CN104759203B - Fluidized bed process and system for directly capturing carbon dioxide in mineralized flue gas - Google Patents
Fluidized bed process and system for directly capturing carbon dioxide in mineralized flue gas Download PDFInfo
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- CN104759203B CN104759203B CN201510116682.7A CN201510116682A CN104759203B CN 104759203 B CN104759203 B CN 104759203B CN 201510116682 A CN201510116682 A CN 201510116682A CN 104759203 B CN104759203 B CN 104759203B
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- flue gas
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- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 239000003546 flue gas Substances 0.000 title claims description 84
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 76
- 239000010881 fly ash Substances 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000003517 fume Substances 0.000 claims abstract description 8
- 230000033228 biological regulation Effects 0.000 claims abstract description 7
- 239000000292 calcium oxide Substances 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 16
- 239000010813 municipal solid waste Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 239000000779 smoke Substances 0.000 claims description 8
- 230000004308 accommodation Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000009257 reactivity Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 235000019504 cigarettes Nutrition 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000002893 slag Substances 0.000 abstract description 11
- 239000004568 cement Substances 0.000 abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 4
- 238000005262 decarbonization Methods 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000010883 coal ash Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000005997 Calcium carbide Substances 0.000 abstract 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 17
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 16
- 229960004424 carbon dioxide Drugs 0.000 description 16
- 239000012530 fluid Substances 0.000 description 13
- 239000002956 ash Substances 0.000 description 10
- 238000005261 decarburization Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 210000004127 vitreous body Anatomy 0.000 description 2
- UUNNUENETDBNPB-HKBOAZHASA-N (2s)-2-[[(2s,3r)-3-amino-2-hydroxy-4-(4-phenylmethoxyphenyl)butanoyl]amino]-4-methylpentanoic acid Chemical compound C1=CC(C[C@@H](N)[C@H](O)C(=O)N[C@@H](CC(C)C)C(O)=O)=CC=C1OCC1=CC=CC=C1 UUNNUENETDBNPB-HKBOAZHASA-N 0.000 description 1
- 239000010754 BS 2869 Class F Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Treating Waste Gases (AREA)
Abstract
A fluidized bed process for directly collecting the carbon dioxide in mineralized fume features that the high-calcium wastes such as powdered coal ash, calcium carbide dregs, steel slag and waste cement are used as raw materials, a by-pass is opened on fume exhaust flue to regulate temp and humidity, the fume after temp and humidity regulation and high-calcium wastes are contacted in fluidized bed reactor to generate calcium carbonate, the dust-contained gas coming out of fluidized bed reactor after reaction is fed to cyclone separator for gas-solid separation, and the gas is returned to original fume exhaust flue and exhausted to flue2The method has the advantages of simple discharge, simple flow, convenient continuous operation, large treatment capacity of the device, small size, small occupied area, convenient combination with the existing system of the power plant, no influence on the original use way of the fly ash of the power plant due to decarbonization, and lower decarbonization cost.
Description
Technical field
The present invention relates to smoke carbon dioxide capture with utilize technical field, particularly to a kind of directly trapping mineralising flue gas
The fluidized-bed process of middle carbon dioxide and system.
Background technology
Atmospheric greenhouse gas concentration raises the Global Greenhouse Effect causing, and causes iceberg thawing, sea level rise, species
Reduce, the multiple climate damage in all parts of the world takes place frequently, bring serious financial consequences and threaten human survival.Carbon dioxide (CO2) make
It is its following overall control of topmost greenhouse gases and Emission Right distribution has become as the emphasis of international climate negotiation.Various countries
Government and energy enterprise have increasingly paid attention to CO2The research of emission control technique, some countries have taken the lead in having started essence
Property decarburization work.Exceed the U.S. and the reinforcement of the international cry reducing discharging with China's carbon emission amount, the Chinese government is 2009
Year the world is made with promise and reduce 40-45% to the year two thousand twenty per GDP carbon emission amount.The resource of China's " rich coal, few oil have gas "
General layout determines the main body that coal is China's energy supply, in China's primary energy coal fired power generation proportion close to 65%, institute
With CO2Discharge, essentially from coal-burning power plant, accounts for the 40-50% always discharging.Power plant's collecting carbonic anhydride is inevitable with Plugging Technology Applied
Become long-term technical need in China's low carbon development strategy.
CO2Mineralising is sealed up for safekeeping will CO2React production carbon with the alkaline-earth metal in Ore or solid waste under certain condition
Hydrochlorate is realizing the technology of carbon sequestration.This technology can achieve CO2Forever seal up for safekeeping, environmental risks are little, and available mineral resources are wide,
Ability of sealing up for safekeeping is strong, is the very potential Technology of Reducing Greenhouse Gas Emissions of one kind.However, the CO due to exploitation at present2Mineralising work
There is long flow path in skill, reaction rate is low, and equipment size is big, severe reaction conditions, high energy consumption, and chemical reagent reclaims difficult, generation
The shortcomings of secondary pollution, and main research abroad to be suitable as the Ores such as serpentine, the olivine of mineralising raw material normal in China
As there being artware to process raw material, lead to cost of material high.These all hamper CO2Mineralising Plugging Technology Applied is in the commercialization of China
Process.
On the other hand, the annual emissions of China's coal-burning power plant's flyash have reached 100,000,000 tons, some flyash calcium oxide
(CaO) content higher (mass fraction is up to more than 20%), is highly suitable for mineralising and seals the CO in coal-fired flue-gas up for safekeeping2.Additionally,
The solid waste also having a large amount of carbides, cement and iron and steel enterprise to be produced, is also enriched in CaO, also can be used as the raw material of mineralising.Institute
So that solid waste can be selected as CO by treatment in accordance with local conditions in China2The raw material that mineralising is sealed up for safekeeping.
Content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of directly trap in mineralising flue gas
The fluidized-bed process of carbon dioxide and system, are raw material using high calcium garbage (flyash, carbide slag, slag, waste and old cement),
Using CO in the trapping of gas-solid phase direct reaction fluidized-bed process simultaneously mineralising flue gas2, the utilization of flyash can not only be effectively improved, and
And CO can be reduced2Discharge, is a kind of novel greenhouse gas abatement technology being especially suitable for China's national situation.
To achieve these goals, the technical solution used in the present invention is：
A kind of fluidized-bed process directly trapping mineralising carbon dioxide in flue gas, comprises the following steps：
The first step, collects the grinding of high calcium garbage stand-by；
Second step, opens bypass on fume emission flue and draws one flue gas through temperature and humidity regulator regulation temperature and humidity, temperature
Degree range of accommodation is 40-90 DEG C, and the range of accommodation of humidity is 5-60% (relative humidity)；
3rd step, in a fluidized bed reactor that the flue gas after temperature and humidity regulation is with described high calcium garbage and anti-to contacting
Should；
4th step, the dusty gas feeding cyclone separator going out fluidized-bed reactor after reaction carries out gas solid separation, gained
Gas is sent former fume emission flue back to and is entered smoke stack emission.
Wherein, described high calcium garbage can be flyash, carbide slag, slag or waste and old cement etc., and general requirement is wherein
CaO mass fraction is more than 20%, and granularity is 20-80 micron, has preferable chemical reactivity.Therefore, depending on concrete condition
See whether need for flyash to carry out pretreatment, preprocess method mainly has three kinds：At fine gtinding, heat treatment and alkaline process desiliconization
Reason.Preprocess method can be used from one or more according to the concrete condition of raw material simultaneously, to reach direct mineralising fluid bed
The requirement of technique.Judge that raw material has grain graininess, crystal phase structure and 3 points of CaO content the need of the standard of pretreatment.Take ash
After sample is analyzed, targetedly adopt different pretreatments method in light of the circumstances.
Flue gas be power-plant flue gas, high calcium garbage be power-plant flue gas electrostatic precipitation after gained flyash when it is achieved that electricity
The trapping to itself carbon dioxide in flue gas for factory's flyash.
For example, when from flyash, analyzed and processed as follows：
(1) whether there is the granularity of 30-80 micron, generally, the granularity of flyash in 40 microns, this granularity
Just it is suitable for minimum fluidization velocity needed for fluid bed it may not be necessary to attrition grinding again, but live sometimes for improving reaction further
Property can using fine gtinding destroy flyash glass phase crystal structure create more lattice defects, grain after further fine gtinding
Degree is reduced to 20 microns.
(2), mainly based on corundum-mullite and glass phase, structure is comparatively dense for the crystalline phase in flyash, and surface activity is not
High.This is primarily due to caused by flyash is the crystal rapidly cooling to form bead shape in flue, can be using high under 600 degree
Warm processes 2 hours crystal structures to destroy bead surface to improve its chemical reactivity.
(3) whether CaO content needs to reach more than 20%, and such as C level flyash can not do pretreatment, and F level flyash need to do
Alkaline process desiliconization is processed, and typically adopts NaOH or NaCO of 0.5-2mol/l3Solution presses solid-to-liquid ratio 100-250g/l by flyash
Hydro-thermal reaction 3 hours under 100 degree, reacted mortar filtration drying had both obtained the flyash after desiliconization, and filtrate contains meta-aluminic acid
Sodium and sodium metasilicate height can carry aluminum and use.
Described bypass is opened on the flue after desulfurization before naturally it is also possible to be opened in desulfurization, determines depending on structure space.Humidity is adjusted
Flue gas first can be carried out water saturation using the form of double platen press bubble towers by section device, then controls the pressure of outlet, pressed by changing
Power takes moisture adjusting flue gas in tower.The flue gas of flue is generally negative pressure (- 40kPa), need to first pass through a compressor
By pressure rise to pressure-fired (200kPa), then the outlet pressure of bubble tower is controlled to take moisture to adjust.Note after bubble tower
Flue gas duct to be incubated to keep moisture stable.
The minimum fluidization velocity of fluidized-bed reactor entrance according to fly ash grain calculate, typically need to 0.004m/s with
On, initial bubbling rate calculates according to fly ash grain, typically need to consider resistance drop in a practical situation in more than 0.012m/s
Etc. factor, selection air velocity is 0.1-0.5m/s, flyash in reactor the time of staying in 3-20min, solid and gas
Charge ratio row (grey gas ratio) be maintained at 5-15kg flyash/m3Flue gas, depending on CO in CaO content and flue gas2Depending on concentration.Due to
Flue gas has certain humidity can form one layer of liquid film in the flyash surface of solids, and the CaO in the surface of solids and duct can be by liquid film
Water power solve Ca+, and liquid film also can absorb the CO in flue gas simultaneously2And ionize out HCO3 -And CO3 2-, at a certain temperature
(60-90 degree Celsius) Ca+And HCO3 -Or CO3 2-Reaction quickly generates Calcium Carbonate.Through fluidized-bed reactor dusty gas warp out
Cyclone separator, gas is discharged from top, lower end be after reaction particle diameter become big (100 microns can be increased to) containing Calcium Carbonate
Flyash.The place passing in and out fluidized system in flue gas takes gaseous sample to survey wherein CO through flue gas analyzer2And SO2Content.Find
CO2It is reduced to 9% from 13% about concentration of entrance, and SO2Concentration is from 100mg/Nm3It is reduced to 35mg/Nm3.
Cyclone separator top decarburization gas out returns to former flue collector and enters smoke stack emission, and some flyash can weigh
Newly enter fluidized bed continue reaction, and collective low to separation solid product partial reflux arrive fluidized-bed reactor circulate make
With., control of reflux ratio is 1:1-5:Between 1.Solid product can be used to pulverized fuel ash cement processed, or makes as ground based filler etc.
With.
Present invention also offers a kind of fluidized system directly trapping mineralising carbon dioxide in flue gas, including：
Pretreatment unit, including for grind dry powder dismembyator and/or for heat treated heating incinerator and/or
For the stirred autoclave of alkaline process desiliconization, pressure filter and rotary drum drier；
Flue-gas temperature humidity adjustment unit, is arranged in the bypass being opened in flue, including the bubble tower equipped with liquid, goes out side
The flue gas on road enters bubble tower and realizes temperature and humidity regulation；
Fluidized-bed reactor, the solid material picking out pretreatment unit and the flue gas going out flue-gas temperature humidity adjustment unit；
Cyclone separator, the dusty gas picking out fluidized-bed reactor realizes gas solid separation, and wherein gained gas delivers to cigarette
Road is discharged from chimney.
Described bypass is arranged on the flue after desulfurization, is provided with compressor in bypass, and compressor needs to be arranged at bubbling
Before tower.
Compared with prior art, the invention has the beneficial effects as follows：
1st, technological process is simple, only comprises pretreatment (as cancelled), warm and humid regulation and fluid bed for C level high-calcium fly ass
And piece-rate system.
2nd, avoid using a large amount of high pressure slurry reactor kettles in traditional mineralising, be easy to continuously grasp using fluidized-bed reactor
Make, and device disposal ability is big, size is little to take up an area less.
3rd, the solid waste selected has had the granularity of very little, it is to avoid pulverizes and grinds the energy consumption brought.
4th, conveniently existing system is combined with power plant, and the quantities of transformation is little, and the equipment of increase is also few.
5th, carbonation reaction is carried out under the conditions of middle temperature 70-90 DEG C and low pressure (less than 2bar), while reducing energy consumption
Realize quick carbonation reaction, CO in flue gas in 5 minutes, can be made2Extrusion rate reaches 30%.
6th, with other CO2Trapping technique is compared, such as organic aminated absorption process, and its cost is in 250-350 yuan/ton of CO2.And
The decarburization cost of this technology is in 40-120 yuan/ton of CO2.As can be deviate from coal-fired plant flue gas 30% CO with relatively low cost2
It is also very attractive.Flyash after decarburization has no effect on fly ash in electric power plant original use approach simultaneously, is equivalent to
Raw material does not have consumption, still can be used with making cement additive and building materials, so the cost of material of this decarbonization process can approximately be neglected
Slightly.
Brief description
Fig. 1 is present configuration schematic diagram.
Specific embodiment
Describe embodiments of the present invention with reference to the accompanying drawings and examples in detail.
As shown in figure 1, a kind of fluidized system directly trapping mineralising carbon dioxide in flue gas of the present invention, high calcium garbage
Using fly ash in electric power plant, including：Pretreatment unit 7, flue-gas temperature humidity adjustment unit 9, fluidized-bed reactor 10 and whirlwind divide
From device 11, raw coal, after coal pulverizer 1, burns in steam generator system 2, produces energy and delivers to turbine 3 and electromotor 4.Burning
Contain substantial amounts of flyash in the flue gas producing, flue gas after SCR reactor 5 denitration, then through electrostatic precipitator 6 dedusting,
The flyash obtaining is sent into pretreatment unit 7 and is carried out pretreatment, and again through FGD absorption tower 8 desulfurization, pretreatment reaches the flue gas after dedusting
Flyash to after standard delivers to fluidized-bed reactor 10 by induction system 12.On the flue behind FGD absorption tower 8
Setting bypass, draws one flue gas to flue-gas temperature humidity adjustment unit 9, after adjusting humiture wherein, is sent to fluid bed
Reactor 10.Flyash and flue gas haptoreaction in fluidized-bed reactor 10, achieve the goal.After reaction, go out fluidized-bed reaction
The dusty gas of device 10 enter cyclone separator 11, complete gas solid separation wherein, separating obtained gas is sent to flue gas main pipeline
Discharge from chimney 13 and can be utilized gas composition analysis instrument 16 to analyze its composition.Wherein, temperature humidity adjustment unit 9 includes compressing
Machine 14 and the bubble tower 15 equipped with liquid.
The fluidized-bed process that the present invention directly traps mineralising carbon dioxide in flue gas can be several using the configuration of said system
Typical process example is as follows：
Embodiment 1
Directly trap the fluidized-bed process of mineralising carbon dioxide in flue gas, the use of coal-powder boiler high-calcium fly ass is raw material, CaO
30% about, principal crystalline phase is mullite to content, quartzy and substantial amounts of vitreous body amorphous Si O2, D50 be 80 microns, specifically
Step is as follows：
The first step, finds CaO with CaSiO after analysis ash sample3Form exists, and reactivity meets requirement, for carrying further
High reaction activity, carries out fine gtinding process to flyash, and particle size reduction to D50 is 20 microns, typically selects dry powder to grind
Machine, grinds 20min.Flyash can be from power plant's ash silo strength soot blower system sample presentation.
Second step, opens bypass on the flue after power plant desulfurization and draws one flue gas, first pass through supercharger and improve pressure
To 2bar, then adjusted by temperature and humidity regulator, temperature adjustment is 90 degrees Celsius, the range of accommodation of humidity is 20%.
3rd step, the flue gas mixing up temperature humidity is introduced from fluidized-bed reactor bottom and is blown into instead through air distribution plate and blast cap
Answer device, flyash adds from fluid bed bottom charging aperture, the charge ratio row of solid and gas are maintained at 5kg flyash/m3Flue
Gas.Flyash fluidizes upwards with flue gas, fluidizing velocity 0.1m/s, keep flyash time of staying in reactor be
5min.Through cyclone dust extractor separation solid, the flyash that flows back is controlled to 1 to fluid bed top dusty gas:1.Pass in and out stream in flue gas
The place changing bed system takes gaseous sample to survey wherein CO through flue gas analyzer2And SO2Content, CO2From entrance 12.3% about is dense
Degree is reduced to 7.5%, and SO2Concentration is from 89mg/Nm3It is reduced to 21mg/Nm3.
4th step, cyclone separator decarburization gas out returns to former flue collector and enters smoke stack emission, and detached solid produces
Product can be used to pulverized fuel ash cement processed, or uses as ground based filler etc..
Embodiment 2
Directly trap the fluidized-bed process of mineralising carbon dioxide in flue gas, the use of fluid-bed sweetening flyash is raw material, CaO
18% about, principal crystalline phase is a large amount of mullites to content, unsetting SiO2And free CaO, D50 be 40 microns, concrete steps
As follows：
The first step, finds that CaO is existed with fCaO form after analysis ash sample, reactivity meets requirement, need not carry out pre- place
Reason.Can be from power plant's ash silo strength soot blower system sample presentation.
Second step, opens bypass on the flue after power plant desulfurization and draws one flue gas, first pass through supercharger and improve pressure
To 2bar, then adjusted by temperature and humidity regulator, temperature adjustment is 90 degrees Celsius, the range of accommodation of humidity is 30%.
3rd step, the flue gas mixing up temperature humidity is introduced from fluidized-bed reactor bottom and is blown into instead through air distribution plate and blast cap
Answer device, flyash adds from fluid bed bottom charging aperture, the charge ratio row of solid and gas are maintained at 10kg flyash/m3Flue
Gas.Flyash fluidizes upwards with flue gas, fluidizing velocity 0.2m/s, keep flyash time of staying in reactor be
10min.Through cyclone dust extractor separation solid, the flyash that flows back is controlled to 2 to fluid bed top dusty gas:1.Pass in and out stream in flue gas
The place changing bed system takes gaseous sample to survey wherein CO through flue gas analyzer2And SO2Content, CO2From entrance 13.3% about is dense
Degree is reduced to 9.5%, and SO2Concentration is from 95mg/Nm3It is reduced to 39mg/Nm3.
4th step, cyclone separator decarburization gas out returns to former flue collector and enters smoke stack emission, and detached solid produces
Product can be used to pulverized fuel ash cement processed, or uses as ground based filler etc..
Embodiment 3
Directly trap the fluidized-bed process of mineralising carbon dioxide in flue gas, the use of coal-powder boiler Class F fly ash is raw material, CaO
5% about, principal crystalline phase is mullite, quartzy and substantial amounts of vitreous body amorphous Si O to content2, D50 be 80 microns, specifically
Step is as follows：
The first step, finds CaO with CaSiO after analysis ash sample3Form exists, but CaO content needs to do at alkaline process desiliconization less
Reason, meets activity and the requirement of grey gas ratio.NaOH solution using 15% dissolves powder under the conditions of 90 degree of 800rpm speeds of agitator
Coal ash, liquid-solid ratio is 5:1, dissolving 2 hours after filter and drying can process after flyash.Live for improving reaction further
Property, can again the flyash processing be heated 2 hours under 600 degree.
Second step, opens bypass on the flue after power plant desulfurization and draws one flue gas, first pass through supercharger and improve pressure
To 2bar, then adjusted by temperature and humidity regulator, temperature adjustment is 80 degrees Celsius, the range of accommodation of humidity is 20%.
3rd step, the flue gas mixing up temperature humidity is introduced from fluidized-bed reactor bottom and is blown into instead through air distribution plate and blast cap
Answer device, flyash adds from fluid bed bottom charging aperture, the charge ratio row of solid and gas are maintained at 15kg flyash/m3Flue
Gas.Flyash fluidizes upwards with flue gas, fluidizing velocity 0.4m/s, keep flyash time of staying in reactor be
20min.Through cyclone dust extractor separation solid, the flyash that flows back is controlled to 3 to fluid bed top dusty gas:1.Pass in and out stream in flue gas
The place changing bed system takes gaseous sample to survey wherein CO through flue gas analyzer2And SO2Content, CO213% about the concentration from entrance
It is reduced to 9%, and SO2Concentration is from 105mg/Nm3It is reduced to 45mg/Nm3.
4th step, cyclone separator decarburization gas out returns to former flue collector and enters smoke stack emission, and detached solid produces
Product can be used to pulverized fuel ash cement processed, or uses as ground based filler etc..
Embodiment 4
Directly trap the fluidized-bed process of mineralising carbon dioxide in flue gas, the use of slag is raw material, CaO content is left 40%
The right side, principal crystalline phase is calcium silicates, calcium oxide, and D50 is 120 microns, comprises the following steps that：
The first step, the reactivity of slag can meet reacts requirement, but needs micro- to 40 through grinding reduction granularity D50
Rice.
Second step, opens bypass on the flue after power plant desulfurization and draws one flue gas, first pass through supercharger and improve pressure
To 2bar, then adjusted by temperature and humidity regulator, temperature adjustment is 60 degrees Celsius, the range of accommodation of humidity is 10%.
3rd step, the flue gas mixing up temperature humidity is introduced from fluidized-bed reactor bottom and is blown into instead through air distribution plate and blast cap
Answer device, slag adds from fluid bed bottom charging aperture, the charge ratio row of solid and gas are maintained at 5kg slag/m3Flue gas.Steel
Slag fluidizes upwards with flue gas, fluidizing velocity 0.4m/s, keeps slag time of staying in reactor to be 5min.On fluid bed
Through cyclone dust extractor separation solid, the slag that flows back is controlled to 1 to portion's dusty gas:1.The place passing in and out fluidized system in flue gas takes
Gaseous sample surveys wherein CO through flue gas analyzer2And SO2Content, CO2It is reduced to 8% from 12% about concentration of entrance, and SO2
Concentration is from 120mg/Nm3It is reduced to 35mg/Nm3.
4th step, cyclone separator decarburization gas out returns to former flue collector and enters smoke stack emission, and detached solid produces
Product can be used to controlling the water circulation mud, or uses as ground based filler etc..
Present invention process directly can be trapped using fly ash in electric power plant (also can use or add other high calcium solid waste)
Mineralising carbon dioxide in flue gas, using having the flyash of certain particle size CO directly and in flue gas after pretreatment2Fast reaction
Generate Calcium Carbonate.First, this technique directly utilizes basicity and the CO of flyash2Acid reaction it is not necessary to again in Ore Leaching raw material
The metal cation such as calcium and magnesium adjust again pH value under alkalescence with CO2Reaction, technological process is shortened.Additionally, can using fluid bed
Improve the treatment quantity in the unit interval to greatest extent, and reduce size and the occupation of land of equipment.Finally, this technique only needs to
The temperature and humidity keeping certain can carry out, it is not necessary to adopt high temperature and high pressure process conditions, reducing the energy consumption of process.Thus gram
Take traditional CO2Mineralization process long flow path, equipment size are big, the shortcoming of energy consumption and high cost.
Claims (5)
1. a kind of fluidized-bed process of direct trapping mineralising carbon dioxide in flue gas is it is characterised in that comprise the following steps：
The first step, collects the grinding of high calcium garbage stand-by；Described flue gas is power-plant flue gas, and high calcium garbage is power-plant flue gas electrostatic
Gained flyash after dedusting, wherein CaO mass fraction are more than 20%, and granularity is 20-80 micron；
Second step, opens bypass on fume emission flue and draws one flue gas through temperature and humidity regulator regulation temperature and humidity, temperature is adjusted
Adjusting range is 40-90 DEG C, and the range of accommodation of humidity is 5-60%；Described bypass is opened on the flue after desulfurization, humidistat
Using double platen press bubble tower forms, first flue gas is carried out water saturation, then control the pressure of outlet, adjust cigarette by changing pressure
Gas takes moisture in tower；
3rd step, in a fluidized bed reactor by the flue gas after temperature and humidity regulation with described high calcium garbage and to haptoreaction；
4th step, the dusty gas feeding cyclone separator going out fluidized-bed reactor after reaction carries out gas solid separation, gained gas
Send former fume emission flue back to and enter smoke stack emission.
If according to claim 1 directly trapping mineralising carbon dioxide in flue gas fluidized-bed process it is characterised in that
In described high calcium garbage, CaO mass fraction is less than 20%, then utilize alkaline process desiliconization to process, that is, adopt the NaOH of 0.5-2mol/l
Or NaCO3Solution press solid-to-liquid ratio 100-250g/l by high calcium garbage hydro-thermal reaction 3 hours at 100 DEG C；Described high calcium gives up
Gurry heat treatment 2 hours under 600 DEG C of high temperature, to destroy the crystal structure on surface thus improving its chemical reactivity.
3. according to claim 1 directly the fluidized-bed process of trapping mineralising carbon dioxide in flue gas it is characterised in that first warp
Crossing flue gas compressor by pressure rise to pressure-fired is 200kPa, then controls the outlet pressure of bubble tower to take moisture to adjust.
4. according to claim 1 directly the fluidized-bed process of trapping mineralising carbon dioxide in flue gas it is characterised in that described
In fluidized-bed reactor, flue gas stream speed is 0.1-0.5m/s, and the high calcium garbage time of staying is 3-20min, solid and gas charge ratio
Example is 5-15kg high calcium garbage/m3Flue gas.
5. according to claim 1 directly the fluidized-bed process of trapping mineralising carbon dioxide in flue gas it is characterised in that by institute
The part stating the solid product of cyclone collection is recycled to fluidized-bed reactor recycling.
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| CN106474912B (en) * | 2016-11-10 | 2019-04-30 | 南京师范大学 | CO in a kind of flyash removing power-plant flue gas2Device and method |
| CN106823774B (en) * | 2017-02-14 | 2023-03-21 | 河钢股份有限公司 | Device and method for fixing carbon dioxide and recovering sensible heat by using blast furnace slag |
| CN107398173B (en) * | 2017-08-27 | 2023-10-27 | 北方民族大学 | Limestone CO in a double tower fluidized bed 2 Circulation trapping device and technology thereof |
| CN107744716B (en) * | 2017-11-15 | 2019-09-06 | 山东大学 | The hollow compound CO of shell-type carbide slag2Absorbent and its synthetic method and application |
| CN108889251B (en) * | 2018-08-20 | 2023-09-29 | 中国华能集团有限公司 | Entrained-flow bed device and method for humidifying and mineralizing carbon dioxide |
| CN109126412B (en) * | 2018-08-20 | 2022-01-14 | 中国华能集团清洁能源技术研究院有限公司 | Method for intensifying mineralization of carbon dioxide by using salt-containing wastewater |
| CN110079371B (en) * | 2019-04-30 | 2021-09-14 | 封金财 | Preparation method of purification particles for biomass fuel |
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| RO135812B1 (en) * | 2021-10-05 | 2023-12-29 | Universitatea "Dunărea De Jos" Din Galaţi | Co2 sequestration mixture using foundry slag |
| CN113773171B (en) * | 2021-10-18 | 2023-10-24 | 青岛维舍环保新能源科技有限公司 | Industrial CO 2 Emission reduction method for recycling |
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| CN114835148B (en) * | 2022-05-23 | 2023-06-20 | 中国华能集团清洁能源技术研究院有限公司 | Gangue power generation and CO 2 Mineralization cooperative utilization system and working method |
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