CN1820821A - High efficiency calciam base absorbant for smoke desulfurizing and its preparing method - Google Patents
High efficiency calciam base absorbant for smoke desulfurizing and its preparing method Download PDFInfo
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- CN1820821A CN1820821A CN 200610200082 CN200610200082A CN1820821A CN 1820821 A CN1820821 A CN 1820821A CN 200610200082 CN200610200082 CN 200610200082 CN 200610200082 A CN200610200082 A CN 200610200082A CN 1820821 A CN1820821 A CN 1820821A
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- high efficiency
- calcium
- hydration
- smoke
- lime
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Abstract
The high efficiency calcium base absorbent for fume desulfurizing consists of particles with pores in the surface and produced with calcium aluminosilicate hydrate and flyash through reaction mainly. These particles includes calcium aluminosilicate hydrate, calcium sulfoaluminate hydrate and aluminum silicate. The high efficiency calcium base absorbent is prepared with flyash and lime in the weight ratio of 1-8, and through reaction in a reactor after adding water to form slurry, heating at 70-140 deg.c while stirring for 8-14 hr to produce hydration reaction, and drying and dewatering. It has great specific surface area, high fume desulfurizing efficiency and high utilization rate.
Description
(1), technical field
The present invention relates to a kind of absorbent and preparation method thereof and the method that is applied to boiler smoke semidry method, dry flue gas desulphurization technology.
(2), background technology
The China recent years atmosphere polluting problem is very serious, and its major pollutants are sulfur dioxide and dust, mainly is the coal-smoke pollution that power plant soot and fuel oil produce.Control SO
2The discharged flue gas desulfur technology can be divided into wet method, semidry method and dry process.Wet method is present most widely used mode, but characteristics such as semidry method and dry process are low with its investment, floor space is little, process system is simple, energy consumption is little, flue gas does not need post bake, corrosivity is little, no sewage have also obtained many application, hang down with desulfurization degree low but its main shortcoming is the absorbent utilization rate.
At semidry method and dry flue gas desulphurization technology desulfurization degree and the low this phenomenon of calcium utilization, observe by experiment and theoretical the derivation, in the explanation to this on the microcosmic mechanism be: in drying process with atomizing, Ca (OH)
2Slurries are sprayed into spray tower and flue gas haptoreaction, and reaction product is CaSO
31/2H
2O and CaSO
4, its molal volume is greater than Ca (OH)
2, will stop up Ca (OH)
2The pore of particle.Carry out Ca (OH) along with reaction
2Particle surface is covered by reaction product, has stoped Ca (OH)
2Dissolving and SO
2To its diffusion inside, thereby reaction is stopped, in final dried particles, still having a large amount of absorbent unreacteds.In dry desulfurization, also be that identical mechanism makes CaO fail fully to participate in reacting.
(3), summary of the invention
The purpose of this invention is to provide a kind of high efficiency calciam base absorbant for smoke desulfurizing and preparation method thereof, solve the low and low problem of calcium-base absorbing agent utilization rate of semidry method and dry flue gas desulphurization technology desulfurization degree.
Technical scheme of the present invention: this high efficiency calciam base absorbant for smoke desulfurizing, it is characterized in that: mainly by forming through the particulate that the surface that hydration reaction generates has micropore with lime and flying dust, the component of these particulates is mainly hydration ca aluminosilicate, hydration calcium sulphoaluminate, hydration ca aluminosilicate and alumina silicate.
The chemical composition of above-mentioned key component is:
Afwillite mCaOnSiO
2AH
2O, wherein m＞0, n＞0, a＞0;
Hydration calcium sulphoaluminate 3CaOAl
2O
3CaSO
412H
2O, CaOAl
2O
33CaSO
43H
2O;
Hydration ca aluminosilicate Ca
6Al
1.5(SO
4, SiO
3, CO
3)
3(OH)
10.515H
2O;
Alumina silicate Al
6Si
2O
13
Outside delime and the flying dust, also can add CaSO in addition
4, form multiple high calcium hydrated compound, as: 6CaO2SiO
23H
2O, 6CaO6SiO
2H
2O and 9CaO5SiO
2H
2O.
The preparation method of this high efficiency calciam base absorbant for smoke desulfurizing is characterized in that:
Flying dust and lime are pressed mass ratio 1～8: 1, in reactor, add the slurries that water is made suspended state, and under 70～140 temperature, heat, stirred 8～14 hours, make it that hydration reaction take place, drying and dehydrating forms then.
Above-mentioned flying dust and lime are 4: 1 by mass ratio.
The water-solid ratio of above-mentioned slurries is 10～20: 1.
The water-solid ratio of above-mentioned slurries is 15: 1.
Above-mentioned flying dust is the CaSO that contains that takes from the flyash of electric cleaner or recovery
4Desulfurization flying ash.
Above-mentioned lime is lime stone CaO or calcium hydroxide Ca (OH)
2
The application process of this calcium-base absorbing agent is characterized in that: the calcium-base absorbing agent of aforesaid right requirement 1 or 2 is used for boiler smoke semidry method, dry flue gas desulphurization technology, and the baking temperature of above-mentioned dry flue gas desulphurization technology is 170 ℃.
Operation principle of the present invention: flying dust is the ashes in coal afterburnt, obtains by under the electric cleaner, mainly by SiO
2, Al
2O
3, Fe
2O
3With compositions such as CaO, SiO
2And Al
2O
3Mostly exist with porous amorphous form.Having under the situation of water, fly ash powder can be at normal temperatures reacts with the hydroxide of alkali metal and alkaline-earth metal, and these reactions are called pozzolanic reaction.In hydration reaction, silicon, aluminium ion be free disengaging from flying dust, with CaO or Ca (OH)
2In Ca
2+Hydration forms multiple hydration ca aluminosilicate.Referring to Fig. 1, after the hydration ca aluminosilicate is fully grown up, be generally the imperfect crystal thing, be the fibrous surface that is deposited on flying dust, form cellular porous particle with very big specific area and high retentiveness.Referring to Fig. 2, the surface micropore size of these cellular porous particles can be effectively with SO about 0.2-1um
2Be transported to granule interior Deng reacting gas, and enough reaction contact-making surfaces are provided, make Ca
2+And SO
2Fully reaction has strengthened SO
2Absorbability, improved desulfurization degree.The specific area of hydration ca aluminosilicate is big more, and activity is big more, reacts abundant more, and it is blocking microporous to be generated thing, does not have the unreacted core, and calcium utilization is improved.The high retentiveness of hydration ca aluminosilicate increases humidity, and the carrying out that has quickened surface reaction significantly strengthened the activity of absorbent, significantly improved semidry method and dry flue gas desulphurization technology desulfurization degree.
Following table is the various calcium-base absorbing agents of the present invention and traditional absorbent activity comparing data:
| The absorbent kind | The hydrate composition | Specific area (m 2/g) | Reaction time |
| The tradition absorbent | Do not have | 2.60 | Unreacted state |
| Absorbent of the present invention | The hydration ca aluminosilicate | 5.31 | Reaction was carried out 6 hours |
| Absorbent of the present invention | Hydration ca aluminosilicate, calcium aluminate, ca aluminosilicate | 35.64 | Reaction was carried out 12 hours |
| Absorbent of the present invention | Hydration ca aluminosilicate, calcium aluminate, ca aluminosilicate | 32.12 | Reaction was carried out 20 hours |
Experiment showed, calcium-base absorbing agent of the present invention, its specific area is by original 1.048m
2/ g is increased to 35.64m
2/ g.The activity of calcium-base absorbing agent is increased greatly, utilize casting bed reactor test shows, compare with CaO, calcium utilization brings up to 92% by original 65%, and desulfurization degree brings up to 89% by original 70%.Significantly improved the utilization rate of calcium-base absorbing agent in semidry method and the dry flue gas desulphurization technology.
(4), description of drawings
Fig. 1 is the microstructure aspect graph of a bead particles in the high efficiency calciam base absorbant of the present invention;
Fig. 2 is the microstructure aspect graph on bead particles surface among Fig. 1.
(5), the specific embodiment
Embodiment: mainly by forming through the particulate that the surface that hydration reaction generates has micropore with lime and flying dust, the component of these particulates is mainly hydration ca aluminosilicate, hydration calcium sulphoaluminate, hydration ca aluminosilicate and alumina silicate to this high efficiency calciam base absorbant for smoke desulfurizing of the present invention.The chemical composition of above-mentioned key component is:
Afwillite mCaOnSiO
2AH
2O, wherein m＞0, n＞0, a＞0;
Hydration calcium sulphoaluminate 3CaOAl
2O
3CaSO
412H
2O, CaOAl
2O
33CaSO
43H
2O;
Hydration ca aluminosilicate Ca
6Al
1.5(SO
4, SiO
3, CO
3)
3(OH)
10.515H
2O;
Alumina silicate Al
6Si
2O
13
The calcium-base absorbing agent sample that is prepared into is carried out the X diffraction analysis, measure its thing phase composition.Measurement result shows: flying dust and lime can mainly form following compound through hydration reaction:
CaO·SiO
2·H
2O、
2CaO·SiO
2·H
2O、
3CaO·Al
2O
3·CaSO
4·12H
2O、
CaO·Al
2O
3·3CaSO
4·3H
2O、
Ca
6Al
1.5(SO
4，SiO
3，CO
3)
3(OH)
10.5·15H
2O、Al
6Si
2O
13。
Add CaSO
4, can form more kinds of high calcium hydrated compounds, as:
6CaO2SiO
23H
2O, 6CaO6SiO
2H
2O and 9CaO5SiO
2H
2O.
Preparation method of the present invention: flying dust and lime are pressed mass ratio n: 1 mixes, and (n is any number greater than 1), best mixing ratio is 4: 1, adds the slurries that water is made suspended state in reactor, and water-solid ratio is 10～20: 1, and optimal proportion is 15: 1.Heat under 70～100 temperature, stirred 8～14 hours, make it that hydration reaction take place, drying and dehydrating forms then.
The flying dust CaSO that contains of the flyash of two, three grades of electric cleaners or recovery that should ask for
4Desulfurization flying ash.Lime is lime stone CaO or calcium hydroxide Ca (OH)
2Calcium-base absorbing agent of the present invention is used for dry desulfurization, and baking temperature is 170 ℃, adds CaSO
4Can strengthen Ca
2+Effect helps the increase of calcium-base absorbing agent specific area, from economic considerations, can will contain CaSO
4The desulfurization flying ash recycling.
Claims (10)
1. high efficiency calciam base absorbant for smoke desulfurizing, it is characterized in that: mainly by forming through the particulate that the surface that hydration reaction generates has micropore with lime and flying dust, the component of these particulates is mainly hydration ca aluminosilicate, hydration calcium sulphoaluminate, hydration ca aluminosilicate and alumina silicate.
2. high efficiency calciam base absorbant for smoke desulfurizing according to claim 1 is characterized in that: the chemical composition of above-mentioned key component is:
Afwillite mCaOnSiO2aH2O, wherein m＞0, n＞0, a＞0;
Hydration calcium sulphoaluminate 3CaOAl2O3CaSO412H2O, CaOAl2O33CaSO43H2O;
Hydration ca aluminosilicate Ca6Al1.5 (SO4, SiO3, CO3) 3 (OH) 10.515H2O;
Alumina silicate Al6Si2O13.
3. high efficiency calciam base absorbant for smoke desulfurizing according to claim 1 is characterized in that: outside delime and the flying dust, other adds CaSO4, forms multiple high calcium hydrated compound, as: 6CaO2SiO23H2O, 6CaO6SiO2H2O and 9CaO5SiO2H2O.
4. the preparation method of a high efficiency calciam base absorbant for smoke desulfurizing is characterized in that:
Flying dust and lime are pressed mass ratio 1～8: 1, in reactor, add the slurries that water is made suspended state, and under 70～140 temperature, heat, stirred 8～14 hours, make it that hydration reaction take place, drying and dehydrating forms then.
5. the preparation method of high efficiency calciam base absorbant for smoke desulfurizing according to claim 4, it is characterized in that: above-mentioned flying dust and lime are 4: 1 by mass ratio.
6. the preparation method of high efficiency calciam base absorbant for smoke desulfurizing according to claim 4, it is characterized in that: the water-solid ratio of above-mentioned slurries is 10～20: 1.
7. the preparation method of high efficiency calciam base absorbant for smoke desulfurizing according to claim 4, it is characterized in that: the water-solid ratio of above-mentioned slurries is 15: 1.
8. the preparation method of high efficiency calciam base absorbant for smoke desulfurizing according to claim 4, it is characterized in that: above-mentioned flying dust is to take from the flyash of electric cleaner or the desulfurization flying ash that contains CaSO4 of recovery.
9. the preparation method of high efficiency calciam base absorbant for smoke desulfurizing according to claim 4, it is characterized in that: above-mentioned lime is lime stone CaO or calcium hydroxide Ca (OH) 2.
10. the application process of a calcium-base absorbing agent is characterized in that: aforesaid right is required 1 or 2 or 3 calcium-base absorbing agent be used for boiler smoke semidry method, dry flue gas desulphurization technology, the baking temperature of above-mentioned dry flue gas desulphurization technology is 170 ℃.
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|---|---|---|---|
| CN 200610200082 CN1820821A (en) | 2006-01-25 | 2006-01-25 | High efficiency calciam base absorbant for smoke desulfurizing and its preparing method |
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|---|---|---|---|
| CN 200610200082 CN1820821A (en) | 2006-01-25 | 2006-01-25 | High efficiency calciam base absorbant for smoke desulfurizing and its preparing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664842A (en) * | 2016-04-07 | 2016-06-15 | 景德镇陶瓷学院 | Calcium-based adsorbent for defluorination and application thereof |
| CN108212075A (en) * | 2018-01-19 | 2018-06-29 | 临沂三禾生物质科技有限公司 | It is a kind of can efficient absorption and catalytic degradation formaldehyde novel porous nano material preparation method |
| CN108404643A (en) * | 2018-05-25 | 2018-08-17 | 华北电力大学 | Coal-fired power station boiler compressed air is atomized calcium-based slurries and removes SO3Device and method |
| CN113856450A (en) * | 2021-09-14 | 2021-12-31 | 中国辐射防护研究院 | Alkaline material for removing acid gas in flue gas and preparation method thereof |
-
2006
- 2006-01-25 CN CN 200610200082 patent/CN1820821A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664842A (en) * | 2016-04-07 | 2016-06-15 | 景德镇陶瓷学院 | Calcium-based adsorbent for defluorination and application thereof |
| CN108212075A (en) * | 2018-01-19 | 2018-06-29 | 临沂三禾生物质科技有限公司 | It is a kind of can efficient absorption and catalytic degradation formaldehyde novel porous nano material preparation method |
| CN108212075B (en) * | 2018-01-19 | 2020-11-27 | 临沂三禾生物质科技有限公司 | Preparation method of novel porous nano material capable of efficiently adsorbing and catalytically degrading formaldehyde |
| CN108404643A (en) * | 2018-05-25 | 2018-08-17 | 华北电力大学 | Coal-fired power station boiler compressed air is atomized calcium-based slurries and removes SO3Device and method |
| CN113856450A (en) * | 2021-09-14 | 2021-12-31 | 中国辐射防护研究院 | Alkaline material for removing acid gas in flue gas and preparation method thereof |
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