CN105727882B - A kind of calcium base CO2Adsorbent and preparation method thereof - Google Patents

A kind of calcium base CO2Adsorbent and preparation method thereof Download PDF

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CN105727882B
CN105727882B CN201610079081.8A CN201610079081A CN105727882B CN 105727882 B CN105727882 B CN 105727882B CN 201610079081 A CN201610079081 A CN 201610079081A CN 105727882 B CN105727882 B CN 105727882B
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calcium
raw material
adsorbent
algae
diameter
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CN105727882A (en
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刘文强
孙健
徐明厚
陈洪强
杨新伟
胡迎超
王文煜
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Huazhong University of Science and Technology
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    • 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
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    • 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
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    • 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
    • B01J20/041—Oxides or hydroxides
    • 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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01J2220/00—Aspects relating to sorbent materials
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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    • 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
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract

The invention discloses a kind of calcium base CO2Adsorbent, the calcium base CO2Adsorbent is spheric granules, the diameter of the spheric granules is 0.3mm~3.5mm, it includes mixed uniformly algae raw material and calcium based raw material, and the mass ratio of the algae raw material and the calcium based raw material is 0.001:1~0.03:1, the calcium based raw material is calcium hydroxide, one of calcium carbonate or white lime or a variety of.The invention also discloses calcium base CO2The preparation method of adsorbent.The present invention is optimized on prilling process by adulterating 0.1%~3% algae raw material in calcium based raw material, so as to improve calcium base CO2The cyclical stability of adsorbent, and preparation method is simple, is suitable for large-scale production.

Description

A kind of calcium base CO2Adsorbent and preparation method thereof
Technical field
The invention belongs to CO2Absorbent fields, more particularly, to a kind of calcium base CO2Adsorbent and preparation method thereof.
Background technique
The CO largely discharged in fossil fuel use process2It is considered as the main reason for causing global warming.In order to allow The use of fossil fuel is received by environment, a series of CO2Trapping and Plugging Technology Applied are developed.Wherein, calcium recycles CO2 Trapping technique is considered as a kind of CO for most having application prospect due to its lower trapping cost and wide applicability2Trap skill Art.
Used calcium base CO in the prior art2Adsorbent main component is calcium oxide, however when adsorbent is applied to calcium There is a problem of when the circulatory system two it is obvious: one be calcium oxide adsorbent cyclical stability it is poor, secondly because oxygen Change calcium adsorbent is during carbonating ciculation fluidized between furnace and calcining furnace, particle and particle, particle and pipeline and heat The influence of stress easily causes the abrasion of adsorbent, leads to the loss of active calcium oxide adsorbent.
The prior art is by the method adulterating or be granulated come to CO2The stability of adsorbent improves.In prilling process In, it is two kinds of granulation modes of one of the most common that extrusion forming, which is granulated and rotates round as a ball be granulated,；However, only being obtained by extrusion forming The absorbent particles obtained are cylindrical to be unfavorable for fluidizing, and only by rotating round as a ball its wear resistance of obtained absorbent particles It is poor.And in doping method, the additive amount of the substance of doping usually requires 5%~20%, causes mentioning for preparation cost in this way It is high.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of calcium base CO2Adsorbent, purpose It is in calcium base CO2Algae raw material is added in adsorbent, to improve calcium base CO2The fluidization characteristic of adsorbent, antiwear property with And cyclical stability.
To achieve the above object, according to one aspect of the present invention, the calcium base CO2Adsorbent is spheric granules, described The diameter of spheric granules is 0.3mm~3.5mm comprising mixed uniformly algae raw material and calcium based raw material, and the algae The mass ratio of raw material and the calcium based raw material is 0.001:1~0.03:1, and the calcium based raw material is calcium hydroxide, calcium carbonate or One of white lime is a variety of.
Preferably, the diameter of the spheric granules is 0.9mm~1.25mm.
Preferably, it is algae pyrolysis lime-ash that the algae raw material, which is the algae raw material,.
As it is further preferred that the preparation method of algae pyrolysis lime-ash is, by dry algae in inert gas 500 DEG C~900 DEG C heating in atmosphere, until devolatilization therein is complete.
Preferably, the calcium based raw material is calcium hydroxide.
Preferably, the mass ratio of the algae raw material and the calcium based raw material is 0.005:1~0.02:1.
It is another aspect of this invention to provide that additionally providing calcium base CO2The preparation method of adsorbent, comprising the following steps:
(1) algae raw material, water and calcium based raw material are uniformly mixed with the mass ratio of 0.001:0.1:1~0.03:0.45:1 It closes, obtains mixed material；Wherein, the calcium based raw material is calcium hydroxide, one of calcium carbonate or white lime or a variety of, grain Diameter is less than 200 μm；
(2) mixed material squeezed, cut and is round as a ball, obtain the spherical mixed material that diameter is less than 4mm；
(3) spheric granules that diameter is 0.3mm~3.5mm will be screened out after the spherical mixed material drying, obtains institute State calcium base CO2Adsorbent.
Preferably, the step (2) is specifically, it is 0.5mm~3.5mm's that the mixed material, which is first squeezed into diameter, Cylinder mixed material, then by the cylinder mixed material cutting and it is round as a ball, obtain diameter be less than 4mm spherical mixed material.
As it is further preferred that the revolving speed of the extruding is 10r/min~120r/min, the revolving speed of the cutting is 1000r/min~1400r/min, the round as a ball revolving speed are 600r/min~1200r/min.
Preferably, method dry in the step (3) is air-dried or 60 DEG C or less drying.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, due in calcium base CO2's Algae raw material is added in preparation process, can achieve the following beneficial effects:
1, CO can be improved well by 0.1%~3% algae raw material only being adulterated in calcium based raw material2The circulation of adsorbent Stability, while its adsorption capacity is not influenced, reduce CO2The cost of adsorbent doping preparation；
2, the mixed material prepared structure denser after squeezing, squeezes the CO of round as a ball acquisition again2Adsorbent with not The CO of direct round as a ball acquisition by extruding2Adsorbent is compared, not only epigranular, be easy to fluidize in the calcium circulatory system and follow Ring, and there is good CO2Adsorption capacity and antiwear property；And the extruding, cutting and round as a ball prilling process are simply easy Row, is suitble to large-scale industrial application；
3, algae pyrolysis lime-ash is usually the waste of algae pyrogenation oil refining, preferably using the material as algae raw material, into One step reduces preparation cost；
4, the present invention does not need to use high temperature or the exacting terms such as closed, and preparation method is simple, and production process does not generate Toxic waste is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the institute after 25 adsorption-desorption cycles of sample prepared by 1-3 of the embodiment of the present invention and comparative example 1-4 The CO obtained2Adsorption capacity figure line；
Fig. 2 is the gained after 25 adsorption-desorption cycles of sample prepared by 4-5 of the embodiment of the present invention and comparative example 1 CO2Adsorption capacity figure line.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of calcium base CO2Adsorbent, the calcium base CO2Adsorbent is the ball of diameter 0.3mm~3.5mm Shape particle comprising mixed uniformly algae raw material and calcium based raw material, the quality of the algae raw material and the calcium based raw material Than for 0.001:1~0.03:1；Wherein, the calcium base CO2The diameter of adsorbent is preferably 0.9mm~1.25mm, excessive, is held Absorption property is easily influenced, it is too small, mechanical strength is easily reduced to influence cyclical stability, the algae raw material and the calcium The mass ratio of based raw material is preferably 0.005:1:1~0.02:1, and doping ratio is excessively high, then is easy to influence its absorption property, and Production cost is improved, doping ratio is too small, and the effect for improving cyclical stability is unobvious；The algae raw material is algae powder (powdered substance that i.e. 100 DEG C of algae or less dehydrations obtain contains the ingredients such as fat, protein and polysaccharide) such as microalgae powder, Or algae pyrolysis lime-ash (500 DEG C in an inert gas atmosphere~900 DEG C of algae i.e. dry heating, until volatile matter therein The coke species obtained after removing completely) such as microalgae pyrolysis lime-ash；The calcium based raw material is calcium hydroxide, calcium carbonate or ripe stone Ash, or the minerals containing these ingredients, such as industrial white lime, lime stone or carbide slag waste.
Calcium base CO2The preparation method of adsorbent the following steps are included:
(1) algae raw material, water and calcium based raw material are uniformly mixed with the mass ratio of 0.001:0.1:1~0.03:0.45:1 It closes, obtains mixed material；Wherein, the calcium based raw material is calcium hydroxide, one of calcium carbonate or white lime or a variety of, grain Diameter is less than 200 μm；
(2) mixed material is squeezed to round as a ball, spherical mixed material of the acquisition diameter less than 4mm；
(3) the spherical mixed material is dry (if air-dried or 60 DEG C or less 5h~10h are dried, in order to avoid temperature is excessively high So that the CO in adsorbent and air2Reaction is to influencing its absorption property) after screen out the ball that diameter is 0.3mm~3.5mm Shape particle obtains the calcium base CO2Adsorbent.
Wherein, the extruding of the step (2) is round as a ball usually using extruding spheronizator operation, the specific steps are that, first by institute It states mixed material and is squeezed into the cylinder mixed material that diameter is 0.5mm~3.5mm with the revolving speed of 10r/min~120r/min, then The cylinder mixed material is cut into 0.5min~2min under 1000r/min~1400r/min revolving speed, makes cylinder mixed material Be cut into pieces, finally by the cylinder mixed material being cut into pieces under the revolving speed of 600r/min~1200r/min round as a ball 5min~ 10min obtains the spherical mixed material that diameter is less than 4mm.
Embodiment 1 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae
(1) 40g partial size is added less than 150 μm of calcium hydroxide powder and the microalgae powder of 0.2g in the deionized water of 15ml In and stir.
(2) by the wet stock of acquisition by single-screw extruder, extrusion die plate aperture is 1mm, and extruding revolving speed is 30r/ Min obtains oval column absorbent particles.Then, long cylinder particle is put into spheronizator, first setting speed is 1400r/ Min simultaneously continues 2min, long cylinder calcium oxide particle 1400r/min 2min is cut into short cylindrical particle, then revolving speed is down to 1000r/min simultaneously continues 5min, and short cylindrical particle is rolled into oxidation calcoglobule.
(3) finally obtained oxidation calcoglobule is sieved by standard screen, particle size range is between 0.9mm~1.25mm Bead be placed in air air-dry for 24 hours, as final calcium oxide-based adsorbent bead CH.
Embodiment 2 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae
Embodiment 1 is repeated with the same steps, difference is, the quality of microalgae powder is 0.4g.
Embodiment 3 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae
Embodiment 1 is repeated with the same steps, difference is, the quality of microalgae powder is 0.8g.
Embodiment 4 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae pyrolysis lime-ash:
Embodiment 1 is repeated with the same steps, difference is, replaces 0.2g's with the microalgae pyrolysis lime-ash of 0.224g Microalgae powder.
Embodiment 5 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae pyrolysis lime-ash:
Embodiment 4 is repeated with the same steps, difference is, the quality that microalgae is pyrolyzed lime-ash doping is 0.9g.
Embodiment 6
Embodiment 4 is repeated with the same steps, difference is, the quality that microalgae is pyrolyzed lime-ash doping is 0.04g, with The calcium carbonate powder that partial size is 150 μm replaces calcium hydroxide powder.
Embodiment 7
Embodiment 4 is repeated with the same steps, difference is, the quality that microalgae is pyrolyzed lime-ash doping is 1.2g, with Carbide slag waste powder replaces calcium hydroxide powder.
Embodiment 8
Embodiment 4 is repeated with the same steps, difference is, the extrusion die plate hole chosen in the step (2) Diameter is 3.5mm, and particle size range is screened out in the step (3) in the oxidation calcoglobule of 0.3mm~3.5mm.
The preparation of 1 carbonate-free lime base adsorbent bead of comparative example
The deionized water of 15ml is added in 40g calcium hydroxide powder and is sufficiently stirred.The wet stock of acquisition is passed through into list Screw extruder, extrusion die plate aperture are 1mm, and extruding revolving speed is 30r/min, obtain oval column absorbent particles.Then, will Long cylinder particle is put into spheronizator, and first setting speed is 1400r/min and continues 2min, and long cylinder calcium oxide particle is cut It is segmented into short cylindrical particle, then revolving speed is down to 1000r/min and continues 5min, short cylindrical particle is rolled into oxidation calcoglobule.Finally Obtained oxidation calcoglobule is sieved by standard screen, bead of the particle size range between 0.9mm~1.25mm is placed in air It air-dries for 24 hours, as final calcium oxide-based adsorbent bead CH.
Comparative example 2 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae
Embodiment 1 is repeated with the same steps, difference is, the quality of microalgae powder is 2g.
Comparative example 3 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae
Embodiment 1 is repeated with the same steps, difference is, the quality of microalgae powder is 4g.
Comparative example 4 adulterates the preparation of the calcium oxide-based adsorbent bead of microalgae
Embodiment 1 is repeated with the same steps, difference is, the quality of microalgae powder is 8g.
Analysis of experimental results
Non-impurity-doped, doping microalgae and doping microalgae prepared by comparative example 1~4 of the present invention and Examples 1 to 5 are pyrolyzed lime-ash Calcium oxide-based adsorbent bead carry out CO on thermogravimetric analyzer (Pyris 1)2Adsorption capacity test, sample quality 20mg Between~30mg.Adsorption reaction condition: temperature is 650 DEG C, CO2Concentration is 15vol.%, gas flow 100ml/min, carbon Acidificatoin time is 30min；Desorption reaction condition: temperature is 850 DEG C, 100vol%N2, gas flow 100ml/min, desorption Time is 2min, the CO measured2Adsorption capacity is as illustrated in fig. 1 and 2.As can be seen from Figure 1 mixing when microalgae and calcium hydroxide When mixed ratio is 0.02:1, adsorbent bead shows best adsorption capacity, its adsorption capacity is 0.348g after 25 circulations CO2/ g adsorbent is 2.07 times of adsorption capacity after pure cerium hydroxide calcoglobule 25 times circulations.From figure 2 it can be seen that when doping When microalgae is pyrolyzed lime-ash, no matter mixing proportion is 0.0056:1 or 0.0225:1, can show stable and good suction Attached ability, 25 times circulation after its adsorption capacity be respectively 0.288g CO2/ g adsorbent and 0.328g CO2/ g adsorbent.However, When the mixing proportion of microalgae and calcium hydroxide is more than 0.05:1, CO will lead to instead2The initial adsorption performance of/g adsorbent drops It is low.Embodiment 6-8 is analyzed, also can get the result similar with embodiment 1-4.
It can be seen that being either pyrolyzed lime-ash by microalgae or microalgae only needs by the test analysis of the above various embodiments Marginally to blend the CO that can effectively improve calcium oxide-based adsorbent bead2Adsorption capacity.Meanwhile using extruding-rolling The process that circule method prepares calcium oxide-based adsorbent bead is simple and easy, and operating cost is low, not will cause environmental pollution.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (7)

1. a kind of calcium base CO2Adsorbent, which is characterized in that the calcium base CO2Adsorbent is spheric granules, the spheric granules Diameter be 0.3mm~3.5mm comprising mixed uniformly algae raw material and calcium based raw material, and the algae raw material with it is described The mass ratio of calcium based raw material is 0.005:1~0.02:1, and the calcium based raw material is calcium hydroxide, one in calcium carbonate or white lime Kind is a variety of；The algae raw material is algae powder, is the powdered substance that algae obtains in 100 DEG C or less dehydrations, includes Fat, protein and polysaccharide component；The calcium base CO2The preparation method of adsorbent, comprising the following steps:
(1) algae raw material, water and the calcium based raw material is equal with the mass ratio of 0.005:0.1:1~0.02:0.45:1 Even mixing obtains mixed material；Wherein, the calcium based raw material partial size is less than 200 μm；
(2) mixed material squeezed, cut and is round as a ball, obtain the spherical mixed material that diameter is less than 4mm；
(3) spheric granules that diameter is 0.3mm~3.5mm will be screened out after the spherical mixed material drying, obtains the calcium Base CO2Adsorbent.
2. calcium base CO as described in claim 12Adsorbent, which is characterized in that the diameter of the spheric granules be 0.9mm~ 1.25mm。
3. calcium base CO as described in claim 12Adsorbent, which is characterized in that the algae raw material is that algae is pyrolyzed lime-ash；Institute The preparation method for stating algae pyrolysis lime-ash is to heat 500 DEG C in an inert gas atmosphere~900 DEG C of dry algae, up to Devolatilization therein is complete.
4. calcium base CO as described in claim 12Adsorbent, which is characterized in that the calcium based raw material is calcium hydroxide.
5. calcium base CO as described in claim 12Adsorbent, which is characterized in that the step (2) is specifically, first by the mixing Material be squeezed into diameter be 0.5mm~3.5mm cylinder mixed material, then by the cylinder mixed material cutting and it is round as a ball, obtain Obtain the spherical mixed material that diameter is less than 4mm.
6. calcium base CO as described in claim 12Adsorbent, which is characterized in that the revolving speed of the extruding is 10r/min~120r/ Min, the revolving speed of the cutting are 1000r/min~1400r/min, and the round as a ball revolving speed is 600r/min~1200r/min.
7. calcium base CO as described in claim 12Adsorbent, which is characterized in that dry method is air-dried in the step (3) Or 60 DEG C or less drying.
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CN109621890A (en) * 2018-12-24 2019-04-16 华中科技大学 A kind of spherical calcium base CO of whole process industrialization2The preparation method of adsorbent
CN110052238A (en) * 2019-04-19 2019-07-26 中南大学 A kind of spherical shape calcium group carbonic anhydride adsorption agent and preparation method thereof
CN110292905A (en) * 2019-07-22 2019-10-01 华中科技大学 A kind of spherical calcium base CO of loaded inert carrier2Adsorbent, its preparation and application
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