CN112125313A - Spherical lithium-based CO2Method for preparing adsorbent - Google Patents
Spherical lithium-based CO2Method for preparing adsorbent Download PDFInfo
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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
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses spherical lithium-based CO2An adsorbent and a method for preparing the same, comprising: (1) preparing precursor slurry; the precursor slurry is a mixed solution of silica sol and lithium oxalate powder; (2) dropwise adding the precursor slurry into liquid nitrogen to obtain quick-frozen slurry ice balls; (3) placing the slurry ice ball into a freeze drying device to sublimate water to obtain a precursor green ball; (4) calcining the green ball in an aerobic environment to obtain the target spherical lithium-based CO2An adsorbent. The preparation process is ingenious in design, and the solid and liquid in the step (1) can be changed under the condition that a production line is not stoppedThe ratio can adjust the size of the spherical adsorbent finally obtained in the step (4) in real time. And the spherical lithium-based CO prepared2Good sphericity of adsorbent, CO2The method has outstanding cyclic adsorption-desorption capacity and excellent mechanical property, and provides good prospect for the application of the formed lithium-based adsorbent in an actual industrialized fluidization cycle system.
Description
Technical Field
The invention belongs to the technical field of preparation and improvement of adsorbents, and particularly relates to spherical lithium-based CO2A preparation method and a flow of the adsorbent.
Background
The greenhouse effect and global warming are becoming more and more of the global environmental concerns of the international society. To reduce global CO2Carbon capture, utilization, sequestration technologies (CCUS) have been proposed. In a large number of CO2In the emission reduction technology, the solid adsorbent is used for treating CO2The cyclic adsorption desorption is considered to be a promising technique. While lithium-based adsorbents are used as a typical high temperature CO2Solid adsorbents have received wide attention from researchers all over the world due to their advantages such as excellent cycle stability and high adsorption performance.
For CO utilization with lithium-based sorbents2The system adopted by the cyclic adsorption and desorption, and the most suitable technology which is currently recognized is the technology adopting a circulating fluidized bed. In the system, CO in the mixed gas2Adsorbing with lithium orthosilicate in a carbonating furnace (about 550 deg.C), circulating the carbonated adsorbent into a regenerating furnace, regenerating lithium orthosilicate at high temperature (about 750 deg.C), and further circulating into the carbonating furnace for next adsorption, wherein the gas from the regenerating furnace is relatively pure CO2Thus facilitating subsequent CO pairing2Compression, transportation, utilization or burial. However, due to the powdered lithium-based CO2In the fluidized process of the fluidized bed, the elutriation phenomenon of the adsorbent is easily carried out of the system by the air flow, which inevitably causes the serious reduction of the utilization rate of the adsorbent, leads to waste and increases the cost. Therefore, for better adsorbents in fluidized bedsFluidization and cost saving, the lithium-based CO must be treated2The forming research of the adsorbent paves the way for the final industrial application of the adsorbent.
Lithium-based CO reported to date2The forming method of the adsorbent mainly comprises an extrusion-rolling method, an agar template method and a graphite bed one-step forming method. Among them, the extrusion-spheronization method (Yingchao Hu et al, Fuel,2019,236, 1043-1049; Long Ma et al, Chemical Engineering Journal,2020,379,122385) can synthesize spherical adsorbents with better performance, but the forming process is complicated and consumes time and energy. For example: the method needs to prepare lithium orthosilicate powder from raw materials such as lithium carbonate, silicon dioxide and the like, and then the powder can be used for forming; although the agar template method (Huying super et al, ZL 201910720523.6; Yingchao Hu et al, Chemical Engineering Journal,2020,380,122538) is easy to realize the streamlined production, the obtained spherical adsorbent has poor mechanical properties and cannot meet the practical fluidization application of the adsorbent; one-step formation of graphite beds (Yangdong et al, ZL 201810277041.3; Yuandong Yang et al, Chemical Engineering Journal,2018,353,92-99) incorporating Li4SiO4The synthesis and forming process has simple steps, high production efficiency, good performance of the obtained adsorbent, high forming rate and loss rate and poor stability;
in addition to the above-mentioned disadvantages of each of these three molding methods, there is a common problem: the size of the obtained spherical adsorbent is not adjustable, namely once the template/mould is determined, the size of the obtained spherical adsorbent is determined to be invariable. In other words, if spherical adsorbents with different sizes need to be produced in the actual production process, the method needs to pause and clean the production line and then replace the template/mold with the corresponding size, so that the production efficiency is undoubtedly greatly reduced, and the production time and the production cost are improved.
Disclosure of Invention
In response to the above-identified deficiencies in the art or needs for improvement, the present invention provides a spherical lithium-based CO with controllable dimensions2The preparation method of the adsorbent aims at synthesizing the spherical adsorbent with better performance in one step by a freeze drying technology and canUnder the condition that the production line is not stopped, the shrinkage rate in the green ball calcining process is changed by adjusting the solid-liquid ratio of the precursor slurry, and the size of the obtained spherical adsorbent is controllable.
To achieve the above objects, according to one aspect of the present invention, there is provided a spherical lithium-based CO2The preparation method of the adsorbent is characterized in that the size of the obtained spherical adsorbent can be simply adjusted by changing the shrinkage rate, and comprises the following steps:
(1) preparing precursor slurry, wherein the precursor slurry is a mixed solution of silica sol and lithium oxalate powder;
(2) dropwise adding the precursor slurry uniformly mixed in the step (1) into a container containing liquid nitrogen, and quickly freezing the liquid drops into ice balls containing the precursor slurry;
(3) putting the ice ball obtained in the step (2) into a freeze drying device until the moisture is completely sublimated to obtain a precursor green ball consisting of a lithium source and a silicon source;
(4) calcining the precursor green ball obtained in the step (3) in an aerobic environment until the precursor is completely reacted into lithium orthosilicate, thus obtaining the target spherical lithium-based CO2An adsorbent.
Further, the precursor slurry in the step (1) is a mixed solution of silica sol and lithium oxalate powder, wherein the silica sol contains 20-40 wt% of silica in percentage by mass; and (3) marking the mass part of the silicon dioxide as 1 part, and then, the part of the lithium oxalate in the precursor slurry is 2-2.5 parts.
Further, the solid-to-liquid ratio of the precursor slurry is 1:2 to 1:8 or 1:2.5 to 1: 7.5.
Further, the freeze-drying device in the step (3) includes a freeze dryer or a vacuum freeze dryer.
Further, in the step (3), the green pellets obtained by drying have a particle diameter of 3mm to 4 mm.
Further, in the step (4), the calcining temperature is 600-1200 ℃, and the calcining time is 3-6 h.
Further, in the step (4), the calcining temperature is 800-950 ℃, and the calcining time is 4-5 hours.
Further, the spherical lithium-based CO obtained in the step (4)2The particle size of the adsorbent is 0.5 mm-2 mm or 0.9 mm-1.5 mm.
Further, under the condition of not stopping the production line, the solid-liquid ratio of the precursor slurry in the step (1) is adjusted to adjust the shrinkage rate of the green pellets in the step (4) in the calcining process, so that spherical lithium-based CO with different sizes is obtained2An adsorbent.
To achieve the above object, according to another aspect of the present invention, there is provided spherical lithium-based CO obtained according to the preparation method as described in any one of the above2An adsorbent.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following advantages:
1. because the synthesis of the lithium-based adsorbent and the molding of the lithium-based adsorbent powder are combined into one step, the one-step molding process is more time-saving, the cost is saved, and the synthesis efficiency is improved;
2. by means of the idea that liquid drops are spherical when falling under the action of gravity, the liquid nitrogen quick-freezing and freeze-drying technology is ingeniously combined, so that the spherical adsorbent with better sphericity can be prepared without a template/mould in the synthesis process;
3. the method can change the shrinkage rate of the green pellets in the calcining process only by changing the solid-to-liquid ratio of the precursor slurry without stopping the production line, thereby adjusting the size of the produced spherical adsorbent in real time;
4. through verification, by adjusting the solid-liquid ratio, the method can obtain the spherical adsorbent with any particle size within the range of 0.9-1.5 mm, and can meet various application occasions and equipment by adjusting the particle size according to actual parameter requirements;
5. proved by verification, the spherical lithium-based adsorbent obtained by the freeze drying one-step forming method keeps high CO2The catalyst has the characteristics of good sphericity, complete appearance, uniform particle size, excellent abrasion resistance and the like, and is suitable for the fluidization circulation process of a calciner-a regenerator in an actual carbon capture system.
Drawings
FIG. 1 is a schematic diagram of a preparation process of the present invention;
FIG. 2 is a laboratory scale actual production route of FIG. 1;
FIG. 3 is the spherical lithium-based CO prepared2Physical photographs of the adsorbents, wherein (a), (b), and (c) are physical photographs of examples 1, 2, and 3, respectively;
FIG. 4 is a graph showing the shrinkage of the spherical adsorbents of examples 1, 2 and 3 during the green pellet calcination stage;
FIG. 5 shows spherical lithium-based CO prepared in examples 1, 2 and 32X-ray diffraction pattern of the adsorbent;
FIG. 6 is the spherical lithium-based CO prepared2The field emission scanning electron microscope pictures of the adsorbent, wherein (a), (b) and (c) are the electron microscope pictures of examples 1, 2 and 3 respectively;
FIG. 7 is the spherical lithium-based CO prepared2Adsorbent at 15 vol.% CO2Adsorption, 100 vol.% N2The change curve of the adsorption capacity along with the cycle times in the 20-cycle adsorption-desorption process under the calcination condition, wherein (a), (b) and (c) are the performance change curves of examples 1, 2 and 3 respectively;
throughout the drawings, the same reference numerals are used to denote the same substances or instruments, wherein:
1-silica sol, 2-lithium oxalate powder, 3-deionized water, 4-precursor slurry, 5-dropper, 6-quick-frozen precursor ice ball, 7-liquid nitrogen, 8-vacuum freeze dryer, 9-precursor green ball, 10-muffle furnace and 11-spherical lithium-based adsorbent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Referring to fig. 1 and fig. 2, a schematic diagram of a preparation process and a laboratory scale actual preparation route thereof of the present invention includes the following steps:
example 1
(1) As shown in fig. 2, the precursor slurry is a mixed solution of silica sol and lithium oxalate powder, wherein the silica sol contains 30 wt% of silica; marking the mass portion of the silicon dioxide as 1 portion, the portion of the lithium oxalate in the precursor slurry is 2 to 2.5 portions, and the solid-to-liquid ratio of the precursor slurry is 1: 2.5;
(2) dropwise adding the slurry into liquid nitrogen by using a 1mL disposable pasteur dropper to obtain a quick-frozen ice slurry ball;
(3) putting the ice balls into an FD-1A-50 desk type freeze dryer to completely sublimate the water to obtain precursor green balls;
(4) calcining the green ball in a muffle furnace at 900 ℃ for 4h in air atmosphere to completely react the precursor to obtain the target spherical lithium-based CO2An adsorbent;
example 2
(1) As shown in fig. 2, the precursor slurry is a mixed solution of silica sol and lithium oxalate powder, wherein the silica sol contains 30 wt% of silica; marking the mass portion of the silicon dioxide as 1 portion, the portion of the lithium oxalate in the precursor slurry is 2 to 2.5 portions, and the solid-to-liquid ratio of the precursor slurry is 1: 5;
(2) dropwise adding the slurry into liquid nitrogen by using a 1mL disposable pasteur dropper to obtain a quick-frozen ice slurry ball;
(3) putting the ice balls into an FD-1A-50 desk type freeze dryer to completely sublimate the water to obtain precursor green balls;
(4) calcining the green ball in a muffle furnace at 900 ℃ for 4h in air atmosphere to completely react the precursor to obtain the target spherical lithium-based CO2An adsorbent;
example 3
(1) As shown in fig. 2, the precursor slurry is a mixed solution of silica sol and lithium oxalate powder, wherein the silica sol contains 30 wt% of silica; marking the mass portion of the silicon dioxide as 1 portion, the portion of the lithium oxalate in the precursor slurry is 2 to 2.5 portions, and the solid-to-liquid ratio of the precursor slurry is 1: 7.5;
(2) dropwise adding the slurry into liquid nitrogen by using a 1mL disposable pasteur dropper to obtain a quick-frozen ice slurry ball;
(3) putting the ice balls into an FD-1A-50 desk type freeze dryer to completely sublimate the water to obtain precursor green balls;
(4) calcining the green ball in a muffle furnace at 900 ℃ for 4h in air atmosphere to completely react the precursor to obtain the target spherical lithium-based CO2An adsorbent;
and (3) analyzing an experimental result:
FIG. 3 shows spherical lithium-based CO prepared in examples 1, 2 and 32Physical diagram of the adsorbent. As can be seen from the figure, the adsorbent pellets have uniform particle size and good sphericity, which proves the feasibility of the freeze-drying one-step forming method related to the invention. In addition, it is easy to find by comparing different examples, spherical adsorbents with different particle sizes can be obtained by adjusting the solid-to-liquid ratio of the precursor slurry: under the condition of the same liquid drop volume, the particle size of the obtained spherical adsorbent is in a remarkable descending trend along with the reduction of the solid-liquid ratio, wherein the average particle size of the obtained adsorbent is about 1.43 mm when the solid-liquid ratio is 1: 2.5; the average grain diameter of the obtained adsorbent is about 1.29 mm when the solid-liquid ratio is 1: 5; the average particle size of the obtained adsorbent is further reduced to about 0.91 mm when the solid-liquid ratio is 1: 7.5;
FIG. 4 is a graph of shrinkage of spherical adsorbents corresponding to examples 1, 2 and 3 during green ball calcination, where the error bars are standard deviations of the data of the repeated experiments under normal distribution. As can be seen from the figure, the shrinkage rate during green pellet calcination significantly increases with decreasing solid-to-liquid ratio: the average shrinkage rate is 51.0 +/-3.0% when the solid-liquid ratio is 1: 2.5; when the solid-liquid ratio is 1:5, the shrinkage rate is increased to 56.7 +/-3.6 percent; the shrinkage rate is further remarkably increased to 69.4 +/-2.5% when the solid-liquid ratio is 1: 7.5. The data in the physical map in conjunction with fig. 3 can demonstrate that: the freeze drying one-step forming method can change the shrinkage rate of the green ball in the calcining process by adjusting the solid-liquid ratio under the condition of not stopping a production line, and further regulate and control the particle size of the target spherical adsorbent in real time.
Lithium-based CO prepared in examples 1, 2 and 3 by X-ray diffraction (XRD)2Adsorbent is smallThe phase composition of the spheres was analyzed, and as a result, as shown in fig. 5, it can be seen that the X-ray diffraction peak of the lithium-based adsorbent prepared according to the method of the present invention is mainly composed of Li4SiO4Diffraction peak composition (2 θ ═ 17 °, 22 °, 24 °, 27 °, 33 °,38 °, 49 °, 61 °), which has a structure to CO2The adsorption capacity of (1). In addition, no diffraction peak of the precursor silicon dioxide or lithium carbonate is detected in the XRD result, which proves that the precursor is completely converted into the target lithium-based adsorbent, and shows that the freeze-drying one-step forming method is completely feasible from the viewpoint of phase composition.
FIG. 6 is a spherical lithium-based CO prepared in examples 1, 2, and 32Field emission scanning electron microscope images of the adsorbent. The figure shows that the lithium-based adsorbent prepared by the method provided by the invention has excellent sphericity and rich surface micro-pore structure, and is suitable for fluidized cycle use in actual working conditions. In addition, it can be obviously found that the particle size of the spherical adsorbent is obviously reduced along with the reduction of the solid-liquid ratio, which is highly consistent with the conclusion of the figure 3 real graph, and the controllability of the method on the particle size of the adsorbent is proved again.
Lithium-based CO prepared in examples 1, 2, 3 was tested by thermogravimetric analysis2The adsorption-desorption regeneration performance of the adsorbent beads. The adsorption working condition is as follows: adsorption temperature is 550 ℃, holding time is 30min, and atmosphere is 15 vol.% CO2And 85 vol.% N2The mixed gas of (3); the desorption conditions are as follows: the desorption temperature is 700 ℃, the heat preservation time is 10min, and the atmosphere is pure N2An atmosphere. The rate of temperature change was fixed at 15 deg.C/min. The cycle test frequency is 20 times, and the adsorption capacity (g CO) of the adsorbent pellets is obtained through the mass change of the adsorbent recorded by thermogravimetry2Per g sorbent, i.e. CO adsorbed per mass of adsorbent2Mass of gas) with respect to the number of cycles, the results are shown in fig. 7, with the adsorption-desorption cycle number on the abscissa and the adsorption capacity on the ordinate. It can be seen that the spherical lithium-based CO of each example was prepared according to the method of the present invention2The adsorbent has excellent adsorption cycle stability, and no obvious performance decline phenomenon appears in 20 cycles. Furthermore, the spherical adsorbent prepared in example 1 has an internal performance of 20 cyclesCan be stabilized in a better range of 0.15-0.18g/g, which is basically equal to the best embodiment of the spherical adsorbent obtained by other reported forming methods.
Therefore, the preparation process of the invention is skillfully designed, and the size of the spherical adsorbent can be adjusted in real time by changing the solid-liquid ratio under the condition of no stop of a production line. And the spherical lithium-based CO prepared2Good sphericity of adsorbent, CO2The method has outstanding cyclic adsorption-desorption capacity and excellent mechanical property, and provides good prospect for the application of the formed lithium-based adsorbent in an actual industrialized fluidization cycle system.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. Spherical lithium-based CO2The preparation method of the adsorbent is characterized by comprising the following steps:
(1) preparing precursor slurry, wherein the precursor slurry is a mixed solution of silica sol and lithium oxalate powder;
(2) dropwise adding the precursor slurry uniformly mixed in the step (1) into a container containing liquid nitrogen, and quickly freezing the liquid drops into ice balls containing the precursor slurry;
(3) putting the ice ball obtained in the step (2) into a freeze drying device until the moisture is completely sublimated to obtain a precursor green ball consisting of a lithium source and a silicon source;
(4) calcining the precursor green ball obtained in the step (3) in an aerobic environment until the precursor is completely reacted into lithium orthosilicate, thus obtaining the target spherical lithium-based CO2An adsorbent.
2. The preparation method according to claim 1, wherein the silica sol in the step (1) contains 20 to 40 wt% of silica, and the part of lithium oxalate in the precursor slurry is 2 to 2.5 parts when the part of silica is 1 part.
3. The method according to claim 2, wherein the solid-to-liquid ratio of the precursor slurry is 1:2 to 1:8 or 1:2.5 to 1: 7.5.
4. The production method according to any one of claims 1 to 3, wherein the freeze-drying device in the step (3) comprises a freeze-dryer or a vacuum freeze-dryer.
5. The production method according to any one of claims 1 to 3, wherein in the step (3), the green pellets obtained by drying have a particle size of 3mm to 4 mm.
6. The method according to any one of claims 1 to 3, wherein in the step (4), the calcination temperature is 600 ℃ to 1200 ℃ and the calcination time is 3 to 6 hours.
7. The preparation method according to claim 6, wherein in the step (4), the calcination temperature is 800 ℃ to 950 ℃ and the calcination time is 4 to 5 hours.
8. The method according to any one of claims 1 to 3, wherein the spherical lithium-based CO obtained in the step (4) is produced2The particle size of the adsorbent is 0.5 mm-2 mm or 0.9 mm-1.5 mm.
9. The preparation method according to any one of claims 1, 3 and 6 to 8, wherein the shrinkage rate of the green pellets in the step (4) in the calcination process is adjusted by adjusting the solid-liquid ratio of the precursor slurry in the step (1) without stopping the production line, so as to obtain spherical lithium-based CO with different sizes2An adsorbent.
10. Spherical lithium-based CO obtained by the method according to any one of claims 1 to 92An adsorbent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414922A (en) * | 2022-08-16 | 2022-12-02 | 华中农业大学 | Spherical Li 4 SiO 4 Radical CO 2 Method for preparing adsorbent |
| CN116864682A (en) * | 2023-08-31 | 2023-10-10 | 华中科技大学 | Three-dimensional spherical crosslinked self-sacrifice type composite lithium supplementing agent, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115414922A (en) * | 2022-08-16 | 2022-12-02 | 华中农业大学 | Spherical Li 4 SiO 4 Radical CO 2 Method for preparing adsorbent |
| CN115414922B (en) * | 2022-08-16 | 2023-06-20 | 华中农业大学 | Spherical Li 4 SiO 4 Based on CO 2 Method for preparing adsorbent |
| CN116864682A (en) * | 2023-08-31 | 2023-10-10 | 华中科技大学 | Three-dimensional spherical crosslinked self-sacrifice type composite lithium supplementing agent, and preparation method and application thereof |
| CN116864682B (en) * | 2023-08-31 | 2023-12-05 | 华中科技大学 | Three-dimensional spherical crosslinked self-sacrifice type composite lithium supplementing agent, and preparation method and application thereof |
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