CN107051158A - A kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas and method - Google Patents
A kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas and method Download PDFInfo
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- CN107051158A CN107051158A CN201710284823.5A CN201710284823A CN107051158A CN 107051158 A CN107051158 A CN 107051158A CN 201710284823 A CN201710284823 A CN 201710284823A CN 107051158 A CN107051158 A CN 107051158A
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- CN
- China
- Prior art keywords
- sulfuric acid
- tail gas
- hydrogen peroxide
- layer
- desulfurizing tower
- Prior art date
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 239000007789 gas Substances 0.000 title claims abstract description 115
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 44
- 239000012530 fluid Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 42
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007921 spray Substances 0.000 claims abstract description 31
- 230000008676 import Effects 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims abstract description 19
- 238000012856 packing Methods 0.000 claims abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003595 mist Substances 0.000 claims description 6
- HTBDEQQYMMCKQW-UHFFFAOYSA-N [S].OO Chemical compound [S].OO HTBDEQQYMMCKQW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 230000003020 moisturizing effect Effects 0.000 claims description 5
- 238000005452 bending Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 claims description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 abstract description 2
- 229960002163 hydrogen peroxide Drugs 0.000 description 40
- 238000010521 absorption reaction Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000001117 sulphuric acid Substances 0.000 description 7
- 235000011149 sulphuric acid Nutrition 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000005945 translocation Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 floor space is big Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
Abstract
The invention discloses a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas, including desulfurizing tower, the inside of the desulfurizing tower includes circulation liquid layer successively from bottom to up, gas mixing layer, absorbing medium layer and foam-removing layer, dioxygen water inlet and circulation fluid outlet are provided with the side wall of desulfurizing tower, the dioxygen water inlet is connected by hydrogen peroxide conveyance conduit with dioxygen water storage tank, sulfuric acid tail gas import and water purification import are additionally provided with the side wall of desulfurizing tower, the absorbing medium layer includes filler and spray equipment, the circulation fluid import connected with spray equipment is provided with the side wall of desulfurizing tower, the circulation fluid outlet connects circulation fluid import by circulation fluid conveyance conduit, the foam-removing layer is from bottom to up successively by cyclone, hollow ball packing layer, baffling demister and demisting silk screen composition, offgas outlet is provided with the top of the desulfurizing tower.Apparatus of the present invention are less than 100mg/Nm to content of sulfur dioxide after sulfuric acid tail gas processing3, meet the relevant criterion of country's formulation.
Description
Technical field
The present invention relates to a kind of hydrogen peroxide desulfurization dress for being used to handle produced tail gas in sulphuric acid process
Put and method, belong to sulfuric acid tail gas process field.
Background technology
Sulfuric acid is one of maximum inorganic chemical of yield, is widely used in fertilizer, chemicals, medicine, detergent, Shui Chu
Manage the productions such as agent.Environmental statistic data shows within 2007, China's sulfuric acid industry year SO2About 100,000 tons of discharge capacity, accounts for the whole nation
SO2The 0.4% of discharge capacity, accounts for chemical industry SO2The 9.0% of total emission volumn, is larger SO in chemical industry2Emission source.
GB26132-2010《Sulfuric acid industry pollutant emission standard》Formally implement on March 1st, 2011.Required according to new national standard,
Stop within 30th existing Sulphuric Acid Enterprises emission standards for sulfur dioxide to September in 2013 from 1 day October in 2011 and perform 860mg/m3, 2013
All Sulphuric Acid Enterprises sulfur dioxide will seek unity of action 400mg/m from October 1,3, developed regions 200mg/m3Discharge standard,
Cut down 58.3% compared with former execution standard, and the double-absorption relieving haperacidity flow exhaust emissions that Sulphuric Acid Enterprises are generally used at present
SO2Concentration is generally 600~2000mg/m3, the implementation of new national standard is a test to sulphuric acid production enterprises.With 220,000 tons/year of sulphur
Exemplified by sulphur relieving haperacidity, operating mode exhaust gas volumn 66360m3/ h, tail row SO2Concentration 1600mg/m3If this partial tail gas is direct without processing
Discharge, can do great damage to environment.
To meet increasingly strict discharging standards, reducing SO2Discharge, is now badly in need of administering sulfuric acid tail gas.When
The method that preceding Chinese sulfuric acid industry is handled for sulfuric acid tail gas has many kinds, including ammonia-acid process, ammonia process, sodium alkali, citric acid
Sodium, limestone-gypsum method, activated coke method etc., wherein most widely used have ammonia-acid process, limestone-gypsum method and activated coke method
It is several.As phosphate fertilizer plant of Nanjing Chemical Industry Company uses ammonia-acid process tail gas recycle, production sulfur dioxide liquid；Kaifeng chemical fertilizer factory,
Taiyuan chemical general factory etc. uses three-level ammonia process tail gas recycle production solid imonium and high concentration bisulfite ammonium salt solution instead；Drum culture
Chemical Co., Ltd. produces solid ammonium sulfite using ammonia-acid process；Jiangxi Copper Company Limited,Guixi Metallurgy Factory 300kt/a
Copper making ancillary engineering facility 660kt/a sulfuric acid project uses active coke absorption method technique, and reclaims high concentration SO2Deng；And it is numerous in
Small-sized sulfuric acid plant then uses alkali absorption method and simple limestone-gypsum method etc..
There is line clogging serious wear in above-mentioned limestone-gypsum method processing sulfuric acid tail gas, floor space is big, flue gas during smelting
Desulfurization wastewater yield is big, complicated component, there is smoke secondary pollution, and desulfurizing byproduct gypsum is the problems such as be difficult to processing.Ammonia-
There is needing ammonia source, using absorbing in acid treatment sulfuric acid tail gas, the technological process of product sulphur ammonium relatively also compared with
It is long, easily form secondary pollution.There is high energy consumption in activated coke desulfurization, operating cost is high, causes secondary pollution problems.
The content of the invention
Based on above-mentioned technical problem, the present invention provides a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas and side
Method.
The adopted technical solution is that：
A kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas, including desulfurizing tower, the inside of the desulfurizing tower from
Under it is supreme successively include circulation liquid layer, gas mixing layer, absorbing medium layer and foam-removing layer, on the side wall of desulfurizing tower correspondence circulation
Dioxygen water inlet and circulation fluid outlet are provided with liquid layer, the dioxygen water inlet passes through hydrogen peroxide conveyance conduit and hydrogen peroxide
Storage tank is connected, and is provided with sulfuric acid tail gas import and water purification import at correspondence gas mixing layer on the side wall of desulfurizing tower, water purification enters
Mouth connection water purification conveying pipeline, the absorbing medium layer includes filler and the spray equipment above filler, in desulfurizing tower
The circulation fluid import connected with spray equipment is provided with the wall of side, the circulation fluid outlet is connected by circulation fluid conveyance conduit
Circulation fluid import, the foam-removing layer is from bottom to up successively by cyclone, hollow ball packing layer, baffling demister and demisting silk screen group
Into being provided with offgas outlet at the top of the desulfurizing tower.
It is preferred that, the sulfuric acid tail gas import connects sulfate system two by sulfuric acid tail gas conveyance conduit and inhales tower outlet, follows
Ring liquid conveyance conduit also conveys branch road by circulation fluid and connects sulfate system circulating slot, and offgas outlet is connected by exhaust emission pipeline
Connect sulfate system tail gas funnel.
It is preferred that, delivery pump and the first motor-operated control valve are provided with hydrogen peroxide conveyance conduit, in water purification conveying pipeline
On be provided with the second motor-operated control valve, be provided with circulating pump on circulation fluid conveyance conduit, circulation fluid conveying branch road on set
Have the 3rd motor-operated control valve, first motor-operated control valve, the second motor-operated control valve and the 3rd motor-operated control valve with PLC controls
Device is connected.
It is preferred that, the spray equipment includes spray liquid main pipeline, and one end and the circulation fluid import of spray liquid main pipeline connect
Connect, the other end closing of spray liquid main pipeline is arranged at intervals with shower nozzle below spray liquid main pipeline.
It is preferred that, the cyclone includes multiple swirl vanes, and one end of the swirl vane is fixed on centre frame, separately
One end is fixed on outer shroud；The swirl vane is in vertical, and the width of swirl vane is by one end of connection outer shroud to connection
One end of centre frame becomes narrow gradually.
It is preferred that, the baffling demister includes the corrugated sheet of multiple parallel layings, is provided with the bending place of corrugated sheet
Fin；Folding line direction of the fin along corrugated sheet is laid, and the section of fin is curved.
It is preferred that, the thickness of the demisting silk screen is 100-120mm, and the thickness of hollow ball packing layer is 150-200mm, is removed
The distance between mist silk screen and baffling demister are 300-500mm, and the distance between baffling demister and hollow ball packing layer are
The distance between 200-300mm, hollow ball packing layer and cyclone are 200-300mm.
A kind of hydrogen peroxide sulfur method handled for sulfuric acid tail gas, using above-mentioned device, comprises the following steps：
Sulfuric acid tail gas of a from the outlet of the suction tower of sulfate system two enters gas mixing in desulfurizing tower through sulfuric acid tail gas import
The liquid risen in layer, with gas mixing layer after gas mixing in absorbing medium layer, circulation liquid layer is through circulation fluid conveyance conduit
It is delivered to spray equipment to be sprayed, the liquid of gas and spray carries out abundant exchange reaction in absorbing medium layer, after reaction
Liquid drop to circulation liquid layer, tail gas rises to foam-removing layer；
B is in foam-removing layer, after tail gas is handled through cyclone, hollow ball packing layer, baffling demister and demisting silk screen successively, will
The mist and dust of entrainment are removed, and subsequent tail gas is emitted into sulfate system tail gas funnel through the offgas outlet at the top of desulfurizing tower；
C is delivered to desulfurizing tower interior circulation according to the hydrogen peroxide added in needs, dioxygen water storage tank through hydrogen peroxide conveyance conduit
Liquid layer, water purification is delivered to gas mixing layer through water purification conveying pipeline；
The partially liq of d desulfurizing tower interior circulation liquid layers is delivered to sulfate system circulating slot through circulation fluid conveying branch road.
In above-mentioned steps, the mass percent concentration of the hydrogen peroxide is 27.5%；In production control, take and continuously add
Plus hydrogen peroxide, continuous moisturizing, the continuous-stable method of controlling operation thereof of continuous row's diluted acid, keep sulfuric acid concentration stable 20%~
In the range of 30%.
In above-mentioned steps, the m of sulfuric acid tail gas treating capacity 600,000,0003/ Nh, sulfuric acid tail gas intake air temperature is 60~80 DEG C,
Admission pressure is 1500Pa, and content of sulfur dioxide is 800~1600mg/Nm3, content of sulfur dioxide is less than 100mg/ after processing
Nm3。
The method have the benefit that：
Hydrogen peroxide desulfurizer of the present invention can be used cooperatively with sulphur-burning sulphuric acid plant etc., and sulfuric acid tail gas treating capacity reaches
600000000 m3Content of sulfur dioxide is 800~1600mg/Nm in/Nh, sulfuric acid tail gas3, content of sulfur dioxide is less than after processing
100mg/Nm3, treatment effect substantially, meet country formulation relevant criterion.
Apparatus of the present invention are designed using single column, and the recovery of absorbing reaction and byproduct is in a tower, and corollary equipment is few
And smart, short flow, simplicity is controlled, it is workable, without extra increase operating personnel, effectively save cost of investment, operation
Cost and floor space.
Efficiently, conveniently, the desulphurizing activated strong, reaction rate of hydrogen peroxide is fast, the concentration of emission of sulfur dioxide for apparatus of the present invention
Far below standard GB/T 26132-2010 requirement, also there is higher removal efficiency to nitrogen oxides, desulphurization denitration is carried out simultaneously.
Desulfuration byproduct is dilute sulfuric acid, the problem of blocking up tower in the absence of crystallization, and absorption tower is large opening rate packed tower or void tower, SR
Small (≤600Pa), saves main blower power consumption.The dilute sulfuric acid that system is produced returns directly to sulfate system dry matter translocation use
Dried in regulation and absorb sour dense, byproduct is not required to secondary operation, and cost recovery is substantially reduced.Do not produced in whole production process
Three new waste products, non-secondary pollution belongs to typical process for cleanly preparing technology.
Brief description of the drawings
The invention will be further described with embodiment below in conjunction with the accompanying drawings：
Fig. 1 is the principle schematic diagram of hydrogen peroxide desulfurizer of the present invention；
Fig. 2 is the principle schematic diagram of baffling demister in hydrogen peroxide desulfurizer of the present invention；
Fig. 3 is the principle schematic diagram of cyclone in hydrogen peroxide desulfurizer of the present invention.
Embodiment
As shown in figure 1, a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas, including desulfurizing tower 1, the desulfurization
The inside of tower includes circulation liquid layer, gas mixing layer, absorbing medium layer and foam-removing layer successively from bottom to up.In the side wall of desulfurizing tower
Dioxygen water inlet 2 and circulation fluid outlet 3 are provided with upper correspondence circulation liquid layer, the dioxygen water inlet 2 is defeated by hydrogen peroxide
Pipeline 4 is sent to be connected with dioxygen water storage tank 5.On the side wall of desulfurizing tower sulfuric acid tail gas import 6 is provided with correspondence gas mixing layer
With water purification import 7, the connection water purification conveying pipeline 8 of water purification import 7.The absorbing medium layer includes filler and above filler
Spray equipment 9.The circulation fluid import 10 connected with spray equipment 9, the circulation fluid discharge are provided with the side wall of desulfurizing tower
Mouth 3 passes through circulation fluid conveyance conduit 24 and connects circulation fluid import 10.The foam-removing layer is from bottom to up successively by cyclone 11, hollow
Ball packing layer 12, baffling demister 13 and demisting silk screen 14 are constituted, and offgas outlet 15 is provided with the top of the desulfurizing tower.
As the further design to the present invention, the sulfuric acid tail gas import 6 is connected by sulfuric acid tail gas conveyance conduit 16
Sulfate system two inhales tower outlet.Circulation fluid conveyance conduit 24 also conveys branch road 17 by circulation fluid and connects sulfate system circulating slot.
Offgas outlet 15 connects sulfate system tail gas funnel by exhaust emission pipeline.
Further, the motor-operated control valve 19 of delivery pump 18 and first is provided with hydrogen peroxide conveyance conduit, in water purification
The second motor-operated control valve 20 is provided with conveyance conduit, circulating pump 21 is provided with circulation fluid conveyance conduit, it is defeated in circulation fluid
Send and the 3rd motor-operated control valve 22 is provided with branch road 17, first motor-operated control valve 19, the second motor-operated control valve 20 and the 3rd
Motor-operated control valve equal 22 is connected with PLC control devices 23.Automatically controlled by PLC control devices 23.
Further, the spray equipment 9 includes horizontally disposed spray liquid main pipeline 901, the one of spray liquid main pipeline
End is connected with circulation fluid import, the other end closing of spray liquid main pipeline, and spray is arranged at intervals with below spray liquid main pipeline
First 902.
Further, the cyclone 11 includes multiple swirl vanes 1101, and one end of the swirl vane 1101 is consolidated
It is scheduled on centre frame 1102, the other end is fixed on outer shroud 1103.The swirl vane 1101 is in vertical, swirl vane
Width is become narrow gradually by one end of connection outer shroud to the one end for connecting centre frame.
Further, the baffling demister 13 includes the corrugated sheet 1301 of multiple parallel layings, in corrugated sheet 1301
Bending place is provided with fin 1302.Folding line direction of the fin 1302 along corrugated sheet is laid, and the section of fin is curved.
Further, the thickness of the demisting silk screen 14 is 100-120mm, and the thickness of hollow ball packing layer 12 is 150-
The distance between 200mm, demisting silk screen 14 and baffling demister 13 are 300-500mm, baffling demister 13 and hollow ball filler
Layer the distance between 12 is 200-300mm, and the distance between hollow ball packing layer 12 and cyclone 11 are 200-300mm.
Foam-removing layer uses cyclone 11, hollow ball packing layer 12, baffling demister 13 and demisting silk screen in apparatus of the present invention
The mode of 14 combinations, and to the distance between demisting silk screen 14 and the thickness of hollow ball packing layer 12, each demisting layer, and baffling
Structure of demister 13 and cyclone 11 etc. is specifically designed, for the mist and powder carried secretly after sulfuric acid tail gas spray process
Dirt separative efficiency is high, and resistance is small, and big with allowable superficial gas velocity, is difficult obstruction, and erection space is small, and economical operation safely may be used
Lean on, the advantages of easy to operate.
A kind of hydrogen peroxide sulfur method handled for sulfuric acid tail gas, using above-mentioned hydrogen peroxide desulfurizer, specifically
Comprise the following steps：
Sulfuric acid tail gas of a from the outlet of the suction tower of sulfate system two enters gas mixing in desulfurizing tower 1 through sulfuric acid tail gas import 6
Layer, the liquid risen to after being mixed with residual gas in gas mixing layer in absorbing medium layer, circulation liquid layer is conveyed through circulation fluid
Pipeline 24 is delivered to spray equipment 9 and sprayed, and the liquid of gas and spray carries out abundant exchange reaction in absorbing medium layer,
Reacted liquid drops to circulation liquid layer, and tail gas rises to foam-removing layer.
B is in foam-removing layer, and tail gas is successively through cyclone 11, hollow ball packing layer 12, baffling demister 13 and demisting silk screen 14
After processing, the mist of entrainment and dust are removed, subsequent tail gas is emitted into sulfate system through the offgas outlet 15 at the top of desulfurizing tower
Tail gas funnel.
C is delivered in desulfurizing tower through hydrogen peroxide conveyance conduit 4 according to the hydrogen peroxide added in needs, dioxygen water storage tank 5 and followed
Ring liquid layer, water purification is delivered to gas mixing layer through water purification conveying pipeline 8.
The partially liq of d desulfurizing tower interior circulation liquid layers is delivered to sulfate system circulating slot through circulation fluid conveying branch road 17.
In the above method, valve on each conveyance conduit etc. carries out centralized automatic control using PLC control devices 23.
In the above method, the mass percent concentration of the hydrogen peroxide is 27.5%；In production control, take and continuously add
Plus hydrogen peroxide, continuous moisturizing, the continuous-stable method of controlling operation thereof of continuous row's diluted acid, keep sulfuric acid concentration stable 20%~
In the range of 30%.
In the above method, the m of sulfuric acid tail gas treating capacity 600,000,0003/ Nh, sulfuric acid tail gas intake air temperature is 60~80 DEG C,
Admission pressure is 1500Pa, and content of sulfur dioxide is 800~1600mg/Nm3, content of sulfur dioxide is less than 100mg/ after processing
Nm3。
The principle content that the present invention relates to is illustrated below：
Gas washing in SA production is to absorb SO in flue gas using the concentrated sulfuric acid3Gas, is substantially water absorption process.With the progress of reaction
The concentration of sulfuric acid is improved constantly, and need to be supplemented moisture content and is diluted to optimal absorption and requires that acid is dense.Sulfuric acid production system is required supplementation with
Add water, this water just produced for hydrogen peroxide method sulfur removal technology (absorbs SO3The dilute sulfuric acid produced after gas) provide outlet.But
It is drying in sulfuric acid production system and absorbs and have strict demand to water balance, i.e., can not surpasses into the moisture for drying absorption system
Go out theoretical amount of water, otherwise production will be made not to be normally carried out.
Realize that the dilute sulfuric acid generated in hydrogen peroxide sweetening process is all reclaimed, it is necessary to ensure that in sulfuric acid production system
The water produced during water balance, tail gas absorption is necessarily less than the dry water for being drawn through range request of sulfuric acid.Using commercially available 27.5%
Hydrogenperoxide steam generator as absorbent when, it is dense that theoretical dilute acid concentration can reach 55%, i.e. this technology by-product diluted acid
Degree can be adjusted in 0-55% concentration.To ensure the water balance of the dry desorption system of gas washing in SA production.Allow the dilute sulfuric acid concentration returned
It can be controlled in and is not less than 2.90%, otherwise produces diluted acid amount excessively, dry absorption cycle system can be destroyed by returning to after sulfate system
Water balance, gas washing in SA production can be deteriorated when serious, stopping production is even resulted in, and diluted acid amount is excessive while will also result in absorbent
Loss.
In production control, continuous addition accurate measurement addition absorbent, continuous moisturizing are taken, continuously row's diluted acid is continuous
Stable operation control technology, keeps sulfuric acid concentration stable in the range of 20~30%.
From reaction mechanism, high-concentration absorbent agent is conducive to the oxidative absorption of sulfur dioxide, it is determined that reasonably operating dense
Degree, so as to reach continuous-stable, low consumption technological requirement it is most important, so hydrogenperoxide steam generator concentration demonstration selection right and wrong
It is often necessary.Determine that absorbing liquid ultimate density is 0.1-1.0% by theoretical calculation and binding tests, this concentration can both ensure
Preferable assimilation effect, controls the unit consumption of absorbent again, and technical and economy obtains unification.Also strictly to control simultaneously
(selection of amount should be in tail gas SO for the addition of hydrogen peroxide processed2Fully absorb theoretical amount and design calculates and absorbs SO2Index
Between theoretical amount), it is ensured that send hydrogen peroxide residual in dilute sulfuric acid to some other department minimum.
Even if in addition, containing minimal amount of hydrogen peroxide in row's dilute sulfuric acid outside, on the one hand from its dilute sulfuric acid amount and sulfuric acid system
System sulfuric acid internal circulating load is compared namely very micro, and part SO is also contained in another aspect sulfate system recycle acid2Carried with dilute sulfuric acid
Trace Hydrogen Peroxide reaction, be completely removed after being circulated through absorption tower.Therefore hydrogen peroxide pair need not be considered completely
The influence of concentrated sulfuric acid quality.
Designed using single column, the recovery of absorbing reaction and byproduct is in a tower, and corollary equipment is fewer but better, flow letter
Short, control is easy, workable, and without extra increase operating personnel, effectively save cost of investment, operating cost and occupation of land are empty
Between.
Efficiently, conveniently, the desulphurizing activated strong, reaction rate of hydrogen peroxide is fast, and the concentration of emission of sulfur dioxide is low for desulfurizer
In below 200mg/m3, far below standard GB/T 26132-2010 requirement, also there is higher removal efficiency to nitrogen oxides, take off
Sulphur denitration is carried out simultaneously.Desulfuration byproduct is dilute sulfuric acid, the problem of blocking up tower in the absence of crystallization, and absorption tower is large opening rate packed tower
Or void tower, SR is small (≤600Pa), saves main blower power consumption.The dilute sulfuric acid that system is produced returns directly to sulphur
Acid system dry matter translocation, which is used to adjust, dries and absorbs sour dense, and byproduct is not required to secondary operation, and cost recovery is substantially reduced.Entirely
Three new waste products are not produced in production process, non-secondary pollution belongs to typical process for cleanly preparing technology.
By taking 220,000 tons/year of sulphur-burning sulphuric acid plants as an example, sulfuric acid tail gas is used in hydrogen peroxide method sulfur removal technology, system tail gas
Sulfur dioxide and hydroperoxidation generation sulfuric acid.Whole process is the completion reactive absorption process in a tower.
1st, sulfuric acid tail gas conveying and reaction and absorption processing
Hydrogen peroxide desulphurization system overall resistance loses about 400~1500pa, and general sulfate system main air blower can be provided
This partial pressure, therefore booster fan is not considered herein.Sulfuric acid tail gas needs to adjust dust content before desulfurizing tower is entered, and water steams
The parameters such as gas, the content of oxygen, and temperature, make tail gas meet desulfurization requirement.Sulfuric acid tail gas does not contain dust, is removed without setting up
Dirt equipment, oxygen content and temperature also comply with desulfurization condition, but due in sulfuric acid tail gas water content it is almost nil, condition is conformed to
Ask, without being adjusted again.
Tail gas enters tower and the mixing contact of substantial amounts of diluted acid circulation fluid, is dissolved in diluted acid (about 1：40 volumes), later fall into and follow
Annular groove and hydroperoxidation, produce dilute sulfuric acid, and dilute sulfuric acid reaches that the outer sulfate system circulation acid system that drains into is adjusted after normal concentration
Acid is dense.
2nd, water balance
Gas washing in SA production is to absorb SO in flue gas using the concentrated sulfuric acid3Gas, is substantially water absorption process.With the progress of reaction
The concentration of sulfuric acid is improved constantly, and need to be supplemented moisture content and is diluted to optimal absorption and requires that acid is dense.Sulfuric acid production system is required supplementation with
Add water, this water just produced for hydrogen peroxide method sulfur removal technology (absorbs SO3The dilute sulfuric acid produced after gas) provide outlet.But
It is drying in sulfuric acid production system and absorbs and have strict demand to water balance, i.e., can not surpasses into the moisture for drying absorption system
Go out theoretical amount of water, otherwise production will be made not to be normally carried out.
Realize that the dilute sulfuric acid generated in hydrogen peroxide sweetening process is all reclaimed, it is necessary to ensure that in sulfuric acid production system
The water produced during water balance, tail gas absorption is necessarily less than the dry water for being drawn through range request of sulfuric acid.Using commercially available 27.5%
Hydrogenperoxide steam generator as absorbent when, it is dense that theoretical dilute acid concentration can reach 55%, i.e. this technology by-product diluted acid
Degree can be adjusted in 0-55% concentration.To ensure the water balance of the dry desorption system of gas washing in SA production.Allow the dilute sulfuric acid concentration returned
It can be controlled in and is not less than 2.90%, otherwise produces diluted acid amount excessively, dry absorption cycle system can be destroyed by returning to after sulfate system
Water balance, gas washing in SA production can be deteriorated when serious, stopping production is even resulted in, and diluted acid amount is excessive while will also result in absorbent
Loss.
In production control, continuous addition accurate measurement addition oxidant, continuous moisturizing are taken, continuously row's diluted acid is continuous
Stable operation control technology, keeps sulfuric acid concentration stable in the range of 20~30%.
It is defeated in order to reduce from data as can be seen that finished product acid concentration need to only reach that more than 9.12% just can meet water balance
Expense is sent, by-product dilute sulfuric acid concentration is set in this scheme as 20~30%.
3rd, desulfurizing tower
The capital equipment of the present apparatus is desulfurizing tower, and the desulfurizing tower is cylindrical tower, and its structure is similar to sulfuric acid absorption tower, root
Suitable tower diameter is selected according to technological parameter.
The present apparatus：Using 1 Ф 4.8m desulfurizing tower, desulfurizing tower point four layers, i.e. circulation fluid room, gas mixer chamber, absorption
Dielectric layer, foam-removing layer.
Medium in desulfurizing tower is mainly：Cigarette gas and water, hydrogen peroxide, dilute sulfuric acid.Because exhaust temperature is 60 in this engineering
DEG C, and due to the severe corrosive of dilute sulfuric acid, special preservative treatment must be carried out to desulfurizing tower.
Claims (10)
1. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas, it is characterised in that：Including desulfurizing tower, the desulfurizing tower
Inside from bottom to up successively include circulation liquid layer, gas mixing layer, absorbing medium layer and foam-removing layer, on the side wall of desulfurizing tower
Dioxygen water inlet and circulation fluid outlet are provided with correspondence circulation liquid layer, the dioxygen water inlet passes through hydrogen peroxide conveyance conduit
It is connected with dioxygen water storage tank, is provided with sulfuric acid tail gas import at correspondence gas mixing layer on the side wall of desulfurizing tower and water purification enters
Mouthful, water purification import connection water purification conveying pipeline, the absorbing medium layer includes filler and the spray equipment above filler,
The circulation fluid import connected with spray equipment is provided with the side wall of desulfurizing tower, the circulation fluid outlet is conveyed by circulation fluid
Pipeline connects circulation fluid import, and the foam-removing layer by cyclone, hollow ball packing layer, baffling demister and is removed successively from bottom to up
Mist silk screen is constituted, and offgas outlet is provided with the top of the desulfurizing tower.
2. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas according to claim 1, it is characterised in that：Institute
State sulfuric acid tail gas import and the outlet of the suction tower of sulfate system two is connected by sulfuric acid tail gas conveyance conduit, circulation fluid conveyance conduit also passes through
Circulation fluid conveying branch road connection sulfate system circulating slot, offgas outlet connects sulfate system exhaust smoke by exhaust emission pipeline
Chimney.
3. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas according to claim 1, it is characterised in that：
Delivery pump and the first motor-operated control valve are provided with hydrogen peroxide conveyance conduit, the second electronic control is provided with water purification conveying pipeline
Valve processed, circulating pump is provided with circulation fluid conveyance conduit, and the 3rd motor-operated control valve, institute are provided with circulation fluid conveying branch road
The first motor-operated control valve, the second motor-operated control valve and the 3rd motor-operated control valve is stated to be connected with PLC control devices.
4. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas according to claim 1, it is characterised in that：Institute
Stating spray equipment includes spray liquid main pipeline, and one end of spray liquid main pipeline is connected with circulation fluid import, spray liquid main pipeline
The other end is closed, and shower nozzle is arranged at intervals with below spray liquid main pipeline.
5. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas according to claim 1, it is characterised in that：Institute
Stating cyclone includes multiple swirl vanes, and one end of the swirl vane is fixed on centre frame, and the other end is fixed on outer shroud；
The swirl vane is in vertical, and the width of swirl vane is gradually become by one end of connection outer shroud to the one end for connecting centre frame
It is narrow.
6. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas according to claim 1, it is characterised in that：Institute
Stating baffling demister includes the corrugated sheet of multiple parallel layings, and the bending place of corrugated sheet is provided with fin；The fin is along ripple
The folding line direction of shape plate is laid, and the section of fin is curved.
7. a kind of hydrogen peroxide desulfurizer handled for sulfuric acid tail gas according to claim 1, it is characterised in that：Institute
The thickness for stating demisting silk screen is 100-120mm, and the thickness of hollow ball packing layer is 150-200mm, demisting silk screen and baffling demisting
The distance between device is 300-500mm, and the distance between baffling demister and hollow ball packing layer are 200-300mm, hollow ball
The distance between packing layer and cyclone are 200-300mm.
8. a kind of hydrogen peroxide sulfur method handled for sulfuric acid tail gas, using any claim in such as claim 1-7
Described device, it is characterised in that comprise the following steps：
Sulfuric acid tail gas of a from the outlet of the suction tower of sulfate system two enters gas mixing layer in desulfurizing tower through sulfuric acid tail gas import, with
The liquid risen in gas mixing layer after gas mixing in absorbing medium layer, circulation liquid layer is delivered to through circulation fluid conveyance conduit
Spray equipment is sprayed, and the liquid of gas and spray carries out abundant exchange reaction, reacted liquid in absorbing medium layer
Circulation liquid layer is dropped to, tail gas rises to foam-removing layer；
B after tail gas is handled through cyclone, hollow ball packing layer, baffling demister and demisting silk screen successively, will be carried secretly in foam-removing layer
Mist and dust remove, subsequent tail gas is emitted into sulfate system tail gas funnel through the offgas outlet at the top of desulfurizing tower；
C is delivered to desulfurizing tower interior circulation liquid layer according to the hydrogen peroxide added in needs, dioxygen water storage tank through hydrogen peroxide conveyance conduit,
Water purification is delivered to gas mixing layer through water purification conveying pipeline；
The partially liq of d desulfurizing tower interior circulation liquid layers is delivered to sulfate system circulating slot through circulation fluid conveying branch road.
9. a kind of hydrogen peroxide sulfur method handled for sulfuric acid tail gas according to claim 8, it is characterised in that：Institute
The mass percent concentration for stating hydrogen peroxide is 27.5%；In production control, continuous addition hydrogen peroxide, continuous moisturizing, company are taken
The continuous-stable method of controlling operation thereof of continuous row's diluted acid, keeps sulfuric acid concentration stable in the range of 20%~30%.
10. a kind of hydrogen peroxide sulfur method handled for sulfuric acid tail gas according to claim 8, it is characterised in that：
The m of sulfuric acid tail gas treating capacity 600,000,0003/ Nh, sulfuric acid tail gas intake air temperature is 60~80 DEG C, and admission pressure is 1500Pa, two
Sulfur oxide content is 800~1600mg/Nm3, content of sulfur dioxide is less than 100mg/Nm after processing3。
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