CN100368061C - Integration method for ammonia process of desulfurizing flue gas and multiple utilizing desulfurized products and equipment - Google Patents
Integration method for ammonia process of desulfurizing flue gas and multiple utilizing desulfurized products and equipment Download PDFInfo
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- CN100368061C CN100368061C CNB031575994A CN03157599A CN100368061C CN 100368061 C CN100368061 C CN 100368061C CN B031575994 A CNB031575994 A CN B031575994A CN 03157599 A CN03157599 A CN 03157599A CN 100368061 C CN100368061 C CN 100368061C
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- flue gas
- solution
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- 238000000034 method Methods 0.000 title claims abstract description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 31
- 239000003546 flue gas Substances 0.000 title claims description 31
- 230000010354 integration Effects 0.000 title 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 69
- 230000023556 desulfurization Effects 0.000 claims abstract description 67
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 8
- 238000009527 percussion Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 239000000779 smoke Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- 229940001482 sodium sulfite Drugs 0.000 claims description 4
- 239000003930 superacid Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 8
- 239000003517 fume Substances 0.000 abstract 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 239000000428 dust Substances 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012805 post-processing Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000003500 flue dust Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The present invention discloses an integrative method for desulfurizing fume by an ammonia method and reclaiming a desulfurized product and a device thereof. The method of the present invention has the technical scheme that 1), boiler fume makes a desulfurization reaction with ammonia water after the dust in the boiler fume is removed, the water solution of ammonium bisulfite and ammonium sulfite is generated by the reaction of the boiler fume and the ammonia water, and the fume which is desulfurized is sent to a fume channel to be exhausted; 2), the water solution containing the ammonium bisulfite and the ammonium sulfite is purified to filter solid suspended substances in the solution; 3), excessive acid solution is added in the purified water solution of the ammonium bisulfite and the ammonium sulfite, and the water solution is sent to a reaction vessel to generate sulfur dioxide gas and ammonium salt water solution containing excessive acid solution; 4), the generated sulfur dioxide gas can be prepared into sulfur dioxide liquid or sodium sulfite without water, and the generated ammonium salt water solution containing the excessive acid can be prepared into a finished product of solid ammonium salt. The method of the present invention has the advantages that desulfurized product is reasonably utilized while the desulfurization efficiency is guaranteed, the problem of the secondary pollution caused by the desulfurized product is solved, and resources are utilized fully.
Description
Technical field
The invention belongs to environmental protection technical field, relate to method, the desulfurization product post processing of flue gas desulfurization, especially the integral method and the associated production equipment thereof of the comprehensive utilization of the flue gas ammonia process of desulfurization and desulfurization product.
Background technology
China is to be the country of main energy sources with the coal, and oxysulfide and flue dust are that main air pollution due to coal combustion is occupied an leading position always, have become one of the most serious country of world's sulfur oxide contamination.Up to the present, develop and multiple sulfur method, mainly be divided into dry method and wet method two big classes.
Dry desulfurization mainly contains lime method and ammonia process, produces a large amount of waste residues after the lime method desulfurization and is difficult to handle, and causes secondary pollution.The ammonia dry type desulfurizing method of dry type ammonia process such as Japan adopts under with the electron beam irradiation.Can be referring to Chinese invention patent application authorization specification CN1011858B and Chinese invention patent ublic specification of application CN1133749A.But this sulfur method investment is big, and operating cost is very high.
The ammonia process of desulfurization is also arranged in the wet desulphurization, contact with flue gas with the aqueous solution that contains ammonia, sulfur dioxide is carried out chemical absorbing, generate ammonium bisulfite and ammonium sulfite solution, because these two kinds of solution are easy to decompose, form secondary pollution in depositing or transporting easily, also cause product to be difficult to be fully utilized.Simultaneously, the processing to desulfurization product in the prior art mainly is to admix flyash to make fertilizer, and this single post-processing approach has limited the abundant application of desulfurization product.In addition, existing wet desulphurization is for guaranteeing desulfuration efficiency, and water consumption is big, makes that desulfurization product is difficult to handle.So, explore the integral method that a kind of more efficiently sulfur method and desulfurization product fully utilize, have important application value.
Summary of the invention
The integral method that the purpose of this invention is to provide the comprehensive utilization of a kind of flue gas ammonia process of desulfurization and desulfurization product, after utilizing ammoniacal liquor to carry out flue gas desulfurization, continuation is carried out innoxious completely and recycling treatment to desulfurization product, produces solid ammonium sulfate production fluid body sulfur dioxide in parallel and anhydrous sodium sulfite simultaneously.
The integral method of the flue gas ammonia process of desulfurization of the present invention and desulfurization product comprehensive utilization, it comprises the steps:
1) after the boiler smoke dedusting, with ammoniacal liquor generation desulphurization reaction, reaction generates the aqueous solution of ammonium bisulfite and ammonium sulfite, and the flue gas after the desulfurization is sent into the flue discharging;
2) contain the aqueous solution of ammonium bisulfite and ammonium sulfite, carry out the solid suspension in the purified treatment filtering solution;
3) through the ammonium bisulfite of purification and the aqueous solution of ammonium sulfite, add excess acid solution, send into reactor, generate sulfur dioxide gas and the ammonium salt aqueous solution that contains excess acid solution;
4) sulfur dioxide gas that is produced, drying, cooling, liquefaction obtain the sulfur dioxide liquid finished product; Or absorb sulfur dioxide gas with alkali lye, the sodium sulfite saturated solution, through concentrate, crystallization, centrifugation get the finished product anhydrous sodium sulfite; What produced contains superacid ammonium salt aqueous solution, and with the ammoniacal liquor neutralization, condensing crystallizing can obtain solid ammonium salt finished product.
According to the method described in the present invention, its reaction principle is as described below:
Flue gas is to use the ammonia process of desulfurization, and its chemical equation is:
SO
2+H
2O+NH
3＝NH
4HSO
3
SO
2+H
2O+2NH
3＝(NH
4)
2SO
3
Desulfurization product is ammonium bisulfite and ammonium sulfite mixed aqueous solution, and wherein ammonium bisulfite accounts for 68% of solute total amount, and ammonium sulfite accounts for 32% of solute total amount.Contain solid impurity in the solution, must be through purified treatment, the solid suspension in the filtering solution.Purification process is very important for the post processing of desulfurization product, not only can improve the comprehensive utilization ratio of desulfurization product, and can obtain comparatively pure product.Purification can adopt any device of above-mentioned purification purpose of realizing to handle, for example horizontal spiral discharge sedimentation centrifuge or automatic plate and frame type filter-press etc.
Desulfurization product after the purification is to handle with excess acid solution, can adopt the concentrated sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid etc., the excessive abundant conversion that can help desulfurization product of acid solution.It is example that the concentrated sulfuric acid with 98% is handled, and has generated the solid ammonium sulfate product.Its chemical equation is:
2NH
4HSO
3+H
2SO
4＝(NH
4)
2SO
4+2SO
2↑+2H
2O
(NH
4)
2SO
3+H
2SO
4＝(NH
4)
2SO
4+SO
2↑+H
2O
Accordingly, if the solid ammonium salt finished product that uses processing desulfurization products such as phosphoric acid, hydrochloric acid or nitric acid to obtain is respectively diammonium hydrogen phosphate and/or ammonium hydrogen phosphate, ammonium chloride or ammonium nitrate.
The sulfur dioxide gas that is generated can liquefy and produce the sulfur dioxide liquid finished product, also can handle generating the anhydrous sodium sulfite finished product with alkali lye, but also both produces simultaneously, and the chemical equation that alkali lye is handled is:
SO
2+ Na
2CO
3=Na
2SO
3+ CO
2Or
SO
2+2NaOH＝Na
2SO
3+H
2O
The aforementioned ammonium sulfate that generates with sulfuric acid treatment obtains the solid sulphuric acid ammonium product behind the evaporative crystallization, can be used for producing magnetization fertilizer.
Another object of the present invention provides the apparatus of the integral method that is used to realize the above-mentioned flue gas ammonia process of desulfurization and desulfurization product comprehensive utilization, comprises following equipment:
1) desulfurizing tower can be used for the flue gas desulfurization reaction, and the percussion flow desulfurizing tower of blast atomizer preferably is housed, and flue gas and desulfurizing agent at this desulphurization reaction take place, and generate ammonium bisulfite and ammonium sulfite;
2) desulfurization product purifier is used for the solid suspension of filtering desulfurization product solution, for example horizontal spiral discharge sedimentation centrifuge or plate and frame type filter-press etc. automatically;
3) reactor is used for the post processing of desulfurization product, and desulfurization product and acid solution react at this, generates sulfur dioxide gas and contains superacid ammonium salt solution, handles respectively again.
The used device of the present invention also comprises drying tower, cooling system, liquefaction system, absorption tower, evaporation and crystallization system, centrifuge, rotary kiln and corresponding heat exchange, power set etc., all is the conventional equipment in this area.
According to method provided by the invention and process units, preferred technological process (can with reference to the process chart of Fig. 1) as described below:
After the boiler smoke dedusting, enter in the reactor in the percussion flow desulfurizing tower that blast atomizer is housed, prepare 5% ammoniacal liquor, through sending into the blast atomizer that is installed in the percussion flow desulfurizing tower internal reaction device for ammonia system as desulfurizing agent.Desulfurizing agent fully clashes into following current and flue gas in the reactor of atomizing shape in tower, mixes contact, and desulfurization chemical reaction takes place, and generates ammonium bisulfite and ammonium sulfite.The flue gas that purifies removes moisture through the dehydration defogging device, sends into smoke stack emission through air-introduced machine again.Desulfurization degree can be more than 95%.The aqueous solution that contains ammonium bisulfite and ammonium sulfite, by flue gas most of water of vaporizing, simmer down to sprayed into the 25-30% of liquid measure originally, entered the desulfurization product purifier.
The aqueous solution of desulfurization product ammonium bisulfite and ammonium sulfite is through purifying the solid suspension in the filtering solution.The desulfurization product purifier can adopt the cleaning equipment that can remove solid suspension in the solution commonly used in this case, for example horizontal spiral discharge sedimentation centrifuge or automatic plate and frame type filter-press etc.
Through the ammonium bisulfite that purifies and the aqueous solution and the excess acid solution of ammonium sulfite, send into reactor, i.e. sulfur dioxide generator, the gas phase that is produced partly is sulfur dioxide, drying, cooling, liquefy the sulfur dioxide liquid finished product; Sulfur dioxide gas also can absorb in the absorption tower with alkali lye, gets the sodium sulfite saturated solution, gets the finished product anhydrous sodium sulfite through concentrated, crystallization, centrifugation.The sulfur dioxide gas that is not absorbed fully can mix along with tail gas from absorption tower is circulated back in the flue gas that enters before the desulfurizing tower, then through desulfurization once more, thereby improves the absorptivity of sulfur dioxide.
The liquid phase part that is generated is for containing superacid ammonium salt solution, with in the ammonia and after, condensing crystallizing gets the solid ammonium product salt.When the used acid solution in front is the concentrated sulfuric acid, can obtain the solid ammonium sulfate product, if in reactor, send phosphoric acid, can generate diammonium hydrogen phosphate or ammonium hydrogen phosphate.If send nitric acid, then can generate ammonium nitrate.If send hydrochloric acid, then can generate ammonium chloride.
Related concrete production equipment is not unique in the said method, to those skilled in the art, can use any equipment or device that can reach equal effect to realize this method fully.
The present invention compared with prior art has remarkable advantages and effect:
1) the present invention by rational technical process with desulfurization and with desulfurization product produce solid ammonium sulfate (diammonium hydrogen phosphate or ammonium hydrogen phosphate, ammonium nitrate, ammonium chloride) coproduction sulfur dioxide liquid and anhydrous sodium sulfite integrated, not only widened the processing method of desulfurization product, and desulfurization product is easy to decompose, cause the difficult problem of secondary pollution in the solution prior art, the chemical products that production national economy is essential, make desulfurization product realize resource, can reduce the actual motion expense significantly or certain economic benefits is arranged.
2) the present invention adopts advanced percussion flow mass transfer principle that flue gas is mixed in the percussion flow desulfurizing tower with ammoniacal liquor, and adopt blast atomizer to spray into ammoniacal liquor, mix with the flue gas following current, not only resistance is little, and has strengthened absorption process, has significantly reduced water consumption, the process that makes desulfurization product produce solid ammonium sulfate coproduction sulfur dioxide liquid and anhydrous sodium sulfite realizes energy-conservationization, high efficiency has solved existing wet desulphurization for guaranteeing desulfuration efficiency, a difficult problem that causes the big desulfurization product of water consumption to be difficult to handle.
When 3) the present invention uses alkali lye to absorb sulfur dioxide gas, owing to form negative pressure state during flue gas emissions, the sulfur dioxide gas that the absorption tower is not absorbed fully, can mix along with tail gas from absorption tower is circulated back in the flue gas that enters before the desulfurizing tower, entering desulfurizing tower then absorbs once more, improved the absorptivity of sulfur dioxide, not only make full use of the sulfur dioxide resource, and reduce sulfur dioxide gas and discharge the pollution that air is caused, the gas that the technology that existing alkali lye absorbs sulfur dioxide often contains this strand sulfur dioxide enters atmosphere, so the present invention has remarkable advantages for prior art.
Description of drawings
Fig. 1 is a process chart of the present invention
The specific embodiment
With reference to process chart, and use following embodiment and describe flue gas desulfurization of the present invention and last handling process in detail, but do not limit the scope of the invention.
As shown in Figure 1; boiler smoke is after electric cleaner removes 99% flue dust; enter percussion flow desulfurizing tower (model: TS-10-1000; the environmental protection machinery instrument factory production of the Far East, Zhenjiang) in the reactor in; the 5% ammoniacal liquor desulfurizing agent for preparing is through supplying ammonia system; be desulfurizing agent preparation and feed system; send into the blast atomizer (model: PZQZ that is installed in the percussion flow desulfurization internal reaction device; Beijing is raised new spraying mechanical Co., Ltd and is produced); desulfurizing agent fully clashes into following current and flue gas in the reactor of atomizing shape in tower, mixes contact, and chemical reaction takes place; generate desulfurization product, i.e. ammonium bisulfite and ammonium sulfite.The flue gas that purifies removes moisture through the dehydration defogging device, sends into smoke stack emission through air-introduced machine again, and desulfurization degree is about 96%.
Desulfurization product be contain ammonium bisulfite and and the aqueous solution of ammonium sulfite, by flue gas most of water of vaporizing, simmer down to sprayed into the 25-30% of liquid measure originally after coming out from desulfurizing tower, behind water sealed tank and centrifuge, in the desulfurization product storage tank, compile, can enter the desulfurization product purifier then according to the actual conditions circular treatment.
The aqueous solution of desulfurization product ammonium bisulfite and ammonium sulfite contains solid suspension, sends into purifier (LW horizontal spiral discharge sedimentation centrifuge, Hefei Talentgroup Science ﹠ Technology Development Co., Ltd. produces) and is purified the filtering solid suspension.
Through the ammonium bisulfite of purification and the aqueous solution and the excessive concentrated sulfuric acid of ammonium sulfite, send into reactor (model: A type four-hole metering retort, non-metal chemical mechinery works, Yixing, Jiangsu produces), it is the sulfur dioxide generator, after the gas phase part sulfur dioxide drying tower drying that produces, the liquefaction of cooling liquid system cools, through the sulfur dioxide liquid gatherer, get the sulfur dioxide liquid finished product, can carry out the finished product bottling.
Liquid phase part is the ammonium sulfate that contains excess sulfuric acid, through the cooling in and still, replenish the liquefied ammonia neutralization, obtain ammonium sulfate, through centrifuge (SXZ 3-foot bottom discharging automatic centrifuge, the newborn machinery plant in Shijiazhuang produces) and rotary kiln (direct-heating type adverse current rotary dryer, Guilin Metallurgy Machinery Principal Station production) carry out condensing crystallizing, obtain the solid ammonium sulfate product after the packing.
The sulfur dioxide gas that had before produced is delivered to (material filling type absorption tower, two sections absorption towers through the sulfur dioxide blower fan, Beijing chemical industry equipment factory produces), alkali lye with 30% concentration, absorb, get the sodium sulfite saturated solution, turn trough in passing through successively, graphite heating evaporimeter (former hole of YKA type graphite heating evaporimeter, the carbon element factory, Nantong produces), centrifuge and rotary kiln concentrates, obtain the finished product anhydrous sodium sulfite after the crystallization, centrifugation, drying, packing.As shown in Figure 1, in this segment process, contain unreacted sulfur dioxide gas A in the tail gas from absorption tower, can be circulated back to enter in the preceding flue gas of desulfurizing tower and mix, then through desulfurization once more.Can improve the rate of recovery of sulfur dioxide.
According to above-mentioned technical process, when using excess acid solution-treated desulfurization product,, can generate diammonium hydrogen phosphate or ammonium hydrogen phosphate if in reactor, send phosphoric acid.If send nitric acid, then can generate ammonium nitrate.If send hydrochloric acid, then can generate ammonium chloride.
Claims (3)
1. the integral method of the flue gas ammonia process of desulfurization and desulfurization product comprehensive utilization comprises the steps:
1) after the boiler smoke dedusting, with ammoniacal liquor generation desulphurization reaction, reaction generates the aqueous solution of ammonium bisulfite and ammonium sulfite, and the flue gas after the desulfurization is sent into the flue discharging;
2) contain the aqueous solution of ammonium bisulfite and ammonium sulfite, carry out purified treatment, the solid suspension in the filtering solution;
3) through the ammonium bisulfite of purification and the aqueous solution of ammonium sulfite, add excess acid solution, send into reactor, generate sulfur dioxide gas and the ammonium salt aqueous solution that contains excess acid solution;
4) sulfur dioxide gas that is produced, drying, cooling, liquefaction obtain the sulfur dioxide liquid finished product; Or absorb sulfur dioxide gas with alkali lye, the sodium sulfite saturated solution, through concentrate, crystallization, centrifugation get the finished product anhydrous sodium sulfite; What produced contains superacid ammonium salt aqueous solution, and with the ammoniacal liquor neutralization, condensing crystallizing can obtain solid ammonium salt finished product.
2. the integral method of the flue gas ammonia process of desulfurization according to claim 1 and desulfurization product comprehensive utilization, it is characterized in that: after the described boiler smoke dedusting, enter in the reactor in the percussion flow desulfurizing tower, ammoniacal liquor following current and flue gas in the reactor of blast atomizer in tower fully clash into, mix contact, desulfurization chemical reaction takes place.
3. the integral method of the flue gas ammonia process of desulfurization according to claim 1 and 2 and desulfurization product comprehensive utilization, it is characterized in that: described acid solution can be the concentrated sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid, accordingly, then described solid ammonium salt finished product is ammonium sulfate, diammonium hydrogen phosphate and/or ammonium hydrogen phosphate, ammonium chloride or ammonium nitrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031575994A CN100368061C (en) | 2003-09-24 | 2003-09-24 | Integration method for ammonia process of desulfurizing flue gas and multiple utilizing desulfurized products and equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031575994A CN100368061C (en) | 2003-09-24 | 2003-09-24 | Integration method for ammonia process of desulfurizing flue gas and multiple utilizing desulfurized products and equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100427391C (en) * | 2006-09-30 | 2008-10-22 | 宁夏英力特电力集团股份有限公司 | Tail gas treatment and reutilization for calcium carbide stove |
| CN101612515B (en) * | 2008-06-28 | 2013-01-02 | 金隆铜业有限公司 | Wet flue gas desulfurization method |
| CN101601964B (en) * | 2009-06-03 | 2012-01-11 | 李鹏举 | Ammonia flue gas desulfurization device |
| CN102211762B (en) * | 2010-04-06 | 2012-11-21 | 山东三维石化工程股份有限公司 | Method for preparing sulfur and processing tail gas by taking ammonium bisulfite as intermediate |
| CN101987278B (en) * | 2010-07-28 | 2013-08-07 | 丁正元 | Method for preparing fertilizer grade monoammonium phosphate from sulfurous gases by ammonia-process desulfurization |
| CN102976359B (en) * | 2012-12-21 | 2015-01-07 | 四川宏达股份有限公司 | Method for producing ammonium sulfate by removing sulfur through ammonia method |
| CN104548909A (en) * | 2014-12-04 | 2015-04-29 | 常州大学 | Gas-liquid phase medium flue gas desulfurization device |
| CN106430246A (en) * | 2016-09-29 | 2017-02-22 | 攀枝花市博信化工有限责任公司 | Method for separating and recycling ammonia sulfate from preparation technology of sodium sulfide adopting solid waste sodium sulfate |
| CN109499289A (en) * | 2018-11-07 | 2019-03-22 | 襄阳泽东化工集团有限公司 | A kind of processing method and processing device of desulfidation tail gas |
| CN109621653A (en) * | 2018-12-29 | 2019-04-16 | 中冶南方都市环保工程技术股份有限公司 | A kind of the coke oven flue gas ammonia method desulfurizing system and method for resourcebility recycling |
| CN114053834B (en) * | 2020-08-05 | 2024-01-02 | 湖南中冶长天节能环保技术有限公司 | External circulation cleaning treatment method and system for cyanogen-containing SRG gas |
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