CN101961638A - Method for preparing wear-resistant nano calcium oxide-based carbon dioxide reaction adsorbent - Google Patents
Method for preparing wear-resistant nano calcium oxide-based carbon dioxide reaction adsorbent Download PDFInfo
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- CN101961638A CN101961638A CN2010105158719A CN201010515871A CN101961638A CN 101961638 A CN101961638 A CN 101961638A CN 2010105158719 A CN2010105158719 A CN 2010105158719A CN 201010515871 A CN201010515871 A CN 201010515871A CN 101961638 A CN101961638 A CN 101961638A
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- reaction adsorbent
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 74
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 65
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 64
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 75
- 238000001354 calcination Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims description 35
- 239000011575 calcium Substances 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- 239000004411 aluminium Substances 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 239000003595 mist Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 238000004513 sizing Methods 0.000 claims description 18
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 10
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 235000012241 calcium silicate Nutrition 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000000629 steam reforming Methods 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000002250 absorbent Substances 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- 230000002745 absorbent Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- -1 calcium aluminate compound Chemical group 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a wear-resistant nano calcium oxide-based carbon dioxide (CO2) reaction adsorbent. The method comprises the following steps of: dispersing calcium carbonate (CaCO3) particles in water; adding aluminasol; stirring until pulp is well distributed; spraying and pelleting to obtain microspherical particles with particle diameter of 20 to 250 mu m; and calcining the microspheric particles to obtain the spherical wear-resistant nano calcium oxide-based CO2 reaction adsorbent. The wear strength of the wear-resistant nano calcium oxide-based CO2 reaction adsorbent can be improved by the method; and the method can be widely applied to industrial processes of removing the CO2 from industrial smoke, removing the CO2 by a reaction, a new adsorption strengthening methane steam reforming hydrogen production process and the like.
Description
Technical field
The present invention relates to material and make the field, especially relate to a kind of nano calcium oxide base CO
2The method of reaction adsorbent.
Background technology
High-temperature oxydation calcium base CO
2Adsorbent can be used for flue gas and removes CO
2, technical processes such as reaction adsorption forced methane steam reforming hydrogen manufacturing and chemical heat pump all have the important application prospect at energy-saving and emission-reduction, environmental protection, energy utilization and conversion, oil refining and chemical industry.
Present high temperature CaO base CO
2The research in adsorbent field mainly contains the following aspects:
(1) CaO and Al
2O
3The compound aspect:
Publication number is that CN 1676210 patents of invention disclose a kind of high active calcium-base CO
2Absorbent and preparation method thereof, this method be with alcohols, distilled water, and aluminium salt, calcium oxide are raw material; 800～1000 ℃ of calcinings 1～4 hour; Add alcohols and distilled water; Dry good sample was calcined 3 hours in 500～700 ℃, ground levigate; Add distilled water again, drying; The sample that drying is good was calcined 1～3 hour down at 700～1100 ℃; Grind porphyrize and be high active calcium-base CO
2Absorbent.This invention does not relate to coating of particles and Wear Resistance.
Yang Mingshan etc. are in " nano-calcium carbonate surface in situ polymerization coating ", (" material engineering ", 2008 10 phases, the page number: 21-24) propose nano-calcium carbonate in the document and carry out the ultrasonic wave dispersion, coated acrylic acid esters co-polymer on the nano-calcium carbonate surface, make the polymerization of nano-calcium carbonate surface in situ and coated product, this method purpose forms nanometer stratum nucleare/Polymer interlayers/polymer shell, outermost shell is owing to have good compatibility with the bigger polymer of PVC isopolarity, thereby can guarantee the nano-dispersed of nano particle in polymeric matrix.
(2) nanometer CaO/Al
2O
3The adsorbent aspect
The inventor has some research report and patents before this, wherein:
1. teacher's fine jade, Wu Sufang etc., " nano-calcium base CO
2Sorbent reactions absorption and decomposition kinetics " (" chemical industry journal ", 2009,60 (3): 641-648), report in the experiment with nanometer CaCO
3Powder is dispersed in the water through ultrasonic, mixes by a certain percentage with the aluminium oxide adhesive, is dried into slurry, behind homemade banded extruder extruded moulding, drying, grinding, with the screening of 74-100 μ m sieve, to average grain diameter be 60-80 μ m be the calcium base CO of presoma with the nano-calcium carbonate
2Absorbent particles.Not only prepare the shape difference of adsorbent, and do not relate to coating of particles and anti-wear performance.
2.Su.F.Wu，Qing.H.Li，Jong.N.Kim，Kwang.B.Yi，Properties?ofNano?CaO/Al2O3?CO2?Sorbent，Ind.Eng.Chem.Res.2008，47(1)180-184。The document is reported a kind of CaO/Al2O3 preparation of adsorbent method, and the 5g nano-calcium carbonate is added beaker, adds 30g aluminium colloidal sol and stirs into suspension.Add the 2g sodium hexametaphosphate dispersant, stir and make the calcium carbonate dispersion evenly.Mixture adds oven dry then, is pressed into particle.Characteristics are the irregular grain shapes of preparation, mainly study the stability of its adsorption capacity and adsorption capacity.Do not relate to anti-wear performance.
3. Wu Su virtue, Wu Rong, publication number are CN1762572A, denomination of invention: " siliceous nano calcium oxide high temperature carbon dioxide adsorbent and this preparation of adsorbent method and the application in hydrogen manufacturing industry ", a kind of siliceous nano calcium oxide high temperature carbon dioxide adsorbent is disclosed, by nanometer CaCO
3With sol-gel process coated Si O
2Or nanometer CaCO
3Directly and nanometer SiO
2Powder is made siliceous nanometer CaCO after evenly mixing
3Powder again with the forming agent mixed-forming, forms at 600-800 ℃ of temperature lower calcination; Described siliceous nanometer CaCO
3Contain SiO in the powder
2Amount is the 2-10 weight portion.
4. Wu Su virtue, Shi Qi, publication number are CN101306309A, and name is called " preparation method of nano-calcium base carbon dioxide absorbent modified by silica precipitation ", a kind of preparation method of nano-calcium base carbon dioxide absorbent modified by silica precipitation is disclosed, with nanometer CaCO
3With Na
2SiO
3Be mixed with suspension, feed CO
2, and stop ventilation, filtration, drying when constantly agitating solution is to suspension PH=7-8, obtain the carbon-dioxide absorbent particle after the screening.The inventive method adopts CO
2Be precipitating reagent, with Na
2SiO
3Feeding CO
2Under the condition of sour gas, generate SiO
2, and be deposited in nanometer CaCO
3The surface, form one deck coating film.
Studies show that natural calcium base CO
2There is major defect in the polishing machine of adsorbent, and changing CaO base adsorbent composition is a research tendency to improve polishing machine.
Summary of the invention
The present invention is directed to CaO base CO with wide application background
2The shape and the tear strength of reaction adsorbent propose the calcium oxide-based CO of a kind of preparation nanometer antiwear
2The method of reaction adsorbent improves the spherical CaO base of preparation CO
2Reaction adsorbent attrition intensity satisfies industrial instructions for use.
The calcium oxide-based CO of a kind of preparation nanometer antiwear
2The method of reaction adsorbent is with CaCO
3Particle disperses with the mode of ultrasonic wave or stirring in water, adds aluminium colloidal sol, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, is prepared into the calcium oxide-based CO of spherical nanometer antiwear after calcining
2The reaction adsorbent.
Preferably, the calcium oxide-based CO of a kind of preparation nanometer antiwear
2The method of reaction adsorbent is with CaCO
3Particle disperses in water with ultrasonic wave, behind the adding aluminium colloidal sol, adds inorganic non-metallic oxide and/or calcium salt again, and addition is with CaCO in the solution
3Al with the conversion of aluminium colloidal sol amount
2O
3The gross weight meter of amount is 1%-50%; Be stirred to uniform sizing material, carry out mist projection granulating, obtain the microsphere particle that particle diameter is 20-250 μ m, be prepared into the calcium oxide-based CO of spherical nanometer antiwear after calcining
2The reaction adsorbent.
Described aluminium colloidal sol is the industrial goods that is formed by aluminium salt and alcoholic solution hydrolysis, and its composition is for containing Al
2O
3Colloidal solution, the preparation method has water or solvent phase preparation method, content commonly used be 10%-20%Al
2O
3Concentration.
Described inorganic non-metallic oxide is α-Al
2O
3, SiO
2Powder or corundum powder, calcium salt are calcium silicates, calcium aluminate; Particles of powder can be micron-sized, also can be nano level.Add inorganic non-metallic oxide or calcium salt with the auxiliary calcium oxide-based CO of spherical nanometer antiwear that improves preparation
2The tear strength of reaction absorbent particles.
The reaction that the inventive method calcination process takes place is:
12CaO+7Al
2O
3→Ca
12Al
14O
33 (1)
3CaO+Al
2O
3→Ca
3Al
2O
6 (2)
The inventive method calcination process granule interior change mechanism as shown in Figure 1, expression be that nano-calcium carbonate is dispersed in the liquid aluminium colloidal sol, well disperseed through stirring.Be thought of as nanometer CaCO
3Particle is surrounded by aluminium colloidal sol, slurry is through high-temperature evaporation water and mist projection granulating, mechanical water removes, form aluminium oxide on the nano-calcium carbonate surface, after high-temperature calcination, nano-calcium carbonate decomposes the generation nano calcium oxide, generates the calcium aluminate layer between nano calcium oxide and aluminium oxide main body, and nanometer calcium aluminate layer has the duct, is beneficial to CO
2Diffusion and react with nanometer CaO surface.
Suitable Ca/Al mol ratio and calcining heat are to improve the main cause of adsorbent wearability.After high-temperature calcination, form 3 calcium (Ca
3Al
2O
6) and 12 calcium (Ca
12Al
14O
33).The formation of calcium aluminate has constituted the framework in the nano calcium oxide outside, is the main cause that improves the adsorbent wearability.
Above-mentioned being reflected under the many situations of calcium content by stoichiometric reaction helps generating 3 calcium, therefore at Ca/Al mol ratio main 3 calcium that form 13.6 or more, less than 13.6 main generation 12 calcium.
The described Ca/Al molar ratio range of the inventive method is 1.0-15.0, and optimum molar ratio is 2.3-3.5, and generating 12 calcium under preferred mol ratio condition is main calcium aluminate compound skeleton, thereby has improved polishing machine.
The scope of described calcining heat is 700-1100 ℃, and preferred temperature range is: 800-1000 ℃.
The fluidized-bed reaction system requires CaO base CO
2The shape and the tear strength of reaction adsorbent all have the higher requirement of ratio.Have only spherical material just can help fluidisation, and the material that wearability is good could reduce the particle experience wear and the trend of fine-powdered.
The present invention is by the calcium oxide-based CO of ball shaped nano of spray-on process preparation
2The reaction adsorbent can be used for fluid bed, and the reaction of reactors such as moving bed and fixed bed removes CO
2Material.
CaO under 600 ℃ of left and right sides high temperature with CO
2Reaction absorption generates CaCO
3, CaCO then
3At 800 ℃ of left and right sides heating and calcining regeneration CaO, so move in circles, can constantly remove the CO in the gas
2Reaction equation is shown in (3).
Can be by CaO and CO
2Carry out chemical reaction metering equation, also can remove CO fast to greatest extent
2, take off CO at flue gas
2, reaction removes CO
2Adsorption forced methane steam reforming hydrogen manufacturing new technology etc. is taken off the charcoal process all important application.
The inventive method adopts nanometer CaCO
3Be raw material, guaranteed CaCO
3Particle is tiny; The adding of aluminium colloidal sol reaches separates each nanometer CaCO
3Purpose; By mist projection granulating, reach the purpose that is prepared into spheric granules; By changing preparation process raw materials of Ca CO
3With the proportional quantity of aluminium colloidal sol, more equably with nanometer CaCO
3The surface coats, and can reach the calcium aluminate compound of developing different content and composition through high-temperature calcination, utilizes the good principle of calcium aluminate intensity simultaneously, improves nanometer CaO/Al
2O
3High temperature CO
2The polishing machine of adsorbent.
The calcium oxide-based CO of preparation nanometer antiwear of the present invention's preparation
2The reaction adsorbent has even coating, and clad has the adsorption capacity height through the calcium aluminate of calcining production nanometer layer, the characteristics that stability is high.
Description of drawings
Fig. 1 is the inventive method calcination process granule interior change mechanism schematic diagram.
Fig. 2 is the calcium oxide-based CO of nanometer antiwear of the embodiment of the invention 3 preparations
2The SEM shape appearance figure of reaction adsorbent.
Fig. 3 is the calcium oxide-based CO of nanometer antiwear of the embodiment of the invention 3 preparations
2XRD figure after the calcining of reaction adsorbent.
Fig. 4 is the preceding TEM figure of the sample CA-6-9 calcining of the present invention's preparation.
Fig. 5 is the sample CA-6-9 calcining back TEM figure of the present invention's preparation.
Fig. 6 is a SEM shape appearance figure before and after Different Ca of the present invention/Al content wear testing.Wherein:
(1) SEM shape appearance figure before the CA-5-9 calcining, (2) CA-5-9 calcining back SEM shape appearance figure,
(3) SEM shape appearance figure before the CA-6-9 calcining, (4) CA-6-9 calcining back SEM shape appearance figure,
(5) SEM shape appearance figure before the CA-8-9 calcining, (6) CA-8-9 calcining back SEM shape appearance figure,
(7) SEM shape appearance figure before the CA-9-9 calcining, (8) CA-9-9 calcining back SEM shape appearance figure.
Fig. 7 is the SEM-EDX result of the sample CA-6-9 wearing and tearing back test of the present invention's preparation.
Fig. 8 is different calcining heats of the sample of the present invention's preparation and adsorption capacity stability relationship.
Fig. 9 is the sample Different Ca/Al ratio of the present invention's preparation and the relation of adsorption capacity.
The specific embodiment
Embodiment 1:
With CaCO
3Particle 50g disperses in water with ultrasonic wave, adds aluminium colloidal sol 15%225g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 2:
With CaCO
3Particle 200g disperses in water with ultrasonic wave, adds aluminium colloidal sol 15%590g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 850 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 3:
With CaCO
3Particle 80g disperses in water with ultrasonic wave, adds aluminium colloidal sol 15%234g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 4:
With CaCO
3Particle 80g disperses in water with ultrasonic wave, adds aluminium colloidal sol 15%165g, adds high-strength nano α-Al
2O
3Powder 8g is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 5:
With CaCO
3Particle 80g disperses in water with ultrasonic wave, adds aluminium colloidal sol 15%120g, adds high-strength nano SiO
2Powder 20g is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 950 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 6:
With CaCO
3Particle 80g disperses in water with ultrasonic wave, adds aluminium colloidal sol 20%173g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 1000 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 7:
With CaCO
3Particle 50g disperses in water with ultrasonic wave, adds aluminium colloidal sol 10%145g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 8:
With CaCO
3Particle 50g disperses in water with ultrasonic wave, adds aluminium colloidal sol 10%85g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 9:
With CaCO
3Particle 150g disperses in water with ultrasonic wave, adds aluminium colloidal sol 10%112g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 10:
With CaCO
3Particle 150g disperses in water with ultrasonic wave, adds aluminium colloidal sol 10%112g, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 1000 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 11:
With CaCO
3Particle 100g stirs the back by brute force to be disperseed in water, adds aluminium colloidal sol 20%300g, adds calcium aluminate powder 20g, be stirred to uniform sizing material, carry out mist projection granulating, obtain the microsphere particle that particle diameter is 20-250 μ m, 1000 ℃ of calcinings down, be prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 12:
With CaCO
3Particle 80g stirs the back by brute force to be disperseed in water, adds aluminium colloidal sol 10%340g, adds calcium silicates powder 115g, be stirred to uniform sizing material, carry out mist projection granulating, obtain the microsphere particle that particle diameter is 20-250 μ m, 900 ℃ of calcinings down, be prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 13
With CaCO
3Particle 100g stirs the back by brute force to be disperseed in water, adds aluminium colloidal sol 20%260g, adds calcium aluminate powder 20g, micron α-Al
2O
3Powder 10g is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 800 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
Embodiment 14
With CaCO
3Particle 90g stirs the back by brute force to be disperseed in water, adds aluminium colloidal sol 20%260g, adds calcium silicates powder 20g, micron α-Al
2O
3Powder 10g is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, 1000 ℃ of calcinings down, is prepared into the calcium oxide-based CO of spherical nanometer antiwear
2The reaction adsorbent.
The polishing machine method of testing:
Absorbent particles adopts air jet cup wearability test device (fluidized bed testingsystem), some gram absorbent particles are placed the jet cup bottom, relative humidity is under 60 ± 5% room temperature (20 ± 5 ℃) gas condition in cup, be blown into air with air pump, under certain air velocity, keep 1 hour after, collection cups substrate material, weigh, can calculate wear rate, the rate of recovery and average grain diameter reduce.Wherein the purpose of determination of recovery rates is the accuracy of judgment data, and the test of wear rate and average grain diameter all is the polishing machine of direct reaction particles.
Parameter calculation formula is listed formula (4) (5) (6) respectively in the table 2, table 3:
Fine powder rate=(20g-mill back adsorbent weight)/20g * 100% (4)
The rate of recovery=(the fine powder quality that wearing and tearing back granular mass+collect the wearing and tearing back)/20g * 100%
(5)
Average grain particle diameter * 100% (6) before average particulate diameter (VMPS) reduction=(average grain particle diameter before the wearing and tearing-wearing and tearing back average grain particle diameter)/wearing and tearing
CO
2The test of adsorption capacity: with the adsorption capacity of thermogravimetric analyzer (TGA) working sample.
Fine powder rate and absorption volume test result such as table 1
Table 1
| |
1 | 2 | 3 | 4 | 5 |
| Numbering | CA-5-9 | CA-6-8 | CA-6-9 | / | / |
| Fine powder rate (%) | 5.9 | 3.9 | 2.09 | 1.9 | 5.4 |
| |
6 | 7 | 8 | 9 | 10 |
| Numbering | CA-6-10 | CA-7-9 | CA-8-9 | CA-9-9 | CA-9-10 |
| Fine powder rate (%) | 1.55 | 2.14 | 3.85 | 11.93 | 9.21 |
Table 2 is adsorbent numbering of the present invention and preparation condition
Table 2
* table is annotated: sample title CA-5-8 is an example, and 5 represent CaCO
3Quality is 50%, is 1.5,8 to represent 800 ℃ of calcining heats with respect to the Ca/Al mol ratio.
Table 3 shows Ca/Al ratio content relative fixed 2.3 for the polishing machine test result of sample under the different calcining heat conditions of the present invention, and after calcining heat was elevated to 1000 ℃ from 800 ℃, the fine powder rate brought up to 1.55% from 3.9%.
Table 3
Table 4 is the polishing machine test result of sample under Different Ca of the present invention/Al mol ratio condition, shows in calcining heat and fixes, and Ca content improves, and the fine powder rate improves.
Table 4
Formed the calcium aluminate of 3 calcium and 12 calcium after the XRD analysis proof high-temperature calcination of Fig. 2.
Fig. 3 and Fig. 4 contrast show nanometer CaO/Al
2O
3Pattern has very big difference before and after the sample CA-6-9 calcining, and reduce intergranular space, calcining back.
Fig. 5 shows that the high sample of sorbent of calcium content has poor polishing machine.
The result of Fig. 6 proves, nano calcium oxide base high temperature CO
2The wearing and tearing that adsorbent exists are mainly the surfacial spalling wearing and tearing, rather than fracture wear.
Fig. 7 shows that adsorbent is at 1000 ℃ of calcinings down, CO
2Adsorption capacity reduces more.
Fig. 8 shows that Ca content is high more in the adsorbent, CO
2Adsorption capacity is big more.But Al content is high more, CO
2Adsorption capacity stability is good more.
Adsorption capacity and adsorption capacity stability test
Get embodiment 9 sample adsorbent 3mg, adopting model is the TGA test adsorption capacity of Pyris 1, is 600 ℃ at adsorption temp, and 750 ℃ of regeneration temperatures are to containing 20%CO
2N
2Mist, measuring for the first time, adsorption capacity is the 4.0mol/kg adsorbent.
Get embodiment 10 sample adsorbent 3mg, adopting model is the TGA test adsorption capacity of Pyris1, is 600 ℃ at adsorption temp, and 750 ℃ of regeneration temperatures are to containing 20%CO
2N
2Mist, measuring for the first time, adsorption capacity is the 1.6mol/kg adsorbent.
Fig. 9 shows under the identical Ca/Al content condition, the CO of the adsorbent that different calcining heats obtain
2The situation of change that adsorption capacity and adsorption capacity increase with cycle-index.Calcining heat is high more, and adsorption capacity obviously reduces, but the stability of adsorption capacity obviously improves.
Application examples
Application examples 1
Adopt the fixed fluidized-bed reactor test to contain 10%CO
2, N
2Use the decarburization effect of adsorbent for the mist of carrier gas.Getting the fresh adsorbent of 15g embodiment 7 preparations, after 780 ℃ of regeneration are finished, is under the 600ml/min condition at mixed gas flow, and reaction temperature is 590 ℃, adsorption time 20min, and the adsorption capacity that records adsorbent is 1.8mol/kg.
Application examples 2
Adopt the fixed fluidized-bed reactor test to contain 10%CO
2, N
2Use the decarburization effect of adsorbent for the mist of carrier gas.Adsorbent to embodiment 7 preparations repeatedly circulates, and the condition of circular response is: reaction temperature is 590 ℃, 780 ℃ of regeneration temperatures.The 7th circulation after regeneration is finished, is under the 600ml/min condition at mixed gas flow, adsorption time 20min, and the adsorption capacity that records adsorbent is 1.65mol/kg.
Claims (10)
1. one kind prepares the calcium oxide-based CO of nanometer antiwear
2The method of reaction adsorbent is with nanometer CaCO
3Particle disperses in water, adds aluminium colloidal sol, is stirred to uniform sizing material, carries out mist projection granulating, obtains the microsphere particle that particle diameter is 20-250 μ m, is prepared into the calcium oxide-based CO of spherical nanometer antiwear after calcining
2The reaction adsorbent.
2. one kind prepares the calcium oxide-based CO of nanometer antiwear
2The method of reaction adsorbent is with nanometer CaCO
3Particle disperses in water, add aluminium colloidal sol after, add again the inorganic non-metallic compound particle and or calcium salt, be stirred to uniform sizing material, carry out mist projection granulating, obtain the microsphere particle that particle diameter is 20-250 μ m, be prepared into the calcium oxide-based CO of spherical nanometer antiwear after calcining
2The reaction adsorbent.
3. the calcium oxide-based CO of preparation nanometer antiwear according to claim 1
2The method of reaction adsorbent, it is characterized in that: described inorganic non-metallic oxide is α-Al
2O
3, SiO
2Powder or corundum powder, described calcium salt are calcium silicates, calcium aluminate.
4. the calcium oxide-based CO of preparation nanometer antiwear according to claim 1 and 2
2The method of reaction adsorbent, it is characterized in that: described Ca/Al mol ratio is 1.0-15.0.
5. the calcium oxide-based CO of preparation nanometer antiwear according to claim 4
2The method of reaction adsorbent, it is characterized in that: described Ca/Al mol ratio is 2.3-3.5.
6. according to claim 2 or the calcium oxide-based CO of 3 described preparation nanometer antiwears
2The method of reaction adsorbent is characterized in that: described inorganic non-metallic oxide and or the addition of calcium salt, with CaCO in the solution
3Al with the conversion of aluminium colloidal sol amount
2O
3The gross weight meter of amount is 1%-50%.
7. the calcium oxide-based CO of preparation nanometer antiwear according to claim 1 and 2
2The method of reaction adsorbent, it is characterized in that: the scope of described calcining heat is 700-1100 ℃.
8. the calcium oxide-based CO of preparation nanometer antiwear according to claim 7
2The method of reaction adsorbent, it is characterized in that: the scope of described calcining heat is 800-1000 ℃.
9. according to the calcium oxide-based CO of the described preparation nanometer antiwear of the arbitrary claim of claim 1-8
2The calcium oxide-based CO of spherical nanometer antiwear of the method preparation of reaction adsorbent
2The reaction adsorbent.
10. the calcium oxide-based CO of nanometer antiwear according to claim 9
2The reaction adsorbent removes CO as the reaction in fluidized-bed reactor, moving-burden bed reactor, the fixed bed reactors
2The application of material.
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| CN102671618A (en) * | 2012-04-28 | 2012-09-19 | 浙江大学 | Preparation method for microspherical nano CaO-based CO2 adsorber for circulating fluidized bed, product and application |
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