17 out, which reveals higher than sulfuric acid
About 15~25 DEG C of temperature of point, rear fuming acid of being sent into absorb the progress of absorption tower 18 absorption process.
Process gas after purified dehumidifying passes through multi-stage oxidizing in combination type reactor 16, makes SO2Process gas is catalyzed oxygen
Metaplasia is at SO3, SO2Overall conversion can reach 99.3% or so.
(4) fuming acid absorbs
The conversion gas come out from 16 third bed 165 of combination type reactor is laggard by the recycling heat of technique Gas Cooler 17
Entering the fuming acid obtained to smoke acid tower 18 is high concentration fuming acid, and dissociate SO in the high concentration fuming acid3Mass percent
Concentration is 26% (being denoted as 26% fuming acid).
Smoke acid tower 18 is Quan Liuta, makes the conversion air-flow of whole high sulfur trioxide concentration through this tower.By fuming acid
Process gas after tower 18 absorbs enters tail gas absorber 20, at the deep purifying that tail gas is carried out using activated carbon adsorption method of reproduction
Reason enters, desulfurization from the tail gas that 18 tower top of smoke acid tower comes from each layer bottom of tail gas absorber 20 (being specifically configured to desulfurizing tower)
SO is adsorbed in agent2After saturation, desulfuration efficiency decline is switched to regeneration.Through 20 deep purifying of tail gas absorber treated tail gas row
Chimney is put, obtained diluted acid goes out battery limit (BL).
(5)SO3Evaporation and condensation
From 22% fuming acid (the i.e. free SO of head tank 243Mass percent concentration be 22% fuming acid) enter
SO3Preheater 28 is evaporated, in SO3It evaporates in preheater 28 and by SO316% fuming acid of low concentration of evaporator 25 is (i.e. free
SO3Mass percent concentration be 16% fuming acid) heat exchange after, 22% fuming acid after heating enters SO3Evaporator 25, SO3
Evaporator 25 is heated with low-pressure saturated steam, evaporates almost 100% gaseous sulfur trioxide.Gaseous sulfur trioxide enters
SO3Condenser 26 is cooled with circulating water obtained liquid SO3, liquid SO3SO is flowed by gravity3Storage tank 27.
SO3Remaining 16% fuming acid is back in fuming acid circulating slot 23 in evaporator 25, with come from smoke acid tower 18
26% fuming acid mixed diluting of high concentration, obtain 22% fuming acid (i.e. free SO3Mass percent concentration be 22% smoke
Acid).22% obtained fuming acid after smoke acid cooler 29 is cooling, come in sorption enhanced gas as circulation fuming acid by a part
Sulfur trioxide, a part enter fuming acid storage tank 19 as 22% fuming acid of product.
Above-mentioned reaction step discharges a large amount of reaction heat, and this programme device is exchanged heat using boiler feedwater by the way of byproduct steam
Carry out heat recovery, byproduct steam.I.e. by setting drum 22, drum 22 connect formation one more than first with waste-heat recoverer 101
Hot collecting loop recycles the heat in cracker 10, i.e. the cold end of waste-heat recoverer 101 is given using the boiler from drum 22
Water, boiler feedwater are back to drum 22 with vaporization after cracking gas heat exchange in waste-heat recoverer 101 and generate saturated vapor；Drum 22
It is connect with technique Gas Cooler 17 and forms one second residual heat collection circuit, the heat in process gas that recycling third bed 165 comes out
Amount, the i.e. cold end of technique Gas Cooler 17 use the boiler feedwater from drum 22, and boiler feedwater is in technique Gas Cooler 17
The generation saturated vapor of drum 22 is back to vaporizing after the heat exchange of the process gas of third bed 165.Pass through the first residual heat collection
The saturated vapor of circuit and the second residual heat collection circuit institute by-product is sent to combination type reactor 16, by exchanging heat with process gas,
The reaction heat of recycling catalysis reaction, while thermal high steam is obtained.
The pressure of drum 22 makes the tube wall temperature contacted with high-concentration sulfur trioxide gas in dew-point temperature in 5.2MPag
On, dew point corrosion occurs for avoiding device.
In the present embodiment, with flow 5t/h, H2SO4Mass percent concentration: 80% is Waste Sulfuric Acid to be processed, can produce hair
Niacin (22wt%) 1279kg/h, liquid SO32146kg/h。
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 Waste Sulfuric Acid wet processing system characterized by comprising a cracker, a purification device, a combined type are anti-
Answer device, a smoke acid tower, a fuming acid storage tank, a tail gas absorber, a fuming acid circulating slot, a SO3Evaporator, a SO3Condensation
Device and a SO3Storage tank；
Cracking gas is made for cracking Waste Sulfuric Acid in the cracker, the gas vent of the cracker with it is described
The gas feed of purification device is connected；
The purification device is used to remove the solid impurity in cracking gas and dehumidifies to cracking gas and is pressurized, the gas of the purification device
Body outlet is connected with the import of the combination type reactor；
The combination type reactor is used for the SO in cracking gas2Catalysis oxidation generates SO3, the outlet of the combination type reactor
It is connected with the smoke acid tower；
The smoke acid tower is used to absorb the SO in the combination type reactor exit gas3High concentration fuming acid, the hair is made
The gas vent of niacin tower is connected with the tail gas absorber, the liquid outlet of the smoke acid tower and the fuming acid circulating slot
It is connected；
The fuming acid circulating slot is used for the high concentration fuming acid from the smoke acid tower and comes from the SO3Evaporator
Mixing fuming acid is made in the mixing of low concentration fuming acid；Outlet one side and the SO of the fuming acid circulating slot3Evaporator
Liquid-inlet is connected, and is on the other hand connected with the fuming acid storage tank；
The SO3Evaporator is used to make the SO in the mixing fuming acid3Part is evaporated, and SO is made3With the low concentration smoke
Acid；The SO3The liquid-inlet of evaporator is connected with the outlet of the fuming acid circulating slot, and liquid outlet is followed with the fuming acid
The import of annular groove is connected, gas vent successively with the SO3Condenser and the SO3Storage tank is connected.
2. Waste Sulfuric Acid wet processing system as described in claim 1, which is characterized in that the upstream of the cracker is also connected with
There is an enrichment facility, for Waste Sulfuric Acid to be carried out concentrate；
And/or the cracker is a pyrolysis furnace；
And/or the tail gas absorber is desulfurizing tower；
And/or the Waste Sulfuric Acid wet processing system further includes a SO3Evaporate preheater, the SO3Evaporate the cold flow of preheater
Body import is connected with the fuming acid circulating slot, cold fluid outlet and the SO3Evaporator is connected, hot fluid inlet and the SO3
Evaporator be connected, hot fluid outlet ports are connected with the fuming acid circulating slot, the mixing oleum from fuming acid circulating slot and
From SO3Enter SO after the low concentration fuming acid heat exchange of evaporator3Evaporator；
And/or the smoke acid tower is additionally provided with a cooling water cooler, for cooling down the phegma in the smoke acid tower；
And/or the Waste Sulfuric Acid wet processing system further includes a head tank, the head tank is connected to the fuming acid circulation
Slot and the SO3Between evaporator；
And/or the Waste Sulfuric Acid wet processing system further includes a smoke acid cooler, the smoke acid cooler and the hair
The outlet of niacin circulating slot is connected.
3. Waste Sulfuric Acid wet processing system as described in claim 1, which is characterized in that the purification device includes being sequentially connected
Washing chilling tower, electrostatic precipitator, cooler, air blower and technique hot-air heater.
4. Waste Sulfuric Acid wet processing system as claimed in claim 3, which is characterized in that the cracker is also connected with more than one
Heat regenerator, for recycling the heat of the Pintsch process gas generated in cracker；
The waste-heat recoverer is connect with the cracker using direct coupled structure；
A process gas heat exchanger is additionally provided between the afterheat heat exchanger and the purification device, for further recycling cracking gas
Heat；
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 and third bed；
The combination type reactor is also connected with a technique Gas Cooler, for recycling the heat of process gas in combination type reactor
Amount, the outlet of the technique Gas Cooler is connected with the smoke acid tower.
5. Waste Sulfuric Acid wet processing system as claimed in claim 4, which is characterized in that described in the technique hot-air heater uses
Process gas heat exchanger；
The import of the cooler is also connected with an air blower, and the air blower in cracking gas after cleaning for filling into
Air, to adjust sulphur oxygen ratio.
6. Waste Sulfuric Acid wet processing system as claimed in claim 4, which is characterized in that the Waste Sulfuric Acid wet processing system is also
Including a drum, the drum connect to form one first residual heat collection circuit with the waste-heat recoverer, the drum with it is described
Technique Gas Cooler connects to form one second residual heat collection circuit, the drum also successively with second sect heat-exchanger, institute
State the connection of the first sect heat-exchanger.
7. a kind of Waste Sulfuric Acid wet processing process, which is characterized in that it uses sulfur waste as described in any one of claims 1 to 6
Sour wet processing system carries out comprising following steps:
(1) Waste Sulfuric Acid carries out cracking reaction by entering cracker after medium atomization, obtains cracking gas；
(2) enter combination type reactor after the purified device purification of the cracking gas and carry out catalytic oxidation, obtain containing SO3Work
Skill gas；
(3) contain SO3Process gas enter smoke acid tower and obtain high concentration fuming acid, tail gas is discharged after tail gas absorber is handled；
(4) the high concentration fuming acid is in fuming acid circulating slot and from SO3The low concentration fuming acid of evaporator mixes, and obtains mixed
Fuming acid is closed, for described mixing fuming acid a part as output of products to fuming acid storage tank, another part enters SO3Evaporator；
In the SO3In evaporator, part SO in the mixing fuming acid3Low concentration fuming acid, the SO evaporated are obtained after being evaporated3
Through SO3Enter SO after condenser condensation3Storage tank；The low concentration fuming acid enters the fuming acid circulating slot and the high concentration
Fuming acid mixing.
8. Waste Sulfuric Acid wet processing process as claimed in claim 7, which is characterized in that in step (1), in the Waste Sulfuric Acid
H2SO4Mass percent concentration >=80%；
In step (1), fuel gas and air are also passed through in the cracker；
In step (1), the temperature of the cracking reaction is 1050~1200 DEG C；
SO in the cracking gas2Concentration of volume percent be 6%~10%；
When the cracker is also connected with a waste-heat recoverer, cracking gas temperature after the waste-heat recoverer drops
To 450~650 DEG C；
Cracking gas volume percent content of water after purification device purification is 2%~3%；
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 and when third bed, the process gas inlet temperature of first bed is 400~410 DEG C, second bed
Process gas inlet temperature is 380~410 DEG C, and the process gas inlet temperature of the third bed is 380~390 DEG C；
When the combination type reactor is also connected with a technique Gas Cooler, contain SO3Process gas through the technique Gas Cooler
It is cooled to 240~250 DEG C.
9. Waste Sulfuric Acid wet processing process as claimed in claim 8, which is characterized in that in step (1), contain in the Waste Sulfuric Acid
Having mass percentage content is 80%~98% H2SO4, mass percentage content be 1%~5% sulfuric ester and quality percentage
Than the water that content is 1%~15%；
The fuel gas is H2S or sulphur；
In step (1), the temperature of the cracking reaction is 1050~1100 DEG C；
SO in the cracking gas2Concentration of volume percent be 8%~10%；
When the cracker is also connected with a waste-heat recoverer, cracking gas temperature after the waste-heat recoverer drops
To 550~650 DEG C；
When the purification device includes sequentially connected washing chilling tower, electrostatic precipitator, cooler, air blower and process gas heating
When device, cracking gas volume percent content of water after the washing chilling tower is 8%~15%, through the electrostatic precipitator
The volume percent content of water is 4%~7% afterwards, and the volume percent content of water is 2%~3% after the cooler；
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 and when third bed, process gas enters the first bed of the combination type reactor with 400~410 DEG C, after reaction
Temperature is improved to 560~580 DEG C, after in the first sect heat-exchanger be cooled to 380~410 DEG C of second beds of feeding, it is warm after reaction
Degree is improved to 430~450 DEG C, after in the second sect heat-exchanger be cooled to 380~390 DEG C of feeding third beds, temperature after reaction
It is 395~405 DEG C.
10. Waste Sulfuric Acid wet processing process as claimed in claim 7, which is characterized in that when Waste Sulfuric Acid wet-treating system
When system further includes a drum, the pressure of the drum is 4.8MPag~5.6MPag；
Dissociate SO in the high concentration fuming acid3Mass percent concentration be 26%~30%；
Dissociate SO in the low concentration fuming acid3Mass percent concentration be 16~20%；
Dissociate SO in the mixing fuming acid3Mass percent concentration be 22~25%.
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|---|---|---|---|
| CN201910567369.3A CN110272027B (en) | 2019-06-27 | Wet process system and process for waste sulfuric acid |
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| CN201910567369.3A CN110272027B (en) | 2019-06-27 | Wet process system and process for waste sulfuric acid |
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| CN110272027B CN110272027B (en) | 2024-04-26 |
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| TWI765711B (en) * | 2021-05-19 | 2022-05-21 | 綠升國際股份有限公司 | Method for preparing high-purity electronic grade sulfuric acid from waste sulfuric acid solution |
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