CN106475041A - A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent and application - Google Patents

A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent and application Download PDF

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CN106475041A
CN106475041A CN201611055158.4A CN201611055158A CN106475041A CN 106475041 A CN106475041 A CN 106475041A CN 201611055158 A CN201611055158 A CN 201611055158A CN 106475041 A CN106475041 A CN 106475041A
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nano
meter sio
adsorbent
cao
calcium carbonate
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蒋建国
颜枫
刘诺
田思聪
李凯敏
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Tsinghua University
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Tsinghua University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/06—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • B01D53/12—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents according to the "fluidised technique"
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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

Abstract

A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent, ball mill crushing, screening Calcium Carbonate and Nano-meter SiO_2 respectively2, Nano-meter SiO_22Specific surface area is more than 200m2/ g, including but not limited to sedimentation method Nano-meter SiO_22, fumed nano SiO2, ZSM 5 molecular sieve, MCM 41 molecular sieve, MCM 48 molecular sieve, MCM 50 molecular sieve and SBA 15 molecular sieve；It is (80 in mass ratio:20)～(95:5) weigh, solid phase mixing Calcium Carbonate (in terms of contained CaO mass) and Nano-meter SiO_22；By mixture in atmosphere of inert gases, 850 950 DEG C of calcining 2 6h, after cooling, obtain adsorbent product；Use it for recirculating fluidized bed, achievable CO2Rapid acquiring and adsorbent reactivation；The method adopts solid phase mixing technology, it is to avoid high energy consumption, the liquid phase reaction course of high cost；This product adsorption rate is fast, adsorbance ratio 20s the quick adsorption stage up to more than 85%, and high-temperature stability is strong, circulation absorption capacity is big, and adsorption capacity remains to reach 0.30g after 30 circulationsCO2/gAdsorbent, it is suitable for realizing scale application in recirculating fluidized bed.

Description

A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent and application
Technical field
The invention belongs to industrial source CO2Trapping and field of material synthesis technology, particularly to a kind of Nano-meter SiO_22/ CaO adsorbs The synthetic method of agent and be used for quick CO2The application of trapping.
Background technology
The substantial amounts of energy resource consumption of the mankind and industrial discharge cause atmospheric greenhouse gas (CO2、CH4、N2O and CFCs etc.) dense Degree increases sharply, and causes global warming, the series change such as sea level rise.Show according to World Bank's public data, the temperature in the whole world Room gas emissions increase sharply year by year, the total emission volumns of 1970,1980,1990,2000 and 2012 be respectively 270.75, 328.34th, 374.62,396.53 and 527.63 hundred million tons (with CO2Work as gauge).Wherein, global CO in 20122Total emission volumn is 354.64 hundred million tons, account for the 67.21% of greenhouse gas emission total amount, be topmost greenhouse gases.For alleviating global warming Problem, its core is the greenhouse gas concentration in the source discharge and control air cut down greenhouse gases, wherein " CO2Trapping, Storage and utilize " be maximally effective solution route at present.
The greenhouse gases of China and CO2Total emission volumn occupies the whole world first since two thousand five always, is faced with huge World opinion pressure.On November 4th, 2016, reply climate change《Reach an agreement in Paris》Formally effective, wherein China promises to undertake About the year two thousand thirty, CO2 emission reaches peak value, and unit GDP CO2 emission declined than 2005 years 60%-65%.China's greenhouse gas emission total amount of 2012 is 124.55 hundred million tons (with CO2Work as gauge), wherein CO2Discharge is total Measure for 100.21 hundred million tons, account for the 80.46% of China's greenhouse gas emission total amount, therefore control the key of China's greenhouse gas emission It is to cut down China CO2Total emission volumn.
Based on the high temperature calcium circulating technology of CaO circulation absorption, desorbing, have that theoretical adsorption capacity is big, trapping cost is low Advantage, is the CO of most large-scale application prospect2Trapping technique.In traditional calcium circulating technology, the natural minerals rich in CaO are One class sorbent material cheap and easy to get, but such material exists that high temperature circulation stability is poor, adsorption capacity decay is fast lacks Point.Study typically with calcium of organic acid and slaine as presoma, using the technology such as sol-gel process and wet mixing conjunction, synthesis cycle The higher Ca-base adsorbent of absorption property.But, the rate of adsorption of such adsorbent is slow, saturated adsorption time is more than 30 minutes, It is not suitable for the fluid bed system (time of contact is less than 1 minute) of sizable application；And, cost of material is high, complex manufacturing, It is also the main cause limiting its scale application.
Nano-meter SiO_22It is a kind of wide variety of additive, have that specific surface area is big, pore structure enriches, heat stability The advantage such as high, with low cost.Therefore, with Nano-meter SiO_22For stabilizer, the cyclical stability of Ca-base adsorbent can be effectively improved With circulation absorption capacity；Meanwhile, Nano-meter SiO_22Abundant, stable pore structure can be CO2Diffusion provide passage, significantly carry The rate of adsorption of high Ca-base adsorbent, shortening adsorption saturation time.Additionally, the method is calcium presoma, is adopted admittedly with limestone Phase hybrid technology, it can be avoided that the liquid phase reaction course of complexity, suitable large-scale production application.At present, the method is at home and abroad Have not been reported.
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 Nano-meter SiO_22/ CaO adsorbent Synthetic method and be used for quick CO2The application of trapping, based on solid phase mixing technology path, can improve material property, reduce life Produce cost, realize CO in industrial source flue gas2The scale application of rapid acquiring, final solution natural calcium base adsorbent stable circulation Property poor, the synthesis Ca-base adsorbent rate of adsorption is slow and the problem of complex manufacturing,
To achieve these goals, the technical solution used in the present invention is：
A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent, comprises the following steps：
(A) raw material crushes, sieves：Using vertical-type planetary ball milling crusher machine Calcium Carbonate and Nano-meter SiO_22, then adopt 400 mesh sieves Divide device, respectively screening Calcium Carbonate and Nano-meter SiO_22, obtain the raw material for standby that particle diameter is less than 37 μm；
(B) solid phase mixing：Weigh the Calcium Carbonate after screening in step (A) and Nano-meter SiO_22, using agate mortar by carbonic acid Calcium and Nano-meter SiO_22It is sufficiently mixed, grind 10-20min；
(C) calcine stabilisation：By the Calcium Carbonate after grinding in step (B) and Nano-meter SiO_22Mixture is placed in tube furnace, After calcination reaction under atmosphere of inert gases, mixture obtains Nano-meter SiO_2 after natural cooling in tube furnace2/ CaO adsorbent.
Gained Nano-meter SiO_2 of the present invention2/ CaO adsorbent can be used for quick CO2Circularly trapping：By the nanometer in step (C) SiO2/ CaO adsorbent is placed in recirculating fluidized bed, is passed through containing CO2Flue gas carry out adsorption reaction, be passed through pure CO after adsorption saturation2 Gas carries out the regenerative response of adsorbent.
In described step (A), in described vertical-type planetary ball mill shattering process, the mass ratio of abrading-ball and material is 3:1, ball Mill speed is 350-400rpm, and Ball-milling Time is 10-30min；Described Nano-meter SiO_22Specific surface area is more than 200m2/ g, including but It is not limited to sedimentation method Nano-meter SiO_22, fumed nano SiO2, ZSM-5 molecular sieve, MCM-41 molecular sieve, MCM-48 molecular sieve, MCM- 50 molecular sieves and SBA-15 molecular sieve.
In described step (B), described Calcium Carbonate and Nano-meter SiO_22Mass ratio be (80:20)～(95:5), wherein carbonic acid Calcareous amount is in terms of contained CaO mass.
In described step (C), described noble gases are nitrogen (N2At least one of) and argon (Ar), described tube furnace Heating rate is 15 DEG C/min, and calcination reaction temperature is 850-950 DEG C, the calcination reaction time is 2-6h；In described calcination process, Calcium Carbonate and Nano-meter SiO_22Dicalcium silicate (Ca is generated after reaction2SiO4) inert component, such as shown in reaction equation (1), Neng Gouti The cyclical stability of high Ca-base adsorbent.
Described quick CO2In circularly trapping reaction, the temperature of adsorption reaction is 650-700 DEG C, the CO of flue gas2Concentration is 15- 20vol%, the temperature of regenerative response is 900-920 DEG C.
Compared with prior art, the invention has the beneficial effects as follows：
1. with Calcium Carbonate and Nano-meter SiO_22For raw material, Nano-meter SiO_2 is synthesized using solid phase mixing technology2/ CaO adsorbent, it is to avoid High energy consumption, the liquid phase reaction course of high cost, suitable large-scale production application.
2. this product possesses quick adsorption performance, and in the quick adsorption stage of 20s, adsorbance ratio reaches more than 85%, Be conducive to realizing quick CO in recirculating fluidized bed2Trapping.
3. this product high-temperature stability is strong, circulation absorption capacity is big, and after 30 circulations, adsorption capacity remains to reach 0.30gCO2/gAdsorbent, improve more than 200% than ordinary calcium carbonate.
Brief description
Fig. 1 is present invention process flow chart.
Fig. 2 is Nano-meter SiO_22The grain size distribution of/CaO adsorbent, corresponding embodiment 3.
Fig. 3 is different proportion Nano-meter SiO_22The X ray diffracting spectrum of/CaO adsorbent, corresponding embodiment 2～4.
Fig. 4 is different proportion Nano-meter SiO_22The circulation absorption performance of/CaO adsorbent, corresponding embodiment 2～4.
Specific embodiment
Describe embodiments of the present invention in detail with reference to the accompanying drawings and examples, but the present invention is not subject to these embodiments Limit.
Embodiment 1
(A) vertical-type planetary ball milling crusher machine Calcium Carbonate and sedimentation method Nano-meter SiO_2 are adopted2(specific surface area is 342m2/ g, hole body Amass as 0.64cm3/ g), regulation drum's speed of rotation is 400rpm, Ball-milling Time is 10min；Using 400 mesh sifters, sieve respectively Divide Calcium Carbonate and sedimentation method Nano-meter SiO_22, obtain the raw material for standby that particle diameter is less than 37 μm.
(B) Calcium Carbonate 142.8g after step (A) screening and sedimentation method Nano-meter SiO_2 are accurately weighed220g (Calcium Carbonate quality In terms of contained CaO mass, mass ratio is 80:20), using agate mortar by Calcium Carbonate and sedimentation method Nano-meter SiO_22Be sufficiently mixed, Grind 10min.
(C) by the Calcium Carbonate after grinding in step (B) and sedimentation method Nano-meter SiO_22Mixture is placed in tube furnace, with 15 DEG C/ramp of min, in N2Under atmosphere, 850 DEG C of calcining 6h, mixture received after natural cooling in tube furnace Rice SiO2/ CaO adsorbent.
(D) Nano-meter SiO_2 in step (C)2/ CaO adsorbent is placed in recirculating fluidized bed, is passed through containing 15vol%CO2Cigarette Gas, at 650 DEG C, carry out adsorption reaction, after adsorption saturation, be passed through pure CO2Gas, the regeneration carrying out adsorbent at 900 DEG C are anti- Should.
Embodiment 2
(A) vertical-type planetary ball milling crusher machine Calcium Carbonate and sedimentation method Nano-meter SiO_2 are adopted2(specific surface area is 342m2/ g, hole body Amass as 0.64cm3/ g), regulation drum's speed of rotation is 400rpm, Ball-milling Time is 10min；Using 400 mesh sifters, sieve respectively Divide Calcium Carbonate and sedimentation method Nano-meter SiO_22, obtain the raw material for standby that particle diameter is less than 37 μm.
(B) Calcium Carbonate 151.7g after step (A) screening and sedimentation method Nano-meter SiO_2 are accurately weighed215g (Calcium Carbonate quality In terms of contained CaO mass, mass ratio is 85:15), using agate mortar by Calcium Carbonate and sedimentation method Nano-meter SiO_22Be sufficiently mixed, Grind 10min.
(C) by the Calcium Carbonate after grinding in step (B) and sedimentation method Nano-meter SiO_22Mixture is placed in tube furnace, with 15 DEG C/ramp of min, in N2Under atmosphere, 900 DEG C of calcining 4h, mixture received after natural cooling in tube furnace Rice SiO2/ CaO adsorbent.
(D) Nano-meter SiO_2 in step (C)2/ CaO adsorbent is placed in recirculating fluidized bed, is passed through containing 15vol%CO2Cigarette Gas, at 650 DEG C, carry out adsorption reaction, after adsorption saturation, be passed through pure CO2Gas, the regeneration carrying out adsorbent at 900 DEG C are anti- Should.
Embodiment 3
(A) vertical-type planetary ball milling crusher machine Calcium Carbonate and sedimentation method Nano-meter SiO_2 are adopted2(specific surface area is 342m2/ g, hole body Amass as 0.64cm3/ g), regulation drum's speed of rotation is 350rpm, Ball-milling Time is 20min；Using 400 mesh sifters, sieve respectively Divide Calcium Carbonate and sedimentation method Nano-meter SiO_22, obtain the raw material for standby that particle diameter is less than 37 μm.
(B) Calcium Carbonate 160.6g after step (A) screening and sedimentation method Nano-meter SiO_2 are accurately weighed210g (Calcium Carbonate quality In terms of contained CaO mass, mass ratio is 90:10), using agate mortar by Calcium Carbonate and sedimentation method Nano-meter SiO_22Be sufficiently mixed, Grind 20min.
(C) by the Calcium Carbonate after grinding in step (B) and sedimentation method Nano-meter SiO_22Mixture is placed in tube furnace, with 15 DEG C/ramp of min, under Ar atmosphere, 900 DEG C of calcining 2h, mixture is received after natural cooling in tube furnace Rice SiO2/ CaO adsorbent.
(D) Nano-meter SiO_2 in step (C)2/ CaO adsorbent is placed in recirculating fluidized bed, is passed through containing 15vol%CO2Cigarette Gas, at 700 DEG C, carry out adsorption reaction, after adsorption saturation, be passed through pure CO2Gas, the regeneration carrying out adsorbent at 920 DEG C are anti- Should.
Embodiment 4
(A) vertical-type planetary ball milling crusher machine Calcium Carbonate and sedimentation method Nano-meter SiO_2 are adopted2(specific surface area is 342m2/ g, hole body Amass as 0.64cm3/ g), regulation drum's speed of rotation is 350rpm, Ball-milling Time is 30min；Using 400 mesh sifters, sieve respectively Divide Calcium Carbonate and sedimentation method Nano-meter SiO_22, obtain the raw material for standby that particle diameter is less than 37 μm.
(B) Calcium Carbonate 169.6g after step (A) screening and sedimentation method Nano-meter SiO_2 are accurately weighed25g (Calcium Carbonate quality In terms of contained CaO mass, mass ratio is 95:5), using agate mortar by Calcium Carbonate and sedimentation method Nano-meter SiO_22It is sufficiently mixed, grind Mill 20min.
(C) by the Calcium Carbonate after grinding in step (B) and sedimentation method Nano-meter SiO_22Mixture is placed in tube furnace, with 15 DEG C/ramp of min, under Ar atmosphere, 950 DEG C of calcining 2h, mixture is received after natural cooling in tube furnace Rice SiO2/ CaO adsorbent.
(D) Nano-meter SiO_2 in step (C)2/ CaO adsorbent is placed in recirculating fluidized bed, is passed through containing 20vol%CO2Cigarette Gas, at 700 DEG C, carry out adsorption reaction, after adsorption saturation, be passed through pure CO2Gas, the regeneration carrying out adsorbent at 920 DEG C are anti- Should.
Embodiment 5
Described step is same as Example 3, and difference is Nano-meter SiO_2 in step (A)2Raw material is fumed nano SiO2(ratio Surface area is 355m2/ g, pore volume are 0.74cm3/g).
Embodiment 6
Described step is same as Example 3, and difference is Nano-meter SiO_2 in step (A)2Raw material (compares table for ZSM-5 molecular sieve Area is 337m2/ g, pore volume are 1.28cm3/g).
Embodiment 7
Described step is same as Example 3, and difference is Nano-meter SiO_2 in step (A)2Raw material is MCM-41 molecular sieve (ratio Surface area is 928m2/ g, pore volume are 1.02cm3/g).
Embodiment 8
Described step is same as Example 3, and difference is Nano-meter SiO_2 in step (A)2Raw material is MCM-48 molecular sieve (ratio Surface area is 858m2/ g, pore volume are 0.98cm3/g).
Embodiment 9
Described step is same as Example 3, and difference is Nano-meter SiO_2 in step (A)2Raw material is MCM-50 molecular sieve (ratio Surface area is 780m2/ g, pore volume are 1.14cm3/g).
Embodiment 10
Described step is same as Example 3, and difference is Nano-meter SiO_2 in step (A)2Raw material is SBA-15 molecular sieve (ratio Surface area is 750m2/ g, pore volume are 1.09cm3/g).
To embodiment product analysis and contrast：
(1) Nano-meter SiO_22/ CaO adsorbent particle diameter distribution is tested
Nano-meter SiO_2 is measured using laser particle analyzer (U.S.'s Beckman Kurt, LS 13320 type)2/ CaO adsorbent Particle diameter distribution.
Fig. 2 is the grain size distribution of sample in embodiment 3.It can be seen that the adsorbent after crushing, sieving Grain diameter is respectively less than 37 μm, the centralized particle diameter of this sample 4.9-34.8 μm, mean diameter be 20.5 μm.
(2) Nano-meter SiO_22/ CaO adsorbent X-ray diffractogram analysis of spectrum
Nano-meter SiO_2 is measured using X-ray high-resolution diffractometer (Siemens, D8Advance type)2/ CaO adsorbent Crystal characteristic.Instrument radiation source selects Cu-K α (λ=0.15406nm), 2 θ angle ranges 10-90 °, and scan mode is continuously to sweep Retouch, scanning speed is 2 °/min.
Fig. 3 is without Nano-meter SiO_22Ordinary calcium carbonate sample and embodiment 2～4 in sample X ray diffracting spectrum. Result shows, in step (C) calcining stabilization procedures, Decomposition of Calcium Carbonate generates calcium oxide to ordinary calcium carbonate sample, therefore schemes The diffraction maximum of CaO crystal is only occurred in that in spectrum.In embodiment 2 and 3, sample removes CaO crystal, all generates quartzy (SiO2) and silicon Sour dicalcium (Ca2SiO4) crystal diffraction maximum.This result confirms during step (C) calcining stabilisation, Calcium Carbonate and receiving Rice SiO2Reaction, generates dicalcium silicate crystal, because dicalcium silicate crystal has the graceful temperature of higher Thailand (929 DEG C) and stronger Anti-sintering property, thus enhancing Nano-meter SiO_22The cyclical stability of/CaO adsorbent, improve its circulation absorption capacity.This Outward, Nano-meter SiO_2 in embodiment 42Addition is relatively low, thus fails to detect the diffraction of dicalcium silicate crystal in sample of sorbent Peak.
(3) Nano-meter SiO_22/ CaO sorbent circulation absorption property is tested
Calcio CO is tested using thermogravimetric analyzer (Switzerland's prunus mume (sieb.) sieb.et zucc. Teller, TGA/DSC 2 type)2The circulation absorption of adsorbent Energy.First, sample is placed in 700 DEG C, 100%CO2Under the conditions of adsorb 5min；Again by sample with the ramp of 100 DEG C/min To 900 DEG C, in 900 DEG C, 100%N2Under the conditions of desorbing 3min.Before starting next circulation, by sample with the speed of 50 DEG C/min Cool to 700 DEG C, circulation absorption 30 times.Thermogravimetric analyzer automatic sample quality of record per second, the quality according to sample becomes Change the adsorption capacity (X calculating n-th circulationN, gCO2/gAdsorbent), as shown in formula (2)；Wherein, m1NAnd m2NRepresent that sample exists respectively Quality (g) after n-th absorption and after desorbing, m0Represent the initial mass (g) of sample.
XN=(m1N-m2N)/m0(2)
Fig. 4 is without Nano-meter SiO_22Ordinary calcium carbonate sample and embodiment 2～4 in sample circulation absorption performance, Compared for different Nano-meter SiO_22The impact to sorbent circulation absorption property for the doping ratio.Result shows, Nano-meter SiO_22/ CaO adsorbs The cyclical stability of agent is obviously improved than ordinary calcium carbonate, is primarily due in sample calcining stabilization procedures, has higher The dicalcium silicate inert component of safe graceful temperature serves the effect of anti-sintering, stabilisation.In CaO and Nano-meter SiO_22Mass ratio is 90:When 10, the circulation absorption performance of adsorbent is optimal, and after 30 circulation absorptions, adsorption capacity still reaches 0.30gCO2/gAdsorbent, Improve 205% than ordinary calcium carbonate sample.
For being further elucidated with Nano-meter SiO_22The quick adsorption performance of/CaO adsorbent, will be quick for the reaction atmosphere of adsorbent sum The stage of reaction (20-60s) and slow reaction stage, the adsorbance ratio in the fast reaction stage for the adsorbent is to evaluate it in circulation The key index of actual absorption property in fluid bed.Table 1 list in ordinary calcium carbonate sample and embodiment 3 sample the 1st, 2, Adsorption time (the Δ t in quick adsorption stage in 15 and 30 circulationsN, s) with adsorbance ratio (ηN, %).The quick adsorption stage Shown in adsorbance ratio such as formula (3), wherein, XFN(gCO2/gAdsorbent) and XN(gCO2/gAdsorbent) it is respectively adsorbent in n-th circulation The adsorbance in middle quick adsorption stage and the adsorption capacity of n-th circulation.
ηN=XFN/XN× 100% (3)
Table 1 result shows, the adsorbance ratio in the quick adsorption stage for the ordinary calcium carbonate sample circulates at the 1st and is 73.08%, quickly fall to 52.13% in the 2nd circulation, and increase continuation decline with cycle-index.But, nanometer SiO2The adsorbance ratio in the quick adsorption stage for/CaO adsorbent circulates as 84.29% at the 1st, and increase with cycle-index Plus and increase, more than 90% after 15 circulations.Add Nano-meter SiO_2 in Ca-base adsorbent2Afterwards, adsorbent is in quick adsorption rank The adsorbance ratio of section is obviously improved, and is conducive to this adsorbent to be applied in recirculating fluidized bed, carries out quick CO2Trapping.
Table 1 sample of sorbent is in the adsorption time in quick adsorption stage and adsorbance ratio

Claims (10)

1. a kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent is it is characterised in that comprise the following steps：
(A) raw material crushes, sieves：By Calcium Carbonate and Nano-meter SiO_22Broken, screening is standby；
(B) solid phase mixing：Weigh the Calcium Carbonate after screening and Nano-meter SiO_22, it is sufficiently mixed, grind 10-20min；
(C) calcine stabilisation：By the Calcium Carbonate after grinding and Nano-meter SiO_22After mixture calcination reaction under atmosphere of inert gases, Nano-meter SiO_2 is obtained after natural cooling2/ CaO adsorbent.
2. Nano-meter SiO_2 according to claim 12The synthetic method of/CaO adsorbent it is characterised in that in described step (A), Crushed using vertical-type planetary ball mill, sieved respectively using 400 mesh sifters, obtained the raw material that particle diameter is less than 37 μm；Institute State in step (B), using agate mortar by Calcium Carbonate and Nano-meter SiO_22Mixed grinding, the carbonic acid in described step (C), after grinding Calcium and Nano-meter SiO_22Mixture calcination reaction in tube furnace.
3. Nano-meter SiO_2 according to claim 22The synthetic method of/CaO adsorbent is it is characterised in that described vertical-type planetary ball In grinding machine shattering process, the mass ratio of abrading-ball and material is 3:1, drum's speed of rotation is 350-400rpm, and Ball-milling Time is 10- 30min.
4. Nano-meter SiO_2 according to claim 12The synthetic method of/CaO adsorbent it is characterised in that in described step (A), Described Nano-meter SiO_22Specific surface area is more than 200m2/ g, including sedimentation method Nano-meter SiO_22, fumed nano SiO2, ZSM-5 molecular sieve, MCM-41 molecular sieve, MCM-48 molecular sieve, MCM-50 molecular sieve and SBA-15 molecular sieve.
5. Nano-meter SiO_2 according to claim 12The synthetic method of/CaO adsorbent it is characterised in that in described step (B), Described Calcium Carbonate and Nano-meter SiO_22Mass ratio be (80:20)～(95:5), wherein Calcium Carbonate quality is in terms of contained CaO mass.
6. Nano-meter SiO_2 according to claim 12The synthetic method of/CaO adsorbent it is characterised in that in described step (C), Described noble gases are nitrogen (N2) or argon (Ar).
7. Nano-meter SiO_2 according to claim 12The synthetic method of/CaO adsorbent is it is characterised in that described calcination reaction liter Warm speed is 15 DEG C/min, and reaction temperature is 850-950 DEG C, the response time is 2-6h.
8. claim 1 synthesis gained Nano-meter SiO_22/ CaO adsorbent is used for quick CO2The application of trapping.
9. Nano-meter SiO_2 according to claim 82/ CaO adsorbent is used for quick CO2The application of trapping is it is characterised in that by institute State Nano-meter SiO_22/ CaO adsorbent is placed in recirculating fluidized bed, is passed through containing CO2Flue gas carry out adsorption reaction, logical after adsorption saturation Enter pure CO2Gas carries out the regenerative response of adsorbent.
10. Nano-meter SiO_2 according to claim 92/ CaO adsorbent is used for quick CO2The application of trapping is it is characterised in that institute The temperature stating adsorption reaction is 650-700 DEG C, the CO of flue gas2Concentration is 15-20vol%, and the temperature of regenerative response is 900-920 ℃.
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