CN102671618B - Preparation method for microspherical nano CaO-based CO2 adsorber for circulating fluidized bed, product and application - Google Patents
Preparation method for microspherical nano CaO-based CO2 adsorber for circulating fluidized bed, product and application Download PDFInfo
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- CN102671618B CN102671618B CN201210133472.5A CN201210133472A CN102671618B CN 102671618 B CN102671618 B CN 102671618B CN 201210133472 A CN201210133472 A CN 201210133472A CN 102671618 B CN102671618 B CN 102671618B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000011069 regeneration method Methods 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims description 105
- 239000004005 microsphere Substances 0.000 claims description 63
- 239000007789 gas Substances 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 39
- 230000003134 recirculating effect Effects 0.000 claims description 21
- 239000003546 flue gas Substances 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 239000003595 mist Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical group [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000000292 calcium oxide Substances 0.000 description 62
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 62
- 239000002250 absorbent Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 230000002745 absorbent Effects 0.000 description 12
- 230000000274 adsorptive effect Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000004087 circulation Effects 0.000 description 9
- 239000002594 sorbent Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 8
- 229960004424 carbon dioxide Drugs 0.000 description 7
- 238000005262 decarbonization Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 235000019738 Limestone Nutrition 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000006028 limestone Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method for a microspherical nano CaO-based CO2 adsorber for a circulating fluidized bed. The preparation method comprises the following steps: dispersing nano CaCO3 in water to obtain suspension; stirring and mixing the suspension, additives and aluminum sol uniformly; performing spray granulation to obtain microspherical granules with the grain size of 20-200 micrometers; and calcining to obtain the microspherical nano CaO-based CO2 adsorber. The invention also discloses the microspherical nano CaO-based CO2 adsorber prepared by the method, and a method for capturing CO2 by using the microspherical nano CaO-based CO2 adsorber. The method is simple and feasible; the prepared adsorber has high adsorption speed, high adsorption capacity, high adsorption property and high wear resistance, the continuous decarbonization-regeneration circulating process can be realized in a circulating fluidized bed system, the capacity and efficiency of treating CO2 are greatly improved and the cost of removing the CO2 is reduced.
Description
Technical field
The present invention relates to material manufacture and environmental protection, chemical process carbon dioxide removal field, be specifically related to a kind of microsphere nano CaO base CO for recirculating fluidized bed
2preparation method, product and the application of adsorbent.
Background technology
CO
2the 280ppm of content in atmosphere before by the industrial revolution risen to present 400ppm left and right, and it is the main cause that causes global warming.CO
2the main source of discharge is the combustion process of fossil fuel, reduces at present CO
2the means of discharge capacity are the CO to producing after combustion of fossil fuel
2trap, store and utilize, thereby reaching the object of effective reduction of discharging.
The CO that commercialization is now comparatively ripe
2capture method is wet method trapping, the CO in using amine aqueous solution as absorption liquid absorption from flue gas
2but the method also has several obvious shortcomings, first, owing to will, to the absorption liquid processing of regenerating, having increased energy consumption, the energy that has reduced whole system utilizes gross efficiency; Secondly,, in order to reduce the pollution of impurity to absorption liquid in flue gas, need to remove to flue gas the pretreatment of sulphur and nitrogen oxide; In addition, also have the problems such as equipment corrosion.The more important thing is and adopt wet method trapping meeting to the contaminated waste water of environmental emission, cause more pollution.
In the last few years, a kind of new CO
2the trapping of trapping technique-dry method receives increasing concern, different from wet method trapping, and dry method trapping adopts solid absorbent to the CO in flue gas
2adsorb, cardinal principle is to utilize the active component in adsorbent to adsorb the CO in flue gas at adsorptive reactor
2formed hydrochlorate, reduces the CO in flue gas
2concentration, subsequently, adsorbent is transported in calcination reactor regenerates, and realizes recycling of adsorbent.It is cheap that dry method trapping technique has raw material, renewable, flexible design, eco-friendly advantage.
CO
2the recirculating fluidized bed system of dry method trapping process using has had certain research at present, circulating fluidized bed technique is widely used in the catalytic cracking (FCC of oil refining, fluid catalytic cracking) and fluidized bed combustion reactor (CFBC, circulating fluidized bed combustion).Therefore circulating fluid bed reactor is used for to CO
2in trapping, do not have technological difficulties, and compare under this individual system, the physical property of adsorbent is still the primary difficult problem solving in world wide as the stability of adsorption capacity as wear rate and chemical property.Because these property relationships are to the Cost Problems of dry method decarburization.
Natural limestone and dolomite etc. taking calcium oxide as active component is considered to have the dry method trapping adsorbent of large development potentiality, but has two larger defects: the easy decay of adsorption capacity and adsorbent are easy to wear.
The people such as Dennis (Lu et al., Fuel Process.Technol.2008,12 of 89,1386-1395) adopt the fluidized-bed reactor CO absorption of lime stone at pilot-scale
2, in practical operation, the temperature of absorber is controlled at 580-720 DEG C, and the temperature in regenerator is controlled at 850-950 DEG C, CO
2volume content is at 15-16%, and after 15 circulations, specific area has declined 31.9%, and after 25 circulations, adsorption efficiency has declined 26.8%, and material has worn and torn 62%.
The people such as Symonds (Symonds et al., Chem.Eng.Sci.2009,15of 64,3536-3543) adopt lime stone CO absorption on fluid bed
2, adsorption temp is 550 DEG C, atmosphere is 8%CO
2, 17%H
2the air of O; Regeneration temperature is 860 DEG C; After three circulations, more than 95% time of adsorption efficiency has declined 80%.
The people such as the Li Zhenshan of Tsing-Hua University (Fang et al., Ind.Eng.Chem.Res.2009,24of48,11140-11147) utilize dolomite as adsorbent CO absorption on two bubbling beds
2, adsorption temp is 600 DEG C, CO
213.4% air); Regeneration temperature is 900 DEG C, and in 250min, adsorbent has lost 11.5%, and the adsorbent average grain diameter of calcining compartment has declined 68%.
It is all the system of quick Bed that the people such as Alonso (Alonso et al., Int.J.Greech.Gas Control.2010,2of 4,167-173) have adopted absorber and regenerator.The operating temperature of absorber is 600-700 DEG C, with air and CO
2gaseous mixture is conveying gas, and the temperature of regenerator is 800-900 DEG C, and fluidized gas is air.CO
2adsorption efficiency all remain on more than 70%, but the CO in adsorbed gas is not described
2concentration, can infer its CO according to other scholars' result of study
2treating capacity should be in a lower level.
People (the Gonz á lez et al. such as Gonz á lez, Fuel 2010,10of89,2918-2924) adopt same device and operating condition, the wear rate of limestone particle of two kinds of different-grain diameters of research: after circulation 40-100 hour, the average grain diameter 38%-50% that declined.
The adsorption capacity of natural limestone adsorbent is low, the rate of adsorption is slow, therefore taking natural limestone adsorbent when recycle stock carrys out reactor design, adsorptive reactor generally adopts the smaller fluid bed form of the gas such as moving bed or bubbling bed agent to ensure CO
2removal effect, but increased Material Cost and the cost of energy of processing unit volume flue gas.And adopt fast fluidized bed as adsorptive reactor, although can increase gas agent ratio, because absorbent particles polishing machine is poor, in order to ensure essential CO
2trapping effect, need to ceaselessly supplement fresh adsorbent, needs more expense of raw materials, has caused CO
2the rising of processing cost, this is one of key that at present cannot industrial applications.The calcium oxide-based carbon dioxide for recirculating fluidized bed of report adsorbs the stability of the adsorption capacity that does not also solve adsorbent and problem easy to wear at present.
For CaO base CO
2adsorbent is decay and shortcoming easy to wear easily, and the inventor (Su F.Wu, Ind.Eng.Chem.Res, 2008,47,180-184) in early-stage Study adopts the presoma that nano-calcium carbonate is calcium oxide-based adsorbent, preparation nanometer CaO/Al
2o
3adsorbent, finds nanometer CaO/Al
2o
3adsorbent has CO
2the advantages such as adsorption rate is high, decomposition temperature is low, the rate of adsorption is fast.The inventor is to disclose respectively employing precipitation of silica and the coated CaTiO in surface in CN101306309A and the publication number Chinese patent that is CN101537339A at publication number
3method nano-calcium base adsorbent is carried out to modification, under TGA test, adsorption capacity and absorption stability are significantly improved, but both not yet propose the adsorbent of modification to make microsphere particle, and the intensity of adsorbent and abrasiveness far do not reach the requirement of fluid bed system.
In the Chinese patent that the inventor is CN101961638A at publication number, disclose one and prepared the calcium oxide-based CO of nanometer antiwear
2the method of adsorbent, by CaCO
3particle ultrasonic wave in water disperses, and adds aluminium colloidal sol, is stirred to uniform sizing material, obtains the microsphere particle that particle diameter is 20-250 μ m, then obtain spherical wear-resisting nano oxidized Ca-base adsorbent by calcining by mist projection granulating.Owing to having formed calcium aluminate in calcination process, the wearability of calcium oxide is improved, but this adsorbent does not solve the problem that adsorption capacity is low, adsorption capacity is less than 2mol/kg.
Tang Qi is in master thesis (Zhejiang University, 2011) in, mention in composite catalyst preparation and adopt aluminium carbonate ammonium, polyethylene glycol, softex kw and activated carbon as expanding agent, but in CaO group carbonic anhydride adsorption agent preparation process, do not use.Other are not reported for the research of circulating fluidized bed technique capturing carbon dioxide about nano oxidized calcium group carbonic anhydride adsorption agent.
Summary of the invention
The invention provides a kind of microsphere nano CaO base CO for recirculating fluidized bed
2the preparation method of adsorbent, simple, the adsorbent of preparation is wear-resistant, the rate of adsorption is fast, adsorption capacity is high.
A kind of microsphere nano CaO base CO for recirculating fluidized bed
2the preparation method of adsorbent, comprising: nanometer CaCO
3be scattered in and in water, form suspension, suspension, additive and aluminium colloidal sol are uniformly mixed to evenly, obtaining particle diameter through mist projection granulating is the microsphere particle of 20～200 microns, then obtains microsphere nano CaO base CO after calcining
2adsorbent.
Described additive is aluminium carbonate ammonium, polyethylene glycol or nano-sized carbon, adds additive to prepare to have the microsphere nano CaO base CO of certain pore size structure and specific area
2adsorbent, strengthens mass transfer, heat-transfer effect in adsorbent and carbon dioxide reaction process, improves wearability, adsorption capacity and stability.
Described aluminium colloidal sol is to be hydrolyzed by aluminium salt and alcoholic solution the industrial goods forming, and its composition is for containing Al
2o
3colloidal solution.Al in conventional aluminium colloidal sol
2o
3mass fraction be 5%～20%.
Described nanometer CaCO
3in Ca and the mol ratio of Al in aluminium colloidal sol be 0.1～50: 1, to improve microsphere nano CaO base CO
2the anti-wear performance of adsorbent.
Described additive and nanometer CaCO
3mass ratio be 0.005～0.2: 1, to strengthen microsphere nano CaO base CO
2the mass transfer of adsorbent, heat-transfer effect, improve adsorption capacity and stability.
Described calcining is at 750～1000 DEG C, to calcine 1～8h, nanometer CaCO after calcining
3resolve into nanometer CaO and make microsphere nano CaO base CO
2adsorbent.
The present invention also provides the microsphere nano CaO base CO that adopts above-mentioned preparation method to prepare
2adsorbent.
Further, the present invention also provides above-mentioned microsphere nano CaO base CO
2adsorbent is applied to and in recirculating fluidized bed, traps CO
2method, comprise the following steps:
(1) by microsphere nano CaO base CO
2adsorbent packs in circulating fluid bed reactor, contains CO to passing in reactor
2fluidized gas, carry out adsorption reaction;
(2) CO absorption in reactor
2after adsorbent and CO
2fluidized gas after being adsorbed enters cyclone separator and separates, and the solid after separation enters regenerator, the gas discharging after separation;
(3) regenerator bottoms passes into N
2, CO
2or the tail gas that regenerator produces is as loosening gas, carries out the regeneration of adsorbent.
Described fluidized gas is for containing CO
2flue gas; The gas speed of described fluidized gas in adsorptive reactor is 1～1000 times of adsorbent microballoon minimum fluidizing velocity; The described CO that contains
2flue gas in CO
2volumetric concentration be 8%～20%, in actual application, need and contain CO according to the space size of reactor
2the choose reasonable microsphere nano CaO base CO such as treating capacity of flue gas
2the consumption of adsorbent.
Different speed, the adsorption effects that can affect absorption of adsorption temp, are the disposal ability that improves carbon dioxide, need to select suitable adsorption temp, and the temperature of the adsorption reaction of described step (1) is 550～650 DEG C.
Described loosening gas is the tail gas that regenerator produces, and described tail gas is the N mixing with arbitrary proportion
2and CO
2mist; The gas speed of described loosening gas is 1～20 times of adsorbent microsphere particle minimum fluidizing velocity, with keep absorbent particles in reactor in fluidized state.
CO absorption
2after adsorbent need to carry out thermal decomposition regeneration again to carry out adsorption reaction, the temperature of the regeneration of described step (4) is 750～950 DEG C.
Principle of the present invention is:
Nanometer CaO base CO
2caO in adsorbent and CO
2reaction generates CaCO
3:
C
aO
(s)+CO
2→C
aCO
3(s) (1)
The CaCO that reaction generates
3by heating disintegrating and regeneration, reaction equation is as follows:
C
aC
O3(s)→C
aO
(s)+CO
2 (2)
Adsorbent after the present invention's regeneration carries out adsorption-regeneration circulation according to step (1)～(4) again; CO in the gas obtaining after cyclonic separation more than 90%
2be removed CO
2concentration remains on below 1%, can directly be disposed to atmosphere; Microsphere nano CaO base CO
2caCO in adsorbent
3cO in the tail gas producing after regeneration
2concentration is more than 50%.
Compared with prior art, the invention has the advantages that:
The inventive method is simple, prepares particle diameter and be the microsphere nano CaO base CO of 20～200 microns
2adsorbent, its specific area can reach 10m
2more than/g, in absorbent particles, pore and large hole count are all increased, and average pore size is in 8～20 nanometers.
Microsphere nano CaO base CO of the present invention
2adsorbent has good polishing machine, according to ASTM D5757 standard (Standard test method for determination of attrition and abrasion of powder catalysts by air jets, ASTM, US) wear rate of absorbent particles of test is below 5%.Microsphere nano CaO base CO of the present invention
2adsorbent has good absorption property, in TGA test, after 50 adsorption-desorption circulations, more than its adsorption capacity still remains on 3mol/kg adsorbent.
Microsphere nano CaO base CO of the present invention
2adsorbent, has good mass transfer, heat transfer property, is applied in recirculating fluidized bed decarbonization process, and compared with natural calcium oxide-based adsorbent, required regeneration temperature and adsorption reaction temperature have reduced by 50～100 DEG C, have reduced and have removed CO
2cost of energy.
Microsphere nano CaO base C of the present invention
o2 adsorbents, than natural base adsorbent, have larger adsorption capacity and adsorption rate faster, have ensured that adsorbent is at recirculating fluidized bed CO
2in trapping technique, can adopt fast fluidized bed decarburization, reach the object that improves reactor for treatment amount; There is better polishing machine, greatly reduce and remove CO
2material Cost.
Microsphere nano CaO base CO of the present invention
2absorbent preparation technique is simple, is applied to and in recirculating fluidized bed, traps CO
2method, can continous-stable operation, mass transfer, heat transfer efficiency are high.
Brief description of the drawings
Fig. 1 is microsphere nano CaO base CO of the present invention
2the preparation method's of adsorbent flow chart.
Fig. 2 is the microsphere nano CaO base CO of the different specific areas prepared of comparative example 1 of the present invention and embodiment 1
2the adsorpting rate curve figure of adsorbent nsorb-1 and sorb-2.
Fig. 3 is the microsphere nano CaO base CO of the different specific areas prepared of comparative example 1 of the present invention and embodiment 1
2the circulation absorption Capacity Plan of adsorbent nsorb-1 and sorb-2.
Fig. 4 is microsphere nano CaO base CO prepared by the embodiment of the present invention 4
2the CO of adsorbent sorb-5 the 40 circulation absorption in fixed bed test
2adsorption efficiency and outlet CO
2concentration map, actual conditions is as follows: adsorbent mass 5g, CO
2concentration is 20%, 600 DEG C of adsorption temps, 800 DEG C of regeneration temperatures.
Fig. 5 is microsphere nano CaO base CO of the present invention
2capture by Sorbents CO
2the schematic diagram of method.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Comparative example 1
Nanometer CaCO
310g is dispersed in 80ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 10.2g mass fraction is 10% aluminium colloidal sol, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 5 microns.Absorbent particles is calcined to 1h at 800 DEG C, obtain microsphere nano CaO base CO
2adsorbent, nsorb-1.
Embodiment 1 microsphere nano CaO base CO
2the preparation of adsorbent
Nanometer CaCO
310g is dispersed in 50ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 51g mass fraction is 20% aluminium colloidal sol and 1.5g aluminium carbonate ammonium, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 20 microns.Absorbent particles is calcined to 1h at 880 DEG C, obtain microsphere nano CaO base CO
2adsorbent, sorb-2.
Microsphere nano CaO base CO prepared by the present embodiment
2absorbent particles wear rate is 4.0%.
Embodiment 2 microsphere nano CaO base CO
2the preparation of adsorbent
Nanometer CaCO
320g is dispersed in 160ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 8.16g mass fraction is 5% aluminium colloidal sol and 4g polyethylene glycol, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 200 microns.Absorbent particles is calcined to 4h at 1000 DEG C, obtain microsphere nano CaO base CO
2adsorbent, sorb-3.
Microsphere nano CaO base CO prepared by the present embodiment
2absorbent particles wear rate is 3.3%.
Embodiment 3 microsphere nano CaO base CO
2the preparation of adsorbent
Nanometer CaCO
320g is dispersed in 100ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 20.4g mass fraction is 10% aluminium colloidal sol and 0.1g Macrogol 2000, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 60 microns.Absorbent particles is calcined to 2h at 850 DEG C, obtain microsphere nano CaO base CO
2adsorbent, sorb-4.
Microsphere nano CaO base CO prepared by the present embodiment
2absorbent particles wear rate is 5.0%.
Embodiment 4 microsphere nano CaO base CO
2the preparation of adsorbent
Nanometer CaCO
315g is dispersed in 150ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 38.25g mass fraction is 5% aluminium colloidal sol and 3g aluminium carbonate ammonium, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 80 microns.Absorbent particles is calcined to 2h at 900 DEG C, obtain microsphere nano CaO base CO
2adsorbent, sorb-5.
Microsphere nano CaO base CO prepared by the present embodiment
2absorbent particles wear rate is 4.8%.
Embodiment 5 microsphere nano CaO base CO
2the preparation of adsorbent
Nanometer CaCO
310g is dispersed in 60ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 15.7g mass fraction is that 5% aluminium colloidal sol and 1.5g particle diameter are the powdered carbon of 100 nanometers, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 80 microns.Absorbent particles is calcined to 2h at 850 DEG C, obtain microsphere nano CaO base CO
2adsorbent, sorb-6.
Microsphere nano CaO base CO prepared by the present embodiment
2absorbent particles wear rate is 3.7%.
Embodiment 6 microsphere nano CaO base CO
2the preparation of adsorbent
Nanometer CaCO
310g is dispersed in 70ml distilled water, forms finely dispersed suspension, to nanometer CaCO
3in suspension, adding 8.5g mass fraction is the powdered carbon that 20% aluminium colloidal sol and 2g particle diameter are 100, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be the solid sorbent particles of 60 microns.Absorbent particles is calcined to 2h at 900 DEG C, obtain microsphere nano CaO base CO
2adsorbent, sorb-7.
Microsphere nano CaO base CO prepared by the present embodiment
2absorbent particles wear rate is 3.1%.
Application examples recirculating fluidized bed decarbonization process
Microsphere nano CaO base CO
2capture by Sorbents CO
2technique, as shown in Figure 5, fresh particles nanometer CaO base CO
2adsorbent, in conveying device enters the reactor of recirculating fluidized bed, meanwhile, passes into and contains CO to adsorptive reactor
2flue gas, CO
2after contacting with adsorbent microballoon, adsorbed rapidly, the gas-solid mixture that leaves adsorptive reactor enters cyclone separator and separates, gas after separation directly discharges atmosphere, adsorbent solids after separation is transported in regenerator, the tail gas of regenerator passes in regenerator as loosening gas, carry out adsorbent reactivation reaction, the adsorbent after regeneration enters adsorption-regeneration circulation next time.
Application examples 1
Adopt the CO in recirculating fluidized bed decarbonization process trapping flue gas
2, the microsphere nano CaO base CO that the adsorbent of use is prepared for the embodiment of the present invention 1
2adsorbent sorb-2, average grain diameter is 20 microns, adsorption reaction condition is: 800 DEG C of regeneration temperatures, loosening gas speed is 30 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that enters adsorptive reactor is than being 0.083L/g, wherein CO
2concentration 15vol%, 600 DEG C of adsorption temps, CO in exit gas
2content is 0.3vol%, CO
2adsorption efficiency 98.3%.
Application examples 2
Adopt the CO in recirculating fluidized bed decarbonization process trapping flue gas
2, the microsphere nano CaO base CO that the adsorbent of use is prepared for the embodiment of the present invention 1
2adsorbent sorb-2, average grain diameter is 20 microns, adsorption reaction condition is: 780 DEG C of regeneration temperatures, loosening gas speed is 40 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that enters adsorptive reactor is than being 0.08L/g, wherein CO
2concentration 15vol%, 550 DEG C of adsorption temps, CO in exit gas
2content 0.5vol%, CO
2adsorption efficiency 97.18%.
Application examples 3
Adopt the CO in recirculating fluidized bed decarbonization process trapping flue gas
2, the microsphere nano CaO base CO that the adsorbent of use is prepared for the embodiment of the present invention 2
2adsorbent sorb-3, average grain diameter is 200 microns, adsorption reaction condition: 800 DEG C of regeneration temperatures, loosening gas speed is 60 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that enters adsorptive reactor is than being 0.05L/g, wherein CO
2concentration 20vol%, 550 DEG C of adsorption temps, CO in exit gas
2content 0, CO
2adsorption efficiency 100%.
Application examples 4
Adopt the CO in recirculating fluidized bed decarbonization process trapping flue gas
2, the microsphere nano CaO base CO that the adsorbent of use is prepared for the embodiment of the present invention 5
2adsorbent sorb-6, average grain diameter is 80 microns, adsorption reaction condition: 850 DEG C of regeneration temperatures, loosening gas speed is 40 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that enters adsorptive reactor is than being 0.06L/g, wherein CO
2concentration 8vol%, 650 DEG C of adsorption temps, CO in exit gas
2content is at 0vol%, CO
2adsorption efficiency 100%.
Application examples 5
Adopt the CO in recirculating fluidized bed decarbonization process trapping flue gas
2, the microsphere nano CaO base CO that the adsorbent of use is prepared for the embodiment of the present invention 4
2adsorbent sorb-5, average grain diameter is 80 microns; Adsorption reaction condition: 750 DEG C of regeneration temperatures, loosening gas speed is 40 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that enters adsorptive reactor is than being 0.075L/g, wherein CO
2concentration 20vol%, 600 DEG C of adsorption temps, the staying volume 2kg of adsorbent in riser, CO in exit gas
2content is at 1vol%, CO
2adsorption efficiency 90%.
Claims (4)
1. a microsphere nano CaO base CO
2adsorbent is applied to and in recirculating fluidized bed, traps CO
2method, it is characterized in that, comprising:
(1) by microsphere nano CaO base CO
2adsorbent packs in circulating fluid bed reactor, contains CO to passing in reactor
2fluidized gas, carry out adsorption reaction;
(2) CO absorption in reactor
2after adsorbent and CO
2fluidized gas after being adsorbed enters cyclone separator and separates, and the solid after separation enters regenerator, the gas discharging after separation;
(3) regenerator bottoms passes into N
2, CO
2or the tail gas that regenerator produces is as loosening gas, carries out the regeneration of adsorbent;
Described fluidized gas is for containing CO
2flue gas, the gas speed of described fluidized gas is 1～1000 times of adsorbent microballoon minimum fluidizing velocity, the described CO that contains
2flue gas in CO
2volumetric concentration be 8%～20%;
Described loosening gas is the tail gas that regenerator produces, and described tail gas is CO
2and N
2mist; The gas speed of described loosening gas is 1～20 times of adsorbent microsphere particle minimum fluidizing velocity;
Described microsphere nano CaO base CO
2the preparation method of adsorbent, comprising: nanometer CaCO
3be scattered in and in water, form suspension, suspension, additive and aluminium colloidal sol are uniformly mixed to evenly, obtaining particle diameter through mist projection granulating is the microsphere particle of 20～200 microns, then obtains microsphere nano CaO base CO after calcining
2adsorbent;
Described additive is aluminium carbonate ammonium, polyethylene glycol or nano-sized carbon;
Described nanometer CaCO
3in Ca and the mol ratio of Al in aluminium colloidal sol be 0.1～50:1, described additive and nanometer CaCO
3mass ratio be 0.005～0.2:1.
2. microsphere nano CaO base CO as claimed in claim 1
2adsorbent is applied to and in recirculating fluidized bed, traps CO
2method, it is characterized in that, described calcining for to calcine 1～8h at 750～1000 DEG C.
3. microsphere nano CaO base CO as claimed in claim 1
2adsorbent is applied to and in recirculating fluidized bed, traps CO
2method, it is characterized in that, the temperature of the adsorption reaction of step (1) is 550～650 DEG C.
4. microsphere nano CaO base CO as claimed in claim 1
2adsorbent is applied to and in recirculating fluidized bed, traps CO
2method, it is characterized in that, the temperature of the regeneration of step (3) is 750～950 DEG C.
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