CN103537185A - Desulfurization and denitrification agent with pickling waste residues from steel and iron plants as main materials and removal method - Google Patents
Desulfurization and denitrification agent with pickling waste residues from steel and iron plants as main materials and removal method Download PDFInfo
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- CN103537185A CN103537185A CN201310529912.3A CN201310529912A CN103537185A CN 103537185 A CN103537185 A CN 103537185A CN 201310529912 A CN201310529912 A CN 201310529912A CN 103537185 A CN103537185 A CN 103537185A
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- desulfurization
- bed
- denitrification agent
- acid cleaning
- cleaning waste
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Links
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 46
- 230000023556 desulfurization Effects 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 22
- 239000010959 steel Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 7
- 238000005554 pickling Methods 0.000 title claims abstract description 7
- 241001232253 Xanthisma spinulosum Species 0.000 title abstract 2
- 238000005243 fluidization Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 239000010431 corundum Substances 0.000 claims abstract description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007921 spray Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims description 32
- 239000002893 slag Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 30
- 239000004615 ingredient Substances 0.000 claims description 11
- 230000005587 bubbling Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 235000021110 pickles Nutrition 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000809 air pollutant Substances 0.000 description 2
- 231100001243 air pollutant Toxicity 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011554 ferrofluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention provides a desulfurization and denitrification agent with pickling waste residues from steel and iron plants as main materials and a removal method. The removal method is characterized by mixing 50-80% of pickling waste residue fine powder, 5-30% of calcium hydroxide fine powder and 5-30% of calcium hypochlorite fine powder by mass, then adding water to the mixture according to a mass ratio of 1/(95-99.5), and stirring the mixture for 10-60 minutes, thus preparing desulfurization and denitrification agent slurry; enabling gases to be removed at 110-140 DEG C to enter a fluidization device with corundum sphere filling height of 1.5-4m from the bottom, wherein the apparent velocity of the gases based on the bed cross section is 0.01-1.0m/s; uniformly spraying the slurry onto the surfaces of the corundum spheres by a spray device arranged 0.5-3m above the charge level of a bed of the fluidization device, wherein the spray density is (1-10)m<3>/(m<2>.h). The desulfurization and denitrification agent and the removal method can be applied to the fields such as steel and iron, power, energy and environmental protection.
Description
Technical field
The present invention relates to a kind of desulfurization denitrification agent and removal methods that steel plant's acid cleaning waste slag is major ingredient of take, be particularly related to a kind of utilize that steel plant's acid cleaning waste slag removes the sulfide in boiler smoke and nitride remove agent and method, belong to iron and steel, electric power, the energy, chemical industry and field of Environment Protection.
Background technology
SO in boiler smoke
2and NO
xit is the main component of atmosphere pollution, < < discharge standard of air pollutants > > (GB16297-1996) in China's issuing and implementation, < < emission standard of air pollutants for boilers > > (GB13271-2001), < < industrial furnace atmosphere pollutants emission standards > > (GB9078-1996), in the series standards such as < < fossil-fuel power plant atmospheric pollutant emission standard > > (GB13223-2003) and rules, all its content is had to clear and definite restriction.Due to SO
2and NO
xbe present in flue gas, if it is taked to the method that removes respectively, by bringing, equipment is various, the problem of complicated operation simultaneously.From SO
2and NO
xfeature, they are all acidic oxides, they are removed feasiblely simultaneously, also have at present some Industrial demonstrations and business running gear.The integrated method of current flue gas desulfurization and denitrification is mainly divided into three kinds of wet desulphurization denitration, dry desulfurization denitration and semi-dry desulfurization and denitrifications.Generally speaking, wet method removal effect is good, but waste liquor contamination is serious; Dry removal is effective, but operating cost is high; Semidry method has the advantage of dry and wet way concurrently, but also has the problem of fluctuation of service.In the process of preparation integration desulfurization denitration agent, most formulas adopt various pure active principles to carry out the method for mixed preparing, cause thus desulfurization denitrification agent cost higher.
China steel mill great majority adopt hydrochloric acid or sulfuric acid solution to clean steel surface, generally contain the H of (0.05～5) g/L in the pickle liquor after cleaning
+the Fe of (60～250) g/L
2+and Fe
3+, and if waste liquid after processing does not reclaim and utilization can cause the wasting of resources and environmental pollution.The method of recycling treatment pickle liquor mainly contains and reclaims molysite, prepares ferrofluid, prepares inorganic polymer flocculant etc. at present.Although the research of pickle liquor recycling treatment report is more, but due to the factor such as simple to operate, with low cost, a lot of steel mills still adopt traditional quick lime, calcium hydroxide or lime stone neutralisation, intractability is larger again for consequent waste residue (being called for short " acid cleaning waste slag "), takies a large amount of soils simultaneously and causes the wasting of resources and secondary pollution.The research of the industrial residue recyclings such as white clay, red mud, carbide slag is more, and aspect boiler flue gas desulfurization, has obtained paying attention to and application, less but acid cleaning waste slag is reported in this respect.
By acid cleaning waste slag being carried out to the result of XRF detection, show, acid cleaning waste slag mainly contains CaSO
4, Ca (OH)
2, CaCO
3, Fe
3o
4and SiO
2, be secondly the trace elements such as Mg, Al, Ti, Mn and Zr, wherein Ca (OH)
2, CaCO
3deng the active ingredient that is desulphurization denitration, the oxide of Fe etc. has significant facilitation to sweetening process.The result of acid cleaning waste slag being tested by BET method shows, being shaped as of acid cleaning waste slag particle hole is cylindric, pore size be take mesoporous as main, micropore and macropore are less, further calculate, in total pore volume distributes, micropore accounts for 2.65%, mesoporously account for 83.3%, macropore accounts for 14.05%, and specific area reaches 43.94m
2/ g, makes the specific area of desulfurization denitrification agent apparently higher than lime stone and shell.Therefore, composition and particle hole characteristic from acid cleaning waste slag, can meet the requirement of boiler flue gas desulfurization denitration.
Active constituent content from acid cleaning waste slag desulphurization denitration, its active ingredient quality percentage composition is 25%～30% left and right, if adopt single acid cleaning waste slag, carry out desulphurization denitration, meeting under the prerequisite of higher denitrification efficiency, the unit amount of removing needs a large amount of acid cleaning waste slag, thereby needs larger equipment and higher operating cost.Therefore, can consider take that acid cleaning waste slag is as major ingredient, then add that the auxiliary material preparation of a certain amount of desulphurization denitration is compound removes agent, thereby realize acid cleaning waste slag recycling, reach the object of the treatment of wastes with processes of wastes against one another.
Summary of the invention
The object of the invention is to, realize the secondary utilization of steel plant's acid cleaning waste slag, for boiler flue gas desulfurization denitration provides a kind of simple, with low cost method that removes agent and efficiently remove of preparing.
Object of the present invention realizes by following approach:
The desulfurization denitrification agent that the steel plant's acid cleaning waste slag of take is major ingredient, is characterized in that major ingredient is steel plant's acid cleaning waste slag, and auxiliary material is calcium hydroxide and calcium hypochlorite; On three kinds of material proportions, described acid cleaning waste slag quality percentage composition is 50%～80%, and the quality percentage composition of described calcium hydroxide is 5%～30%, and the quality percentage composition of described calcium hypochlorite is 5%～30%.
Described acid cleaning waste slag is steel plant's hydrochloric acid pickling waste liquor or the waste residue product of sulfuric acid pickling waste liquid after calcium hydroxide neutralisation treatment, and after grinding, fine powder footpath is less than 200 μ m; Described calcium hydroxide and calcium hypochlorite are the powder that particle diameter is less than 100 μ m, and purity is 90%～99%.
A kind ofly take the desulfurization denitrification agent removal methods that steel plant's acid cleaning waste slag is major ingredient, it is characterized in that desulfurization denitrification agent to stir and make slurries with water under normal temperature, normal pressure, the mass ratio of desulfurization denitrification agent and water is 1/ (95～99.5), and mixing time is (10～60) min; Denitration gas to be desulfurization enters by bottom the fluidization equipment that an inside is filled with corundum ball, slurries are evenly sprayed at corundum ball surface through being arranged on the spray equipment of fluidization equipment upper space, denitration gas to be desulfurization once removes and reacts with the desulfurization denitrification agent that sticks to corundum ball surface, and the denitration gas to be desulfurization after primary first-order equation flows out to contact with the slurries of bed superjacent air space after fluidized-bed layer and carries out secondary and remove reaction; Gas after desulphurization denitration and partial desulfurization denitration solid product are through being arranged on the gas-solid separating device separation of fluidization equipment outlet.
Described denitration gas intake air temperature to be desulfurization is (110～140) ℃, and the gas superficial flow velocity based on fluidization equipment bed sectional area is (0.01～1.0) m/s; Described fluidization equipment is bubbling bed, turbulent bed or spouted bed, and bed loading height is (1.5～4) m; Described corundum spherolite footpath is (0.5～3) mm; The space length of described spray equipment and fluidized-bed bed boundary is (0.5～3) m, and the desulfurization denitrification agent slurries sprinkle density based on fluidization equipment bed sectional area is (1～10) m
3/ (m
2.h).
The present invention compared with prior art, exists obvious advantage to be: (1) has realized the secondary utilization of acid cleaning waste slag, has reached the object of the treatment of wastes with processes of wastes against one another; (2) with low cost, the preparation of desulfurization denitrification agent and removal methods are simple; (3) in desulphurization denitration process, can also realize the object of boiler smoke dedusting simultaneously.
Accompanying drawing explanation
Accompanying drawing is desulfurization denitrification agent slurries preparation of the present invention and desulphurization denitration schematic flow sheet.
The specific embodiment
Below by specific embodiment, also describe by reference to the accompanying drawings the present invention in detail.
A: desulphurization denitration slurries preparation process
Referring to accompanying drawing, acid cleaning waste slag from Bazhou, Hebei steel plant is pulverized, grinds, sieved, take the fine powder mass M 1=18kg that particle diameter is less than 200 μ m, the calcium hydroxide and the calcium hypochlorite that take respectively again purity and be 95%, diameter of particle are all less than 100 μ m, quality is respectively M2=M3=6kg, take again the water that quality is M4=3000kg, the acid cleaning waste slag taking, calcium hydroxide, calcium hypochlorite, water are added to agitator, put into storage tank stir 30min under normal temperature, normal pressure after standby.
B: desulphurization denitration flow process
Referring to accompanying drawing, the fluidization equipment of desulphurization denitration adopts bubbling bed, and bubbling bed body interior is filled with the corundum ball that particle diameter is 2mm, and loading height is 1.5m; Above corundum ball charge level, 2m place is provided with 1 sprinkle nozzle spray equipment.Gas to be removed is boiler smoke, wherein SO
2content is 3600mg/m
3, NO content is 1200mg/m
3, NO
2content is 800mg/m
3, flue gas enters bubbling bed desulfuring and denitrifying apparatus by bottom, and feeding temperature is 120 ℃, and the apparent velocity based on bubbling bed cross section is 0.1m
3/ s.The desulfurization denitrification agent slurries that prepare, spray in bubbling bed through sprinkle nozzle spray equipment, based on the long-pending sprinkle density of bubbling bed main body section, are 1.0m
3/ (m
2h).Flue gas once removes and reacts with the desulfurization denitrification agent that sticks to corundum ball surface, and flue gas after primary first-order equation flows out to contact with the slurries of bed superjacent air space after bed and carries out secondary and remove reaction; Flue gas after desulphurization denitration and partial desulfurization denitration solid product are through being arranged on the gas-solid separating device separation of bubbling bed main body outlet, and flue gas enters subsequent treatment system, and solid product is collected.Adopt flue gas analyzer to detect exit gas concentration, testing result demonstration, adopts desulfurization denitrification agent provided by the invention and removal methods, and desulfurization degree is 90%～98%, and denitration rate is 65%～81%.
Finally it should be noted that: above embodiment is only in order to illustrate the present invention and unrestricted technical scheme described in the invention; Therefore, although this description has been described in detail the present invention with reference to each above-mentioned embodiment,, those of ordinary skill in the art should be appreciated that still and can modify or be equal to replacement the present invention; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (4)
- The desulfurization denitrification agent that 1.Yi Zhongyi steel plant acid cleaning waste slag is major ingredient, is characterized in that major ingredient is steel plant's acid cleaning waste slag, and auxiliary material is calcium hydroxide and calcium hypochlorite; On three kinds of material proportions, described acid cleaning waste slag quality percentage composition is 50%～80%, and the quality percentage composition of described calcium hydroxide is 5%～30%, and the quality percentage composition of described calcium hypochlorite is 5%～30%.
- 2. a kind of desulfurization denitrification agent that steel plant's acid cleaning waste slag is major ingredient of take according to claim 1, it is characterized in that described acid cleaning waste slag is steel plant's hydrochloric acid pickling waste liquor or the waste residue product of sulfuric acid pickling waste liquid after calcium hydroxide neutralisation treatment, after grinding, fine powder footpath is less than 200 μ m; Described calcium hydroxide and calcium hypochlorite are the powder that particle diameter is less than 150 μ m, and purity is 90%～99%.
- The desulfurization denitrification agent removal methods that 3.Yi Zhongyi steel plant acid cleaning waste slag is major ingredient, it is characterized in that desulfurization denitrification agent to stir and make slurries with water under normal temperature, normal pressure, the mass ratio of desulfurization denitrification agent and water is 1/ (95～99.5), and mixing time is (10～60) min; Denitration gas to be desulfurization enters by bottom the fluidization equipment that an inside is filled with corundum ball, slurries are evenly sprayed at corundum ball surface through being arranged on the spray equipment of fluidization equipment upper space, denitration gas to be desulfurization once removes and reacts with the desulfurization denitrification agent that sticks to corundum ball surface, and the denitration gas to be desulfurization after primary first-order equation flows out to contact with the slurries of bed superjacent air space after fluidized-bed layer and carries out secondary and remove reaction; Gas after desulphurization denitration and partial desulfurization denitration solid product are through being arranged on the gas-solid separating device separation of fluidization equipment outlet.
- 4. a kind of desulfurization denitrification agent removal methods that steel plant's acid cleaning waste slag is major ingredient of take according to claim 3, it is characterized in that described denitration gas intake air temperature to be desulfurization is for (110～140) ℃, the gas superficial flow velocity based on fluidization equipment bed sectional area is (0.01～1.0) m/s; Described fluidization equipment is bubbling bed, turbulent bed or spouted bed, and bed loading height is (1.5～4) m; Described corundum spherolite footpath is (0.5～3) mm; The space length of described spray equipment and fluidized-bed bed boundary is (0.5～3) m, and the desulfurization denitrification agent slurries sprinkle density based on fluidization equipment bed sectional area is (1～10) m 3/ (m 2h).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310529912.3A CN103537185B (en) | 2013-10-30 | 2013-10-30 | It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310529912.3A CN103537185B (en) | 2013-10-30 | 2013-10-30 | It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103537185A true CN103537185A (en) | 2014-01-29 |
| CN103537185B CN103537185B (en) | 2018-07-27 |
Family
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| CN201310529912.3A Expired - Fee Related CN103537185B (en) | 2013-10-30 | 2013-10-30 | It is a kind of using steel plant's acid cleaning waste slag as the desulfurization denitrification agent of major ingredient and removal methods |
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Cited By (3)
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| CN107573980A (en) * | 2017-09-11 | 2018-01-12 | 天津市职业大学 | A kind of coal supply chain combustion adjuvant and preparation method thereof |
| CN108905615A (en) * | 2018-08-31 | 2018-11-30 | 江苏绿景环保设备有限公司 | Smoke processing system and method after a kind of dangerous waste incineration |
| CN114082288A (en) * | 2020-06-08 | 2022-02-25 | 广东赛珐生物科技有限公司 | New application of folic acid wastewater |
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| CN101703886A (en) * | 2009-10-29 | 2010-05-12 | 太原理工大学 | Desulfuration method by directly utilizing magnesium slags in circulating fluidized bed boiler |
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| CN1268387A (en) * | 1999-03-29 | 2000-10-04 | 青岛海洋大学 | Method for removing sulfur oxides from flue-gas by utilizing waste sludge of soda plant |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103537185B (en) | 2018-07-27 |
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