CN102639211B - Flue gas desulphurisation - Google Patents
Flue gas desulphurisation Download PDFInfo
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- CN102639211B CN102639211B CN201080025110.3A CN201080025110A CN102639211B CN 102639211 B CN102639211 B CN 102639211B CN 201080025110 A CN201080025110 A CN 201080025110A CN 102639211 B CN102639211 B CN 102639211B
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- Prior art keywords
- tca6
- slurries
- gas
- water
- stream
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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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
Abstract
A process for desulphurisation of a gas containing sulphur oxides (SOx) in a wet scrubbing unit is described. The process comprises the step of: contacting said gas with an aqueous tricalcium aluminate hexahydrate (TCA6) scrubbing slurry to remove SOx from the gas by reaction with TCA6 to form a spent scrubbing solution comprising a calcium compound containing sulphur and oxygen, and a aluminium compound containing oxygen and hydrogen.
Description
Technical field
The present invention relates to the method and apparatus of flue gas desulfurization, wherein by reacting and remove the sulfur oxide (SO being included in flue gas in wet purifying decice with six water tricalcium aluminates (TCA6)
x, be generally SO
2or SO
3).
Background technology
Aluminium is the metal using in the world more than second, annual global aluminium oxide demand output > 70MT, and Australia accounts for > 20MT/ at present.By Bayer process, extract aluminium oxide energy consumption large, need electric power and steam, make most of aluminium oxide refinery autogenous energy resources.Therefore, aluminum oxide industry is the main emission source of greenhouse gases, and is that under coal or heavy fuel oil condition, aluminum oxide industry is SO at fuel
xmain emission source.Can before and after burning or between main combustion period, take SO
xemission control measure.The SO carrying out after burning
xan example of emission control measure is called " flue gas desulfurization " (FGD).Adopt art methods, by economically feasible and ready-made alkaline medium, promote FGD, wherein lime or lime stone slurry are occupied an leading position in existing system.
According to the whole world to the lasting demand of aluminium and stricter legislations of environmental protection, the research and development that aluminium industry processed is more and more paid attention to environmental management and managed the sustainable scheme of its discarded object and emission.It is a kind of to SO that employing comes the height alkaline red mud waste stream of self-alumina refinery to carry out emission control
2and CO
2the feasible program of successful execution.Yet, adopt red mud can not fully remove SO
2, because a large amount of non-reactive material unnecessarily circulate by system, implementation cost is high.This method also causes sulphite and sulfate anion undesirably to circulate being back to the liquid stream of refinery.
The wet purification method that adopts lime and magnesium do purification composition to remove the sulfur dioxide in the flue gas of power station is well-known.For example, European Patent Publication No 0162536, European Patent Publication No 0697234 and United States Patent (USP) 5,648,048 have been described and have been adopted lime stone, quick lime or white lime to carry out the equipment of wet flue gas desulfurization, and the accessory substance of generation is gypsum.United States Patent (USP) 3,914,378; 3,919,393; 3,919,394; 4,487,784; 4,976,936; 4,996,032; 5,047,221 and 5,645,807 have described several different methods, and wherein moisture magnesium fortified lime washing slurries contact with the gas that contains sulfur dioxide in wet purifying decice, form calcium sulfite, and it is abandoned into or is oxidized to and be converted to gypsum.Alternatively, the aqueous solution that magnesium purifies composition can be used for identical object, utilizes lime or magnesium fortified lime regenerated solution as United States Patent (USP) 5,039, and 499 and 5,084, described in 255.Although these methods are feasible technically and certain methods has found to have business application, but still will constantly seek the improvement to purification efficiency, raw material use, fund cost and useless absorbing medium whereabouts.
Summary of the invention
According to a first aspect of the invention, provide oxidation-containing sulfur (SO in a kind of wet purifying decice (wet scrubbing unit)
x) process for desulfurizing gas, the method comprises the following steps:
Described gas is contacted with water-based six water tricalcium aluminate (TCA6) washing slurries, by reacting with TCA6, from gas, remove SO
x, form and comprise the calcium compound that contains sulphur and oxygen and the spend scrub stream (spent scrubbing solution) that contains the aluminium compound of aerobic and hydrogen.
In one form, the calcium compound that contains sulphur and oxygen is that solubility calcium sulfite and the method are further comprising the steps: to be enough to promoting solubility calcium sulfite oxidation to become the amount of solid calcium sulphate that oxygen source is added in spend scrub stream.Being enough to promote solubility calcium sulfite oxidation to become the amount of solid calcium sulphate is every two moles of sulfur dioxide to be removed from gas, at least one mole oxygen.In one form, the aluminium compound that contains aerobic and hydrogen is aluminium hydroxide, and it exists with solid form in spend scrub stream.
The method is further comprising the steps: from spend scrub stream, remove solid calcium sulphate and solid aluminum hydroxide.
Filter aid (filter aid) or the useless filter aid (spent filter aid) of the TCA6 Wei Lai self-alumina refinery advantageously, existing in water-based TCA6 washing slurries.Alternatively or additionally, the TCA6 and the calcium carbonate that in water-based TCA6 washing slurries, exist are present in causticizer underflow mud (causticizer underflow sludge).
In one form, wet purifying decice comprises absorption tower and dust arrester, in dust arrester, by the gas that gas is contacted purifying with the logistics of spend scrub stream, carries out partial desulfurization and cooling.
In one form, the step that gas and water-based TCA6 washing slurries is contacted comprises and TCA6 slurries is sprayed into absorption tower to realize water-based TCA6 slurries being uniformly distributed in the cross section on absorption tower.
In one form, spend scrub stream is collected in and approaches in the circulating tank that the foot on absorption tower arranges for circulation.Optimally, continue circulation water-based TCA6 washing slurries step until the pH of TCA6 washing slurries be reduced to lower than pH5.5 or 5.0.Alternatively or additionally, can continue to circulate the step of water-based TCA6 washing slurries until be disposed to the predetermined maximum discharge limit of reduction of discharging exceedance of levels of the processed gas stream of atmosphere from wet purifying decice.
In one form, from wet purifying decice, be disposed to content of sulfur dioxide that the processed gas stream of atmosphere has and be fed to the oxidation-containing sulfur (SO wet purifying decice
x) gas compares and reduced 90%-100%.Alternatively or additionally, in temperature, be that at 70-90 ℃, processed gas stream is disposed to atmosphere from wet purifying decice.
In one form, by the circulation spend scrub stream of TCA6 source and make-up water source and clarification being mixed together to prepare water-based TCA6 washing slurries.
In one form, a part of spend scrub stream is extracted out to control the time of staying in the water-based TCA6 washing slurries absorption tower in wet purifying decice in place from wet purifying decice continuously.
In one form, by absorption tower circulation TCA6 washing slurries, make the time of staying of water-based TCA6 washing slurries in wet purifying decice about 15 to 90 minutes scopes.
In one form, a part of spend scrub stream of wet purifying decice is imported to retort, wherein by adding sulfuric acid stream to decompose remaining unreacted TCA6 to form the slurries of neutralization.The slurries of neutralization can react with oxygen source, and any residue solubility calcium sulfite being present in the slurries of neutralization is converted into solid calcium sulphate.
In one form, every three moles of sulfur dioxide to be removed from gas, water-based TCA6 washing slurries comprise at least one mole of six water tricalcium aluminates.
According to a second aspect of the invention, provide a kind of with reference to oxidation-containing sulfur (SO in accompanying drawing and the wet purifying decice substantially as described herein as shown in accompanying drawing and example
x) process for desulfurizing gas.
Accompanying drawing explanation
For the ease of understanding in more detail essence of the present invention, only with reference to accompanying drawing, the embodiment of the present invention is described in detail by way of example now, wherein:
Fig. 1 is the indicative flowchart of one embodiment of the present invention.
The specific embodiment
Specifically with reference to TCA6 filter aid, for aluminium oxide refinery flue gas desulfurization (being only example), the specific embodiment of method and system of the present invention is described.The present invention is equally applicable to remove sulfur oxide from the gas of other types, comprises the flue gas of waste gas and power station flue gas Huo Lai self-alumina refinery any fixedly combustion of fossil fuel facility.Term used herein, for describing the specific embodiment, is not only to limit the scope of the invention.Except as otherwise noted, all scientific and technical terminologies used herein all have the identical meanings of conventionally understanding as those skilled in the art.In the accompanying drawings, should be appreciated that identical drawing reference numeral refers to identical parts.
Term " SO
x" refer to sulfur oxide, be generally sulfur dioxide (SO
2) or sulfur trioxide (SO
3).
Term " TCA " refers to pure anhydrous tricalcium aluminate, and having general formula is Ca
3al
2o
6, be also typically expressed as 3CaO.Al
2o
3.
Term " TCA6 " refers to six water tricalcium aluminates, and its general formula is Ca
3[Al (OH)
6]
2, be also typically expressed as 3CaO.Al
2o
3.6H
2o.
Term " gypsum " refers to calcium sulphate dihydrate, and its general formula is CaSO
42H
2o.
Term " gibbsite " refers to the modal form of aluminium hydroxide, and general formula is Al (OH)
3.If while mentioning gibbsite in context, should note other forms of aluminium hydroxide, crystallization and noncrystalline, all applicable equally.
Referring now to indicative flowchart shown in Fig. 1 to oxidation-containing sulfur (SO in a kind of wet purifying decice (14)
x) gas (12) sulfur method (technique) (10) is described.In this example, gas (12) is flue gas.Method (10) comprises the following steps: flue gas (12) is contacted, by reacting the SO containing in gas with TCA6 with water-based six water tricalcium aluminate (TCA6) washing slurries (16)
xremove, form and comprise the solid calcium compound that contains sulphur and oxygen and the spend scrub stream (18) that contains the solid aluminium compound of aerobic and hydrogen.Utilize slush pump (22) to be fed to wet purifying decice (14) preparation water-based TCA6 washing slurries (16) in serum pot (20) before via slurries supply pipe (24).
Adopt method of the present invention, when water-based TCA6 washing slurries (16) are when being present in sulfur dioxide in flue gas (12) and contacting, CaSO
3according to following two kinds of general formulas, form insoluble calcium salt:
SO
2+2H
2O→HSO
3 -+H
3O
+ ...(1)
Ca
3[Al(OH)
6]
2+3HSO
3 -+3H
3O
+→3CaSO
3.
1/
2H
2O+2Al(OH)
3+7
1/
2H
2O...(2)
The sulfur trioxide that meanwhile, can also be present in flue gas will react according to following two kinds of general formulas:
SO
3+2H
2O→HSO
4 -+H
3O
+ ...(3)
Ca
3[Al(OH)
6]
2+3HSO
4 -+3H
3O
+→3CaSO
4.2H
2O+2Al(OH)
3+3H
2O...(4)
By adding oxygen source to promote calcium sulfite to be converted into sulfate precipitate calcium.This is by carrying out according to following formula oxidation calcium sulfite with oxygen (gas):
CaSO
3.
1/
2H
2O+
1/
2O
2+1
1/
2H
2O→CaSO
4.2H
2O ...(5)
Therefore, in a preferred form of the invention, the TCA6 being present in water-soluble serous (16) reacts and adds oxygen source to make solid sulphuric acid calcium precipitate according to following general formula with the sulfur dioxide being present in flue gas (12):
Ca
3[Al(OH)
6]
2+3SO
2+1
1/
2O
2→3CaSO
4.2H
2O+2Al(OH)
3(s)+3H
2O ...(6)
From above-mentioned formula (6), two kinds of product are all solid, specifically contain the solid calcium compound of sulphur and oxygen and the solid aluminium compound containing aerobic and hydrogen of aluminium hydroxide form.Solid can utilize the perfect solid/liquid separation technique in this area separated with spend scrub stream (18).Advantageously, gypsum and aluminium hydroxide are all valuable renewable product.
The TCA6 of useless filter aid form is the waste products of aluminium oxide refinery.In most of aluminium oxide refinery, bauxite digestion in caustic solution (digest) under the temperature and pressure raising.This has produced the mud slurries in concentrating sodium aluminate solution, and it must be clarified and prepare solid-free liquid subsequently, and the thickened drilling fluid that cleans subsequently and abandon.The existing technology of slurries clarification comprises makes solid sedimentation in gravity concentration tank (or heavy mud device), and the decant of clarified solution.Adopt flocculant to assist separated mud and concentrate, only containing " raw (green) " liquid (or mother liquor) of the thinnest suspended solid, from heavy mud device, overflow simultaneously.Generally adopt subsequently filtration method, conventionally adopt filter press further to clarify decant liquid.The importance of this so-called " meticulous (polishing) " filtration step is to guarantee that mother liquor is not containing mud in suspension particle, otherwise can pollute product aluminium oxide.Independently, the cloth fast blocking adopting in these filters.In this, situation is because the thin suspended solid in the liquid of making a living (green liquor) can be captured in the braiding structure of cloth, then continues to continue to form closely knit resistive formation at filter surfaces.For preventing this situation, the common way of aluminium oxide refinery is to fine filter, to supplement charging with so-called " filter aid ", and the solid layer of catching mud particle by continuous formation prevents that cloth from stopping up, and allows liquid Free-flow to cross the space of layer simultaneously.Carefully control the generation of filter aid so that control particle size and form limit limit and the free caustic losses of system of aluminium oxide simultaneously.
In most of aluminium oxide refinery, utilize " newly " water-based six water tricalcium aluminates (TCA6) that filter aid is played a role, (general formula is Ca (OH) to make lime
2) (general formula is NaAl (OH) with sodium aluminate solution
4) reaction formation TCA6.The solubility of TCA6 in Bayer-liquid is extremely low, chemical reactivity is also lower, quite cheap, and the passage that its size makes to be formed between filter aid particle is just enough little to catch mud particle, but no smallly make flowing of their confined liquids, or cause filter cloth self to stop up.The TCA6 filter aid producing has particle diameter relatively uniformly, and each aluminium oxide refinery can be produced into thousands of tons of TCA6 every year as filter aid.After using, filter aid has become " waste product ", and useless TCA6 filter aid is treated as waste products and abandons.Although other silicate, solid oxide and the organic matter that comprise sodalite and minute quantity (conventionally < 1wt%), it is relatively clean and be easy to separated waste material logistics that useless TCA6 filter aid is Bayer process.From simplifying measuring angle, above-mentioned formula (3) shows that every mole of TCA6 can absorb the SO of about three moles
2.Therefore, for about 10, the 000 tons of SO of annual discharge
2aluminium oxide refinery, annual about 20,000 tons of TCA6 can be used for this object.Oxygen (gas) theoretical amount that need to be fed to aqueous slurry can be calculated according to above-mentioned formula (6).Therefore,, when the inventive method is during for the gas sweetening in aluminium oxide refinery the waste gas of its reserve power station (or for the treatment of), useless TCA filter aid becomes very effective desulfurization medium from waste product.
Other TCA6 sources in the waste products that most of aluminium oxide refinery produces are causticizer underflow mud.This waste products comprises the TCA6 of being combined with calcium carbonate.
Get back to Fig. 1, wet purifying decice (14) comprises absorption tower (26) and dust arrester (28).The gas washing (12) is fed to dust arrester (28) via gas access (30).Lid or awning (not shown) can be set above (30) in gas access helps tentatively to make the flue gas (12) of introducing to deflect down to impel gas to flow through more equably wet purifying decice (14).When flue gas (12) enters dust arrester (28), utilize nozzle (32) that flue gas (12) is contacted with the logistics of circulation spend scrub stream (33) to come cooling and remove particulate or " dust ".The temperature of the flue gas (12) that dust arrester (28) entrance (30) is located, between 60 ℃ to 200 ℃, is preferably 70 ℃ to 130 ℃, most preferably is 90 ℃.
According to above-mentioned reaction (1), (2), (3) and (4), any be present in residue in circulation spend scrub stream (33) or unreacted TCA6 can with the sulfur oxide reaction being present in gas (12), during consequently by dust arrester (28), gas (12) is by partial desulfurization.
After gas (12) in dust arrester (28) contacts, circulation waste pulp (33) is collected in dust arrester slurries collecting tank (34) and is convenient to reuse.Then (partially desulphurised) gas (12) of leader desulfurization flows into absorption tower (26), wherein this gas utilizes injection apparatus (38) again to contact with water-based TCA6 washing slurries (16), in this example, a plurality of nozzles (36) realization being set is evenly distributed on water-based TCA6 slurries (16) on the whole cross section on absorption tower (26).Injection apparatus (38) is further arranged to guide water-based TCA6 slurries downwards by absorption tower (26) so that mobile along the direction of smoke gas flow (12) adverse current with the mobile partial desulfurization that makes progress.Processed gas stream (40) is disposed in atmosphere through after one or more fog clearness devices (42).The residue content of sulfur dioxide that processed gas (40) out has from absorption tower (26) is compared and has been reduced 90% to 100% with the content of sulfur dioxide that is fed to the gas (12) in wet purifying decice (14).From absorption tower (26) out time, the temperature of processed gas stream (40) is the scope of 70 ℃ to 90 ℃.
In stirring arm flow container (20), by by the TCA6 source (44) of solid form or thick slurries form and make-up water source (46), the circulation spend scrub stream (48) of for example fresh water (FW) of aluminium oxide refinery and clarification is mixed together to prepare water-based TCA6 and washs slurries (16).
Utilize slush pump (22), water-based TCA6 washing slurries (16) are pumped to circulating tank (50) from serum pot (20), the bottom (52) that circulating tank (50) approaches absorption tower (26) arranges.Then utilize circulating pump (54) that water-based TCA6 washing slurries (16) are pumped to the nozzle (36) of injection apparatus (38) from circulating tank (50).When water-based TCA6 slurries are recycled by absorption tower (26), the reaction of confirming in the formula that reacts (1) and (2) or (3) and (4).By this way, by react the sulfur oxide of removing in gas (12) with TCA6.In circulating tank (50) and inside, absorption tower (26), the time of staying of water-based TCA6 washing slurries (16) was the scope of about 15 to 90 minutes, preferably approximately 25 minutes.
Utilize draw-off pump (58) to extract continuously a part (56) for TCA6 cleaning solution out to control the time of staying of water-based TCA6 washing slurries (16) in absorption tower (26).To utilize a part (56) for the TCA6 cleaning solution of draw-off pump (58) extraction to import dust arrester slurries collecting tanks (34).Utilize pump (62) that the stream (33) of useless washing slurries is circulated to nozzle (32) to carry out cooling to it by the way when gas (12) enters dust arrester (28).To import retort (60) from the remainder waste pulp (61) of dust arrester slurries collecting tank (34), wherein by adding sulfuric acid (64) stream to decompose remaining unreacted TCA6.According to the amount that is present in the remaining unreacted TCA6 in waste pulp (61), add sufficient sulfuric acid (64) to meet above-mentioned reaction equation (4).
Via pump (68), the slurries (66) of neutralization are pumped to oxidizing tower (70), wherein slurries utilize hair-dryer (72) and oxygen source, for example air reaction.According to above-mentioned reaction equation (5), add oxygen source that the solvable calcium sulfite of any residue being present in the slurries (66) of neutralization is converted into solid gypsum.Then via slush pump (74), consequent gypsum and aluminum hydroxide slurry are pumped to suitable solid/liquid separation means (76), produce the spend scrub stream (48) of solid product (73) and clarification.As mentioned above, solid product (78) comprises the solid calcium compound that contains sulphur and oxygen of gypsum form and the solid aluminium compound containing aerobic and hydrogen of aluminium hydroxide form.The recycling or be dropped respectively of gypsum and aluminium hydroxide.The spend scrub stream (48) of clarification can be circulated to by the way serum pot (20) or be dropped.
Continue circulation cleaning slurries (16) until the predetermined maximum discharge limit of the reduction of discharging exceedance of levels of desulfurization fume (40) or until the pH of the spend scrub stream of measuring in slurries collecting tank (34) be reduced to lower than pH5.5 or 5.0.Alternatively, continue circulation cleaning slurries (16) until the pH of the spend scrub stream of measuring in circulating tank (50) is reduced to lower than pH5.5 or 5.0.
Owing to the preferred embodiment of the present invention being have been described in detail, the present invention compared with prior art has a plurality of advantages, comprising:
A) TCA6 reacts with oxidation of sulfur compounds within the scope of very large pH, makes it have Billy by the larger absorbability of the art methods of lime or magnesium;
B) can be by reducing the SO from the flue gas of any fixedly combustion of fossil fuel facility
xthe mode of discharge reclaims useless TCA6 filter aid.When flue gas comes self-alumina refinery, this has solved two environmental problems simultaneously;
C) accessory substance of the method (finally for gypsum and gibbsite) be environmental protection and can be repeated to utilize;
D) TCA6 is with respect to CaCO
3reactivity higher, more allow to set up the facility less, cost is lower;
E) the pattern the method that reclaims aluminium oxide value by providing is very likely brought benefit to aluminum oxide industry, otherwise, if abandon useless TCA filter aid, will lose its value;
While f) being applied to aluminium oxide refinery, do not need new raw material.
Owing to several embodiments of the present invention being have been described in detail, those skilled in the relevant art be it is evident that, in the situation that not deviating from basic inventive concept, can make various changes and modifications.For example, the particle diameter of the gypsum producing is wanted the impact of oxidated speed, and when oxidation rate is high, particle diameter is little.Therefore, if desired trickle grade gypsum accessory substance, can introduce air according to 1.5 to 3 times of the required theoretical amount of above-mentioned formula (6).All these type of modifications and variations are regarded as within the scope of the present invention, according to foregoing description and claims, determine essence of the present invention.
All patents of quoting in description are incorporated to herein by reference.Will be clear that understanding, although quoted a large amount of prior art publications herein, this is quoted and is not admitted that any one document forms this area, a part for Australia or any other national general knowledge.In summary of the invention, description and claim, unless separately there is requirement in context, due to language performance or inevitable implication, term " comprises " or its modified example is used as comprising meaning as " comprising " or " containing ", specify the existence of described feature, but do not get rid of the existence of other features in each embodiment of the present invention or add.
Claims (20)
1. an oxidation-containing sulfur (SO in wet purifying decice
x) sulfur method of gas, the method comprises the following steps:
Described gas is contacted, by reacting from described gas and remove SO with TCA6 with water-based six water tricalcium aluminate (TCA6) washing slurries
xto form, comprise the calcium compound that contains sulphur and oxygen and the spend scrub stream that contains the aluminium compound of aerobic and hydrogen.
2. method according to claim 1, the wherein said calcium compound that contains sulphur and oxygen is that solubility calcium sulfite and the method are further comprising the steps: to be enough to impelling solubility calcium sulfite oxidation to become the amount of solid calcium sulphate that oxygen source is added in described spend scrub stream.
3. method according to claim 2, wherein said to be enough to impel solubility calcium sulfite oxidation to become the amount of solid calcium sulphate be every two moles of at least one mole oxygen of sulfur dioxide needs to be removed from described gas.
4. method according to claim 1, the aluminium hydroxide of the wherein said aluminium compound containing aerobic and hydrogen for existing with solid form in described spend scrub stream.
5. method according to claim 1, further comprises the step of removing solid calcium sulphate and solid aluminum hydroxide from described spend scrub stream.
6. method according to claim 1, filter aid or the useless filter aid of wherein said TCA6 Wei Lai self-alumina refinery.
7. method according to claim 1, wherein said TCA6 and calcium carbonate are present in causticizer underflow mud.
8. method according to claim 1, wherein said wet purifying decice comprises absorption tower and dust arrester, in described dust arrester, by the gas that described gas is contacted purifying with the logistics of described spend scrub stream, carries out partial desulfurization and cooling.
9. method according to claim 1, the step that wherein makes described gas and described water-based TCA6 washing slurries contact comprises and described TCA6 slurries is sprayed into absorption tower to realize described water-based TCA6 slurries being uniformly distributed in the cross section on described absorption tower.
10. method according to claim 8, is wherein collected in described spend scrub stream and approaches in the circulating tank that the foot on described absorption tower arranges for circulation.
11. methods according to claim 1, comprise the following steps: the described water-based TCA6 that circulates washs slurries until the pH of described TCA6 washing slurries is reduced to lower than 5.5 or 5.0.
12. methods according to claim 1, comprise the following steps: the described water-based TCA6 washing slurries that circulate are until be disposed to the predetermined maximum discharge limit of reduction of discharging exceedance of levels of the processed gas stream of atmosphere from described wet purifying decice.
13. methods according to claim 1, are wherein disposed to content of sulfur dioxide that the processed gas stream of atmosphere has and are fed to the oxidation-containing sulfur (SO described wet purifying decice from described wet purifying decice
x) gas compares and reduced 90%-100%.
14. methods according to claim 13, wherein at temperature 70-90 ℃, processed gas stream is disposed to atmosphere from wet purifying decice.
15. methods according to claim 1, wherein by being mixed together the circulation spend scrub stream of TCA6 source and make-up water source and clarification to prepare described water-based TCA6 washing slurries.
16. methods according to claim 1, wherein a part of described spend scrub stream is extracted out to control the time of staying in the described water-based TCA6 washing slurries absorption tower in described wet purifying decice in place from described wet purifying decice continuously.
17. methods according to claim 16, wherein make the time of staying of described water-based TCA6 washing slurries in described wet purifying decice 15 to 90 minutes scopes by the absorption tower described TCA6 washing slurries that circulate.
18. methods according to claim 1, wherein import retort by useless washing slurries described in a part for described wet purifying decice, wherein by adding sulfuric acid stream to decompose remaining unreacted TCA6 to form the slurries of neutralization.
19. methods according to claim 18, wherein, the slurries of described neutralization react with oxygen source, and any residue solubility calcium sulfite being present in the slurries of described neutralization is converted into solid calcium sulphate.
20. methods according to claim 1, every three moles of sulfur dioxide to be removed from gas wherein, described water-based TCA6 washing slurries comprise at least one mole of six water tricalcium aluminates.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2009902853A AU2009902853A0 (en) | 2009-06-19 | Flue Gas Desulphurisation | |
| AU2009902853 | 2009-06-19 | ||
| PCT/AU2010/000758 WO2010144967A1 (en) | 2009-06-19 | 2010-06-17 | Flue gas desulphurisation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102639211A CN102639211A (en) | 2012-08-15 |
| CN102639211B true CN102639211B (en) | 2014-08-27 |
Family
ID=43355609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080025110.3A Expired - Fee Related CN102639211B (en) | 2009-06-19 | 2010-06-17 | Flue gas desulphurisation |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN102639211B (en) |
| AU (1) | AU2010262762B2 (en) |
| BR (1) | BRPI1016040B1 (en) |
| WO (1) | WO2010144967A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108686488B (en) * | 2017-04-12 | 2021-01-01 | 北京华石联合能源科技发展有限公司 | Suspension bed wet desulphurization and regeneration integrated system |
| CN108686474B (en) * | 2017-04-12 | 2021-01-29 | 北京华石联合能源科技发展有限公司 | Efficient desulfurization and regeneration integrated system using suspension bed |
| CN108744863B (en) * | 2018-08-02 | 2024-02-23 | 北京高能时代环境技术股份有限公司 | Wastewater reduction treatment device and method |
| CN109248554A (en) * | 2018-10-17 | 2019-01-22 | 东方希望(三门峡)铝业有限公司 | Flue gas desulfurization device and flue gas desulphurization system |
| CN109675425B (en) * | 2018-12-06 | 2021-06-29 | 昆明理工大学 | System and method for integrated treatment and resource utilization of red mud for flue gas desulfurization and denitrification |
| CN111747432A (en) * | 2019-03-29 | 2020-10-09 | 沈阳铝镁设计研究院有限公司 | Method for improving decomposition yield of alumina plant |
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- 2010-06-17 CN CN201080025110.3A patent/CN102639211B/en not_active Expired - Fee Related
- 2010-06-17 WO PCT/AU2010/000758 patent/WO2010144967A1/en active Application Filing
- 2010-06-17 AU AU2010262762A patent/AU2010262762B2/en not_active Ceased
- 2010-06-17 BR BRPI1016040-0A patent/BRPI1016040B1/en not_active IP Right Cessation
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| US4420465A (en) * | 1981-06-22 | 1983-12-13 | Mitsubishi Jukogyo Kabushiki Kaisha | Process for desulfurizing an exhaust gas |
| US4931264A (en) * | 1986-11-07 | 1990-06-05 | Board Of Regents, The University Of Texas System | Process for removing sulfur from sulfur-containing gases |
| US5047222A (en) * | 1986-11-07 | 1991-09-10 | Board Of Regents, The University Of Texas System | Process for removing sulfur from sulfur-containing gases: high calcium fly-ash |
| US5270015A (en) * | 1986-11-07 | 1993-12-14 | Board Of Regents, The University Of Texas System | Apparatus for removing sulfur from sulfur containing gases |
| CN1344228A (en) * | 1999-03-19 | 2002-04-10 | 沃斯利矾士控股有限公司 | Process for removal of oxalate and/or sulphate from bayer liquors |
| CN1420804A (en) * | 1999-11-12 | 2003-05-28 | 格林威治大学 | Silicate/aluminate materials |
| CN1562446A (en) * | 2004-04-15 | 2005-01-12 | 史汉祥 | Absorbent for 'red mud' sulfur dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010144967A1 (en) | 2010-12-23 |
| BRPI1016040A2 (en) | 2016-05-10 |
| BRPI1016040B1 (en) | 2020-02-18 |
| BRPI1016040A8 (en) | 2017-12-19 |
| CN102639211A (en) | 2012-08-15 |
| AU2010262762A1 (en) | 2011-11-24 |
| AU2010262762B2 (en) | 2013-06-13 |
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