CN102671618A - 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 PDF

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CN102671618A
CN102671618A CN2012101334725A CN201210133472A CN102671618A CN 102671618 A CN102671618 A CN 102671618A CN 2012101334725 A CN2012101334725 A CN 2012101334725A CN 201210133472 A CN201210133472 A CN 201210133472A CN 102671618 A CN102671618 A CN 102671618A
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adsorbent
gas
fluidized bed
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nano cao
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CN102671618B (en
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吴素芳
史余耀
吴嵘
薛孝宠
王燕
王樟茂
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Zhejiang University ZJU
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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

A kind of microsphere nano CaO base CO that is used for recirculating fluidized bed 2Preparation of adsorbent method, product and application
Technical field
The present invention relates to made and environmental protection, chemical process removes the carbon dioxide field, is specifically related to a kind of microsphere nano CaO base CO that is used for recirculating fluidized bed 2Preparation of adsorbent method, product and application.
Background technology
CO 2The 280ppm of content in atmosphere before by the industrial revolution risen to about present 400ppm, and it is the main cause that causes global warming.CO 2The main source of discharging is the combustion process of fossil fuel, reduces CO at present 2The means of discharge capacity are the CO to producing behind the combustion of fossil fuel 2Capture, store and utilize, thereby reach the purpose of effective reduction of discharging.
Commercialization now is mature C O comparatively 2Capture method is that wet method captures, with amine aqueous solution as the CO in the absorption liquid absorption from flue gas 2But this method also has several significant disadvantages, at first owing to will carry out Regeneration Treatment to absorption liquid, has increased energy consumption, and the energy that has reduced whole system utilizes gross efficiency; Secondly, impurity need remove the preliminary treatment of sulphur and nitrogen oxide to flue gas to the pollution of absorption liquid in the flue gas in order to reduce; In addition, also has problem such as equipment corrosion.The more important thing is and adopt wet method capture meeting, cause more pollution to the contaminated waste water of environmental emission.
In the last few years, a kind of new CO 2Trapping technique-dry method captures and receives increasing concern, and is different with the wet method capture, and dry method captures and adopts solid absorbent to the CO in the flue gas 2Adsorb, cardinal principle is the CO of active component in adsorptive reactor absorption flue gas that utilizes in the adsorbent 2Generate carbonate, reduce the CO in the flue gas 2Concentration, subsequently, adsorbent is transported in the calcination reactor regenerates, and realizes recycling of adsorbent.It is cheap, renewable that the dry method trapping technique has a raw material, flexible design, eco-friendly advantage.
CO 2The recirculating fluidized bed system that dry method captures process using has had certain research at present; Catalytic cracking (the FCC that circulating fluidized bed technique is widely used in refining oil; Fluid catalytic cracking) and fluidized bed combustion reactor (CFBC, circulating fluidized bed combustion).Therefore circulating fluid bed reactor is used for CO 2Do not have technological difficulties in the capture, and compare under this individual system, the stability of the physical property of adsorbent such as wear rate and chemical property such as adsorption capacity is still a primary difficult problem that solves in the world wide.Because these property relationships are to the cost problem of dry method decarburization.
Natural limestone and the dolomite etc. that with the calcium oxide are active component are considered to have the dry method of large development potentiality to capture adsorbent, but have two bigger defectives: adsorption capacity be prone to decay and adsorbent easy to wear.
(12 of 89 1386-1395) adopt the fluidized-bed reactor CO absorption of lime stone at pilot-scale to people such as Dennis for Lu et al., Fuel Process.Technol.2008 2, in practical operation, the temperature of absorber is controlled at 580-720 ℃, and the temperature in the regenerator is controlled at 850-950 ℃, CO 2Volume content is at 15-16%, and after 15 circulations, specific area has descended 31.9%, and after 25 circulations, adsorption efficiency has descended 26.8%, and material has worn and torn 62%.
(15of 64 for Symonds et al., Chem.Eng.Sci.2009,3536-3543) adopt lime stone CO absorption on fluid bed for people such as Symonds 2, adsorption temp is 550 ℃, atmosphere is 8%CO 2, 17%H 2The air of O; Regeneration temperature is 860 ℃; After three circulations, the time of adsorption efficiency more than 95% has descended 80%.
(24of48 11140-11147) utilizes dolomite as adsorbent CO absorption on twin drum bubble bed to people such as the Li Zhenshan of Tsing-Hua University for Fang et al., Ind.Eng.Chem.Res.2009 2, adsorption temp is 600 ℃, CO 213.4% air); Regeneration temperature is 900 ℃, and in 250min, adsorbent has lost 11.5%, and the adsorbent average grain diameter of calcining compartment has descended 68%.
(2of 4 for Alonso et al., Int.J.Greech.Gas Control.2010, and 167-173) having adopted absorber and regenerator all is the system of quick fluidised form bed for people such as Alonso.The operating temperature of absorber is 600-700 ℃, with air and CO 2Gaseous mixture is for carrying gas, and the temperature of regenerator is 800-900 ℃, and fluidized gas is an air.CO 2Adsorption efficiency all remain on more than 70%, but the CO in the adsorbed gas is not described 2Concentration can be inferred its CO according to other scholars' result of study 2Treating capacity should be in a lower level.
People (Gonz á lez et al. such as Gonz á lez; Fuel 2010, and 10of89 2918-2924) has adopted 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 descended.
Therefore the adsorption capacity of natural limestone adsorbent is low, the rate of adsorption is slow, is recycle stock when coming reactor design with the natural limestone adsorbent, and adsorptive reactor generally adopts the smaller fluid bed forms of gas agent such as moving bed or bubbling bed to guarantee CO 2Removal effect, but increased Material Cost and the cost of energy of handling unit volume flue gas.And adopt fast fluidized bed as adsorptive reactor, though can increase gas agent ratio, because the absorbent particles polishing machine is poor, in order to guarantee essential CO 2Capture effect, need ceaselessly to replenish fresh adsorbent, need the more raw materials expense, caused CO 2The rising of processing cost, this is one of key that at present can't industrial applications.The calcium oxide-based carbon dioxide that is used 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.
To CaO base CO 2Adsorbent is prone to decay and shortcoming easy to wear, the inventor in early-stage Study (Su F.Wu, Ind.Eng.Chem.Res, 2008,47,180-184) adopting nano-calcium carbonate is the presoma of calcium oxide-based adsorbent, prepares nanometer CaO/Al 2O 3Adsorbent is found nanometer CaO/Al 2O 3Adsorbent has CO 2Advantages such as adsorption rate is high, decomposition temperature is low, the rate of adsorption is fast.The inventor is that CN101306309A and publication number are to disclose the employing precipitation of silica in the Chinese patent of CN101537339A respectively to coat CaTiO with the surface at publication number 3Method the nano-calcium base adsorbent is carried out modification; Under the TGA test; Adsorption capacity and absorption stability are significantly improved, but both do not propose the adsorbent of modification is made microsphere particle as yet, and the intensity of adsorbent and abrasiveness far do not reach the requirement of fluid bed system.
The inventor discloses the calcium oxide-based CO of a kind of preparation nanometer antiwear in publication number is the Chinese patent of CN101961638A 2The method of adsorbent is with CaCO 3Particle is ultrasonic dispersing in water, adds aluminium colloidal sol, is stirred to uniform sizing material, obtains the microsphere particle that particle diameter is 20-250 μ m through mist projection granulating, obtains spherical wear-resisting nano oxidized Ca-base adsorbent through calcining again.Owing in calcination process, formed calcium aluminate, the wearability of calcium oxide is improved, but this adsorbent does not solve the low problem of adsorption capacity, adsorption capacity is less than 2mol/kg.
Tang Qi is in master thesis (Zhejiang University; 2011) mention in the composite catalyst preparation and adopt aluminium carbonate ammonium, polyethylene glycol, softex kw and activated carbon, do not use but prepare in the process at the CaO group carbonic anhydride adsorption agent as expanding agent.The research that other relevant nano oxidized calcium group carbonic anhydride adsorption agents are used for the circulating fluidized bed technique capturing carbon dioxide is not reported.
Summary of the invention
The invention provides a kind of microsphere nano CaO base CO that is used for recirculating fluidized bed 2The preparation of adsorbent method, 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 that is used for recirculating fluidized bed 2The preparation of adsorbent method comprises: nanometer CaCO 3Be scattered in and form suspension in the water, suspension, additive and aluminium colloidal sol are mixed to evenly, obtaining particle diameter through mist projection granulating is 20～200 microns microsphere particle, after calcining, obtains microsphere nano CaO base CO again 2Adsorbent.
Described additive is aluminium carbonate ammonium, polyethylene glycol or nano-sized carbon, adds additive and can prepare the microsphere nano CaO base CO with certain pore size structure and specific area 2Adsorbent strengthens mass transfer, heat-transfer effect in adsorbent and the carbon dioxide reaction process, improves wearability, adsorption capacity and stability.
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.Al in the aluminium colloidal sol commonly used 2O 3Mass fraction be 5%～20%.
Described nanometer CaCO 3In Ca and the mol ratio of the Al in the 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 to calcine 1～8h, nanometer CaCO after calcining down at 750～1000 ℃ 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 capture in the recirculating fluidized bed CO 2Method, may further comprise the steps:
(1) with microsphere nano CaO base CO 2Adsorbent is packed in the circulating fluid bed reactor, in reactor, feeds and contains CO 2Fluidized gas, carry out adsorption reaction;
(2) CO absorption in the reactor 2After adsorbent and CO 2Fluidized gas after being adsorbed gets into cyclone separator separates, and the solid after the separation gets into regenerator, and the gas after the separation effluxes;
(3) regenerator bottoms feeds N 2, CO 2Or the tail gas that regenerator produces carries out the regeneration of adsorbent as loosening gas.
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 according to the space size of reactor and contain CO 2Choose reasonable microsphere nano CaO such as the treating capacity base CO of flue gas 2The consumption of adsorbent.
Different speed, the adsorption effects that can influence 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 ℃.
Described loosening gas is the tail gas that regenerator produces, and described tail gas is the N that mixes with arbitrary proportion 2And CO 2Mist; The gas speed of described loosening gas is 1～20 times of adsorbent microsphere particle minimum fluidizing velocity, in reactor, is in fluidized state to keep absorbent particles.
CO absorption 2After adsorbent need carry out thermal decomposition regeneration to carry out adsorption reaction once more, the temperature of the regeneration of described step (4) is 750～950 ℃.
Principle of the present invention is:
Nanometer CaO base CO 2CaO in the adsorbent and CO 2Reaction generates CaCO 3:
C aO (s)+CO 2→C aCO 3(s) (1)
The CaCO that reaction generates 3Through heating and decomposition regeneration, reaction equation is following:
C aC O3(s)→C aO (s)+CO 2 (2)
Adsorbent after the present invention's regeneration carries out the adsorption-regeneration circulation according to step (1)～(4) once more; CO in the gas that obtains after the 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 the adsorbent 3CO in the tail gas that the regeneration back produces 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 20～200 microns microsphere nano CaO base CO 2Adsorbent, its specific area can reach 10m 2More than/the g, pore all obtains increasing with big hole count in the absorbent particles, 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 the absorbent particles of test is below 5%.Microsphere nano CaO base CO of the present invention 2Adsorbent has good absorption property, and in the TGA test, after 50 adsorption-desorption circulations, its adsorption capacity still remains on more than the 3mol/kg adsorbent.
Microsphere nano CaO base CO of the present invention 2Adsorbent has good mass transfer, heat transfer property, is applied in the recirculating fluidized bed decarbonization process, compares with natural calcium oxide-based adsorbent, and required regeneration temperature and adsorption reaction temperature have reduced by 50～100 ℃, have reduced removing CO 2Cost of energy.
Microsphere nano CaO base C of the present invention O2 adsorbents than natural base adsorbent, have bigger adsorption capacity and adsorption rate faster, have guaranteed that adsorbent is at recirculating fluidized bed CO 2Capture in the technology and can adopt the fast fluidized bed decarburization, reach the purpose that improves the reactor for treatment amount; Have better polishing machine, greatly reduce and remove CO 2Material Cost.
Microsphere nano CaO base CO of the present invention 2Adsorbent preparation technology is simple, is applied to capture in the recirculating fluidized bed CO 2Method, can continous-stable operation, mass transfer, heat transfer efficiency are high.
Description of drawings
Fig. 1 is microsphere nano CaO base CO of the present invention 2The flow chart of preparation of adsorbent method.
Fig. 2 is the microsphere nano CaO base CO of the Comparative Examples 1 of the present invention and the different specific areas of embodiment 1 preparation 2The adsorpting rate curve figure of adsorbent nsorb-1 and sorb-2.
Fig. 3 is the microsphere nano CaO base CO of the Comparative Examples 1 of the present invention and the different specific areas of embodiment 1 preparation 2The circulation adsorption capacity figure of adsorbent nsorb-1 and sorb-2.
Fig. 4 is the microsphere nano CaO base CO of the embodiment of the invention 4 preparations 2The CO of adsorbent sorb-5 the 40 circulation absorption in the fixed bed test 2Adsorption efficiency and outlet CO 2Concentration map, actual conditions is following: adsorbent mass 5g, CO 2Concentration is 20%, 600 ℃ of adsorption temps, 800 ℃ of regeneration temperatures.
Fig. 5 is microsphere nano CaO base CO of the present invention 2Adsorbent captures CO 2The sketch map of method.
The specific embodiment
Specify the present invention below in conjunction with embodiment, but the present invention is not limited to this.
Comparative Examples 1
Nanometer CaCO 310g is dispersed in the 80ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Adding 10.2g mass fraction is 10% aluminium colloidal sol in the suspension, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 5 microns solid sorbent particles.Absorbent particles is calcined 1h down at 800 ℃, obtain microsphere nano CaO base CO 2Adsorbent, nsorb-1.
Embodiment 1 microsphere nano CaO base CO 2Preparation of adsorbent
Nanometer CaCO 310g is dispersed in the 50ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Adding 51g mass fraction is 20% aluminium colloidal sol and 1.5g aluminium carbonate ammonium in the suspension, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 20 microns solid sorbent particles.Absorbent particles is calcined 1h down at 880 ℃, obtain microsphere nano CaO base CO 2Adsorbent, sorb-2.
The microsphere nano CaO base CO of present embodiment preparation 2The absorbent particles wear rate is 4.0%.
Embodiment 2 microsphere nano CaO base CO 2Preparation of adsorbent
Nanometer CaCO 320g is dispersed in the 160ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Adding 8.16g mass fraction is 5% aluminium colloidal sol and 4g polyethylene glycol in the suspension, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 200 microns solid sorbent particles.Absorbent particles is calcined 4h down at 1000 ℃, obtain microsphere nano CaO base CO 2Adsorbent, sorb-3.
The microsphere nano CaO base CO of present embodiment preparation 2The absorbent particles wear rate is 3.3%.
Embodiment 3 microsphere nano CaO base CO 2Preparation of adsorbent
Nanometer CaCO 320g is dispersed in the 100ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Adding 20.4g mass fraction is 10% aluminium colloidal sol and 0.1g Macrogol 2000 in the suspension, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 60 microns solid sorbent particles.Absorbent particles is calcined 2h down at 850 ℃, obtain microsphere nano CaO base CO 2Adsorbent, sorb-4.
The microsphere nano CaO base CO of present embodiment preparation 2The absorbent particles wear rate is 5.0%.
Embodiment 4 microsphere nano CaO base CO 2Preparation of adsorbent
Nanometer CaCO 315g is dispersed in the 150ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Adding 38.25g mass fraction is 5% aluminium colloidal sol and 3g aluminium carbonate ammonium in the suspension, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 80 microns solid sorbent particles.Absorbent particles is calcined 2h down at 900 ℃, obtain microsphere nano CaO base CO 2Adsorbent, sorb-5.
The microsphere nano CaO base CO of present embodiment preparation 2The absorbent particles wear rate is 4.8%.
Embodiment 5 microsphere nano CaO base CO 2Preparation of adsorbent
Nanometer CaCO 310g is dispersed in the 60ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Adding 15.7g mass fraction is that 5% aluminium colloidal sol and 1.5g particle diameter are the powdered carbon of 100 nanometers in the suspension, fully mixes, and forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 80 microns solid sorbent particles.Absorbent particles is calcined 2h down at 850 ℃, obtain microsphere nano CaO base CO 2Adsorbent, sorb-6.
The microsphere nano CaO base CO of present embodiment preparation 2The absorbent particles wear rate is 3.7%.
Embodiment 6 microsphere nano CaO base CO 2Preparation of adsorbent
Nanometer CaCO 310g is dispersed in the 70ml distilled water, forms finely dispersed suspension, to nanometer CaCO 3Add the 8.5g mass fraction in the suspension and be 20% aluminium colloidal sol and 2g particle diameter and be 100 powdered carbon, fully mixing forms uniform slurry.Slurry is through mist projection granulating, obtains grain diameter and be 60 microns solid sorbent particles.Absorbent particles is calcined 2h down at 900 ℃, obtain microsphere nano CaO base CO 2Adsorbent, sorb-7.
The microsphere nano CaO base CO of present embodiment preparation 2The absorbent particles wear rate is 3.1%.
Application examples recirculating fluidized bed decarbonization process
Microsphere nano CaO base CO 2Adsorbent captures CO 2Technology, as shown in Figure 5, fresh particles nanometer CaO base CO 2Adsorbent simultaneously, contains CO to the adsorptive reactor feeding in transport gets into the reactor of recirculating fluidized bed 2Flue gas, CO 2Contact the back with the adsorbent microballoon by absorption rapidly; The gas-solid mixture that leaves adsorptive reactor gets into cyclone separator to be separated; Gas after the separation directly discharges atmosphere, and the adsorbent solids after the separation is transported in the regenerator, and the tail gas of regenerator feeds in the regenerator as loosening gas; Carry out the adsorbent reactivation reaction, the adsorbent after the regeneration gets into adsorption-regeneration circulation next time.
Application examples 1
Adopt the recirculating fluidized bed decarbonization process to capture the CO in the flue gas 2, the adsorbent that uses is the microsphere nano CaO base CO of the embodiment of the invention 1 preparation 2Adsorbent sorb-2, average grain diameter is 20 microns, and the adsorption reaction condition is: 800 ℃ of regeneration temperatures, loosening gas speed are 30 times of adsorbent microballoon minimum fluidizing velocity, and the gas agent that gets into adsorptive reactor is than being 0.083L/g, wherein CO 2Concentration 15vol%, 600 ℃ of adsorption temps, CO in the exit gas 2Content is 0.3vol%, CO 2Adsorption efficiency 98.3%.
Application examples 2
Adopt the recirculating fluidized bed decarbonization process to capture the CO in the flue gas 2, the adsorbent that uses is the microsphere nano CaO base CO of the embodiment of the invention 1 preparation 2Adsorbent sorb-2, average grain diameter is 20 microns, and the adsorption reaction condition is: 780 ℃ of regeneration temperatures, loosening gas speed are 40 times of adsorbent microballoon minimum fluidizing velocity, and the gas agent that gets into adsorptive reactor is than being 0.08L/g, wherein CO 2Concentration 15vol%, 550 ℃ of adsorption temps, CO in the exit gas 2Content 0.5vol%, CO 2Adsorption efficiency 97.18%.
Application examples 3
Adopt the recirculating fluidized bed decarbonization process to capture the CO in the flue gas 2, the adsorbent that uses is the microsphere nano CaO base CO of the embodiment of the invention 2 preparations 2Adsorbent sorb-3, average grain diameter is 200 microns, the adsorption reaction condition: 800 ℃ of regeneration temperatures, loosening gas speed are 60 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that gets into adsorptive reactor is than being 0.05L/g, wherein CO 2Concentration 20vol%, 550 ℃ of adsorption temps, CO in the exit gas 2Content 0, CO 2Adsorption efficiency 100%.
Application examples 4
Adopt the recirculating fluidized bed decarbonization process to capture the CO in the flue gas 2, the adsorbent that uses is the microsphere nano CaO base CO of the embodiment of the invention 5 preparations 2Adsorbent sorb-6, average grain diameter is 80 microns, the adsorption reaction condition: 850 ℃ of regeneration temperatures, loosening gas speed are 40 times of adsorbent microballoon minimum fluidizing velocity, the gas agent that gets into adsorptive reactor is than being 0.06L/g, wherein CO 2Concentration 8vol%, 650 ℃ of adsorption temps, CO in the exit gas 2Content is at 0vol%, CO 2Adsorption efficiency 100%.
Application examples 5
Adopt the recirculating fluidized bed decarbonization process to capture the CO in the flue gas 2, the adsorbent that uses is the microsphere nano CaO base CO of the embodiment of the invention 4 preparations 2Adsorbent sorb-5, average grain diameter is 80 microns; The adsorption reaction condition: 750 ℃ of regeneration temperatures, loosening gas speed are 40 times of adsorbent microballoon minimum fluidizing velocity, and the gas agent that gets into adsorptive reactor is than being 0.075L/g, wherein CO 2Concentration 20vol%, 600 ℃ of adsorption temps, the stop amount 2kg of adsorbent in the riser, CO in the exit gas 2Content is at 1vol%, CO 2Adsorption efficiency 90%.

Claims (10)

1. microsphere nano CaO base CO who is used for recirculating fluidized bed 2The preparation of adsorbent method is characterized in that, comprising: nanometer CaCO 3Be scattered in and form suspension in the water, suspension, additive and aluminium colloidal sol are mixed to evenly, obtaining particle diameter through mist projection granulating is 20～200 microns microsphere particle, after calcining, obtains microsphere nano CaO base CO again 2Adsorbent.
2. the microsphere nano CaO base CO that is used for recirculating fluidized bed as claimed in claim 1 2The preparation of adsorbent method is characterized in that, described additive is aluminium carbonate ammonium, polyethylene glycol or nano-sized carbon.
3. the microsphere nano CaO base CO that is used for recirculating fluidized bed as claimed in claim 1 2The preparation of adsorbent method is characterized in that, described nanometer CaCO 3In Ca and the mol ratio of the Al in the aluminium colloidal sol be 0.1～50: 1, described additive and nanometer CaCO 3Mass ratio be 0.005～0.2: 1.
4. the microsphere nano CaO base CO that is used for recirculating fluidized bed as claimed in claim 1 2The preparation of adsorbent method is characterized in that, described calcining is to calcine 1～8h down at 750～1000 ℃.
5. microsphere nano CaO base CO like the described preparation method of the arbitrary claim of claim 1～4 preparation 2Adsorbent.
6. microsphere nano CaO as claimed in claim 5 base CO 2Adsorbent is applied to capture in the recirculating fluidized bed CO 2Method, it is characterized in that, comprising:
(1) with microsphere nano CaO base CO 2Adsorbent is packed in the circulating fluid bed reactor, in reactor, feeds and contains CO 2Fluidized gas, carry out adsorption reaction;
(2) CO absorption in the reactor 2After adsorbent and CO 2Fluidized gas after being adsorbed gets into cyclone separator separates, and the solid after the separation gets into regenerator, and the gas after the separation effluxes;
(3) regenerator bottoms feeds N 2, CO 2Or the tail gas that regenerator produces carries out the regeneration of adsorbent as loosening gas.
7. microsphere nano CaO base CO as claimed in claim 6 2Adsorbent is applied to capture in the recirculating fluidized bed CO 2Method, it is characterized in that 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%.
8. microsphere nano CaO base CO as claimed in claim 6 2Adsorbent is applied to capture in the recirculating fluidized bed CO 2Method, it is characterized in that the temperature of the adsorption reaction of described step (1) is 550～650 ℃.
9. microsphere nano CaO base CO as claimed in claim 6 2Adsorbent is applied to capture in the recirculating fluidized bed CO 2Method, it is characterized in that described loosening gas is the tail gas that regenerator produces, 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.
10. microsphere nano CaO base CO as claimed in claim 6 2Adsorbent is applied to capture in the recirculating fluidized bed CO 2Method, it is characterized in that the temperature of the regeneration of described step (4) is 750～950 ℃.
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CN104190208A (en) * 2014-08-12 2014-12-10 清本环保工程(杭州)有限公司 Method for treating organic waste gas by using circulating fluidized bed
CN104289173A (en) * 2014-09-30 2015-01-21 浙江大学 Lithium salt doped nano-calcium carbonate-based carbon dioxide adsorbent precursor and application of adsorbent precursor
CN106475041A (en) * 2016-11-25 2017-03-08 清华大学 A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent and application
CN114162825A (en) * 2020-09-11 2022-03-11 北京清创硅谷科技有限公司 Method and device for producing nano-coating material or nano-hollow material

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Publication number Priority date Publication date Assignee Title
CN104190208A (en) * 2014-08-12 2014-12-10 清本环保工程(杭州)有限公司 Method for treating organic waste gas by using circulating fluidized bed
CN104289173A (en) * 2014-09-30 2015-01-21 浙江大学 Lithium salt doped nano-calcium carbonate-based carbon dioxide adsorbent precursor and application of adsorbent precursor
CN106475041A (en) * 2016-11-25 2017-03-08 清华大学 A kind of Nano-meter SiO_22The synthetic method of/CaO adsorbent and application
CN114162825A (en) * 2020-09-11 2022-03-11 北京清创硅谷科技有限公司 Method and device for producing nano-coating material or nano-hollow material
CN114162825B (en) * 2020-09-11 2023-07-04 北京清创硅谷科技有限公司 Method and device for producing nano-coated material or nano-hollow material

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