CN117000197A - A preparation method of calcium-based adsorbent based on supercritical CO2 extraction technology - Google Patents
A preparation method of calcium-based adsorbent based on supercritical CO2 extraction technology Download PDFInfo
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Abstract
本发明公开了一种基于超临界CO2萃取技术的钙基吸附剂制备方法，采用超临界CO2萃取后的橘皮残渣作为制备钙基CO2吸附剂的前驱体模板，实现了对钙基CO2吸附剂微观孔隙结构的优化，既提高了钙基CO2吸附剂的吸附能力，又省去了常规制备方法中的持续煅烧的步骤，通过燃烧替代煅烧，有利于降低制备所需的能耗和加快制备速率；且橘皮残渣属于萃取工艺的废渣，相较于目前常规的前驱体模板，具备孔隙结构优良和经济成本低廉的优势；另外，通过在钙基CO2吸附剂中掺杂硝酸钇和硝酸镁，有利于提高钙基CO2吸附剂的抗烧结能力和循环稳定性，实现钙基材料CO2吸附性能的较大提升；该制备方法简单，适用于大规模工业化生产。
The invention discloses a calcium-based adsorbent preparation method based on supercritical CO 2 extraction technology. The orange peel residue after supercritical CO 2 extraction is used as a precursor template for preparing calcium-based CO 2 adsorbent, realizing the calcium-based CO 2 adsorbent preparation method. The optimization of the micropore structure of the CO2 adsorbent not only improves the adsorption capacity of the calcium-based CO2 adsorbent, but also eliminates the continuous calcination step in the conventional preparation method. By replacing calcination with combustion, it is beneficial to reduce the energy required for preparation. consumption and speed up the preparation rate; and the orange peel residue is a waste residue of the extraction process. Compared with the current conventional precursor template, it has the advantages of excellent pore structure and low economic cost; in addition, by doping in the calcium-based CO 2 adsorbent Yttrium nitrate and magnesium nitrate are conducive to improving the sintering resistance and cycle stability of the calcium-based CO 2 adsorbent, achieving a greater improvement in the CO 2 adsorption performance of the calcium-based material; the preparation method is simple and suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of solid adsorbent compositions, and particularly relates to a supercritical CO-based catalyst 2 The preparation method of the calcium-based adsorbent by the extraction technology.
Background
Under the situation of global warming, control is carried out by CO 2 The emission of the first greenhouse gases has great significance, so that the carbon dioxide capturing and storing technology (CCS) is rapidly developed, namely, the CCS technology is used for separating and capturing CO emitted in the production process 2 And will capture CO 2 Stored in geological reservoirs or injected into the deep sea.
In a plurality of technical schemes for capturing carbon dioxide, solid adsorbent is adopted to separate CO in flue gas 2 Compared with an amine adsorption method, the method has better economy; the solid adsorbent has wide source of calcium-based adsorbent, low cost, and low CO content 2 Is large, and therefore, the calcium-based adsorbent is used for separating CO from flue gas by a cyclic carbonation/calcination method (CaL) 2 Is of increasing interest to researchers. But research has found that natural calcium-based adsorbents adsorb CO 2 The conversion of (c) decreases dramatically with increasing cycle times, has a major impact on the economics and stability of the CaL technology, and limits to some extent the large-scale industrial application of the CaL technology. In order to enhance and stabilize the adsorption capacity of the calcium-based adsorbent, the design of a precursor template and the metal doping modification of the calcium-based adsorbent are research hot spots in the field of preparation of the calcium-based adsorbent at present, so how to obtain the calcium-based adsorbent with more stable adsorption capacity through the design of the precursor template and the metal doping modification is a problem to be solved in the following urgent need.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, it is an object of the present invention to provide a supercritical CO-based process 2 The preparation method of the calcium-based adsorbent by the extraction technology solves the technical problem that the existing calcium-based adsorbent has poor adsorption capacity and stability, and improves the calcium-based adsorbentStability effects.
In order to solve the technical problems, the invention adopts the following technical scheme:
supercritical CO-based 2 The preparation method of the calcium-based adsorbent by the extraction technology comprises the following steps:
1) Supercritical CO treatment of pericarpium Citri Tangerinae 2 Extracting and drying to obtain orange peel residues;
2) Dissolving and mixing soluble yttrium salt, soluble magnesium salt and soluble calcium salt to obtain a mixed solution;
3) Placing orange peel residues into the mixed solution, and absorbing the mixed solution by the orange peel residues to obtain a body to be calcined;
4) Calcining the body to be calcined to self-ignite to obtain calcium-based CO 2 An adsorbent.
Further, step 1) comprises the following sub-steps:
11 Cleaning pericarpium Citri Tangerinae, oven drying, and pulverizing to obtain pericarpium Citri Tangerinae granule;
12 Placing the orange peel particles into an extraction kettle for supercritical CO 2 Extracting;
13 Filtering the extractive solution, collecting and oven drying pericarpium Citri Tangerinae particles, and subjecting to supercritical CO 2 Extracting to obtain pericarpium Citri Tangerinae residue, and preparing calcium-based CO from the pericarpium Citri Tangerinae residue 2 Precursor templates for adsorbents.
Further, step 12) specifically includes: selecting 30-40 mesh pericarpium Citri Tangerinae granule, placing into extraction kettle, using absolute ethanol as entrainer, and setting flow rate of entrainer to 0.7-0.8mL/min and CO 2 The flow rate of the water is 2.8-3.2L/min, the extraction pressure is 30-40MPa, the extraction temperature is 35-40 ℃, and the extraction is carried out after the set value is reached.
Further, in the step 2), the concentration of the soluble yttrium salt, the soluble magnesium salt and the soluble calcium salt in the mixed solution is 2.40-2.60 mol/L, and the calcium-based CO obtained in the step 4) 2 Y in adsorbent 2 O 3 The mass ratio of MgO to CaO is 1:1:3.
Further, in the step 3), the solid-to-liquid ratio of the orange peel residue to the mixed solution is 1g:6ml to 1g:5ml.
Further, in the step 4), the calcination temperature is 700-900 ℃, the calcination temperature rising rate is 10 ℃/min, and the calcination time is 5-10 min.
Further, the calcium-based CO 2 The adsorbent is used for separating carbon dioxide by the adsorption of the calcium-based adsorbent and absorbing the carbon dioxide generated in the chemical chain reforming enhanced hydrogen production process.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is based on supercritical CO 2 Preparation method of calcium-based adsorbent by extraction technology adopts supercritical CO 2 The extracted orange peel residue is used for preparing calcium-based CO 2 Precursor template of adsorbent for realizing calcium-based CO 2 The optimization of the micro-pore structure of the adsorbent not only improves the adsorption capacity of the calcium-based CO2 adsorbent, but also has low economic cost; in addition, the body to be calcined is spontaneously combusted after being calcined for a short time of 5-10 min, and continuous calcination in a conventional preparation method (the conventional preparation method needs continuous calcination decomposition for 60-90 min to realize CaO generation) is replaced by the spontaneous combustion of the body to be calcined, so that the energy consumption required by preparation is reduced and the preparation rate is accelerated.
2. The invention is based on supercritical CO 2 The preparation method of the calcium-based adsorbent by the extraction technology loads materials for generating calcium oxide and metal auxiliaries on orange peel residues through an impregnation method, so that the prepared calcium-based CO2 adsorbent also has two metal auxiliaries, namely Y2O3 and MgO, besides the main component CaO, and is beneficial to improving the sintering resistance and the circulation stability of the calcium-based CO2 adsorbent and realizing the larger improvement of the CO2 adsorption performance of the calcium-based material.
3. The invention is based on supercritical CO 2 The preparation method of the calcium-based adsorbent by the extraction technology is simple, is suitable for large-scale industrial production, can be used for capturing carbon dioxide by the adsorption method of the calcium-based adsorbent and the combined synergistic process of chemical chain reforming enhanced hydrogen production, and has the characteristics of high adsorption efficiency, good circulation stability and the like.
Drawings
FIG. 1 is a supercritical CO-based embodiment 2 A flow chart of a preparation method of the calcium-based adsorbent by an extraction technology;
FIG. 2 shows a calcium-based C prepared according to the present inventionO 2 Adsorption amount comparison chart of adsorbent and other adsorbents;
FIG. 3 shows the calcium-based CO produced by the present invention 2 Comparison of adsorbent to other adsorbents for specific surface area, pore volume and average particle size.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures. In the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are directions or positional relationships based on those shown in the drawings, or are directions or positional relationships conventionally put in use of the inventive product, are merely for convenience of describing the present invention and simplifying the description, and are not indicative or implying that the apparatus or element to be referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance. Furthermore, the terms "horizontal," "vertical," and the like do not denote a requirement that the component be absolutely horizontal or overhang, but rather may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined. In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Examples:
referring to FIG. 1, a supercritical CO-based process 2 Preparation method of calcium-based adsorbent by extraction technology, and prepared calcium-based CO 2 The adsorbent is mainly used for adsorbing and separating carbon dioxide and carbon dioxide generated in a chemical chain reforming enhanced hydrogen production process by a calcium-based adsorbent, and the method comprises the following steps of:
1) Extracting pericarpium Citri Tangerinae with supercritical CO2, oven drying to obtain pericarpium Citri Tangerinae residue, and preparing calcium-based CO from pericarpium Citri Tangerinae residue 2 Precursor templates for adsorbents; the method comprises the following specific steps:
11 Cleaning pericarpium Citri Tangerinae, oven drying, and pulverizing to obtain pericarpium Citri Tangerinae granule.
12 Placing the orange peel particles into an extraction kettle for supercritical CO 2 Extracting; the method comprises the following steps: selecting 30-40 mesh pericarpium Citri Tangerinae granule, placing into extraction kettle, using absolute ethanol as entrainer, and setting flow rate of entrainer to 0.7-0.8mL/min and CO 2 The flow rate of the water is 2.8-3.2L/min, the extraction pressure is 30-40MPa, the extraction temperature is 35-40 ℃, and the extraction is carried out after the set value is reached;
in practice, the entrainer flow rates may be set at 0.7L/min, 0.75L/min and 0.8mL/min, CO 2 The flow rates of (a) may be set to 2.8L/min, 3.0L/min and 3.2L/min, the extraction pressures may be set to 30MPa, 35MPa and 40MPa, and the extraction temperatures may be set to 35 ℃, 38 ℃ and 40 ℃.
13 Filtering the extractive solution, collecting and oven drying pericarpium Citri Tangerinae particles, and subjecting to supercritical CO 2 Extracting to obtain pericarpium Citri Tangerinae residue, and preparing calcium-based CO from the pericarpium Citri Tangerinae residue 2 Precursor templates for adsorbents.
2) Dissolving and mixing soluble yttrium salt, soluble magnesium salt and soluble calcium salt to obtain a mixed solution; the amount of soluble yttrium salt, soluble magnesium salt and soluble calcium salt in the mixed solution depends on the calcium-based CO to be prepared 2 Y in adsorbent 2 O 3 The mass ratio of MgO to CaO is determined, and the concentrations of the soluble yttrium salt, the soluble magnesium salt and the soluble calcium salt are all 2.40-2.60 mol/L;
in practice, the concentration of soluble yttrium salt, soluble magnesium salt and soluble calcium salt may be 2.40 mol/L, 2.50mol/L and 2.60mol/L; in this example, yttrium nitrate and magnesium nitrate were used as the soluble yttrium salt and the soluble magnesium salt, respectively.
3) Placing orange peel residues into the mixed solution, and absorbing the mixed solution by the orange peel residues to obtain a body to be calcined; specifically, the solid-to-liquid ratio of orange peel residues to the mixed solution is 1g:6 ml-1 g:5ml; in practice, the solid to liquid ratio of orange peel residue to mixed solution may be 1g:5ml, 1g:5.5ml and 1g:6ml.
4) Calcining the body to be calcined to self-ignite to obtain calcium-based CO 2 The adsorbent is specifically calcined at 700-900 ℃, the temperature rising rate of calcination is 10 ℃/min, and the calcination time is 5-10 min; in practice, the calcination temperature may be 700 ℃, 750 ℃, 800 ℃, 850 ℃ and 900 ℃, and the calcination time may be 5 min, 7 min and 10 min; in this example, a calcium-based CO was produced 2 Y in adsorbent 2 O 3 The mass ratio of MgO to CaO is 1:1:3.
The invention is based on supercritical CO 2 Preparation method of calcium-based adsorbent by extraction technology, and calcium-based CO prepared by the method 2 Adsorbent and conventional adsorbent and calcium-based CO using the method of the present invention but with metal promoters based on yttrium and aluminum 2 The comparison of the specific surface area, pore volume and average particle size of the adsorbent is shown in figures 3 a, b and c, respectively, and it can be seen that the calcium-based CO prepared by the method of the present invention 2 Adsorbent ratioThe surface area, the pore volume and the average particle size are better; this is due to the supercritical CO 2 The extracted orange peel residues have good specific surface area and pore volume, and the plant fibers formed after extraction can be used as biomass templates to prepare high-performance and high-stability calcium-based CO 2 An adsorbent; not only improve the calcium-based CO 2 The adsorption capacity of the adsorbent is low in economic cost; in addition, the precursor template is orange peel residues and can be used for assisting combustion, the body to be calcined is spontaneous-burned after being calcined for a short time of 5-10 min, and the spontaneous combustion of the body to be calcined is utilized to replace continuous calcination in a conventional preparation method (the conventional preparation method needs continuous calcination and decomposition for 60-90 min to realize CaO generation), so that the energy consumption required by preparation is reduced and the preparation rate is accelerated;
loading materials for generating calcium oxide and metal auxiliary agent on orange peel residue by impregnation method, i.e. adding yttrium nitrate and magnesium nitrate into mixed solution to obtain calcium-based CO 2 The adsorbent contains Y in addition to CaO as a main component 2 O 3 And MgO, and the calcium-based CO prepared by the method 2 Adsorbent and conventional adsorbent and calcium-based CO using the method of the present invention but with metal promoters based on yttrium and aluminum 2 The adsorption amount of the adsorbent is compared with that of FIG. 2, and the calcium-based CO prepared by the method of the invention 2 The adsorption capacity and the circulation stability of the adsorbent are better; in addition, the calcium-based CO prepared by the method of the invention 2 The metal auxiliary agent in the adsorbent is mainly yttrium and magnesium, and is obviously superior to calcium-based CO with the metal auxiliary agent mainly yttrium and aluminum 2 An adsorbent; namely, the metal auxiliary agent is mainly yttrium and magnesium, which is beneficial to improving calcium-based CO 2 The sintering resistance and the cycling stability of the adsorbent can realize the CO of the calcium-based material 2 The adsorption performance is greatly improved; the preparation method is simple, can be used for capturing carbon dioxide by a calcium-based adsorbent adsorption method and a chemical chain reforming enhanced hydrogen production combined synergistic process, and is suitable for large-scale industrial production.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (7)
1. Supercritical CO-based 2 The preparation method of the calcium-based adsorbent by the extraction technology is characterized by comprising the following steps of: the method comprises the following steps:
1) Supercritical CO treatment of pericarpium Citri Tangerinae 2 Extracting and drying to obtain orange peel residues;
2) Dissolving and mixing soluble yttrium salt, soluble magnesium salt and soluble calcium salt to obtain a mixed solution;
3) Placing orange peel residues into the mixed solution, and absorbing the mixed solution by the orange peel residues to obtain a body to be calcined;
4) Calcining the body to be calcined to self-ignite to obtain calcium-based CO 2 An adsorbent.
2. A supercritical CO-based process according to claim 1 2 The preparation method of the calcium-based adsorbent by the extraction technology is characterized by comprising the following steps of: step 1) comprises the following sub-steps:
11 Cleaning pericarpium Citri Tangerinae, oven drying, and pulverizing to obtain pericarpium Citri Tangerinae granule;
12 Placing the orange peel particles into an extraction kettle for supercritical CO 2 Extracting;
13 Filtering the extractive solution, collecting and oven drying pericarpium Citri Tangerinae particles, and subjecting to supercritical CO 2 Extracting to obtain pericarpium Citri Tangerinae residue, and preparing calcium-based CO from the pericarpium Citri Tangerinae residue 2 Precursor templates for adsorbents.
3. A supercritical CO-based process according to claim 2 2 The preparation method of the calcium-based adsorbent by the extraction technology is characterized by comprising the following steps of: the step 12) is specifically as follows: selecting 30-40 mesh pericarpium Citri Tangerinae granule, placing into extraction kettle, using absolute ethanol as entrainer, and setting flow rate of entrainer to 0.7-0.8mL/min and CO 2 The flow rate of the water is 2.8-3.2L/min, the extraction pressure is 30-40MPa, the extraction temperature is 35-40 ℃, and the extraction is carried out after the set value is reached.
4. A supercritical CO-based process according to claim 1 2 The preparation method of the calcium-based adsorbent by the extraction technology is characterized by comprising the following steps of: in the step 2), the concentration of the soluble yttrium salt, the soluble magnesium salt and the soluble calcium salt in the mixed solution is 2.40-2.60 mol/L, and the calcium-based CO obtained in the step 4) 2 Y in adsorbent 2 O 3 The mass ratio of MgO to CaO is 1:1:3.
5. A supercritical CO-based process according to claim 1 2 The preparation method of the calcium-based adsorbent by the extraction technology is characterized by comprising the following steps of: in the step 3), the solid-to-liquid ratio of the orange peel residues to the mixed solution is 1 g/6 ml-1 g/5 ml.
6. A supercritical CO-based process according to claim 1 2 The preparation method of the calcium-based adsorbent by the extraction technology is characterized by comprising the following steps of: in the step 4), the calcination temperature is 700-900 ℃, the calcination temperature rising rate is 10 ℃/min, and the calcination time is 5-10 min.
7. The calcium-based CO of any one of claims 1-6 2 The use of an adsorbent in the adsorptive separation of carbon dioxide from a calcium-based adsorbent and in the adsorption of carbon dioxide produced in a chemical chain reforming enhanced hydrogen production process.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN202310940909.4A CN117000197B (en) | 2023-07-28 | 2023-07-28 | A method for preparing calcium-based adsorbents based on supercritical CO2 extraction technology |
| ZA2023/10087A ZA202310087B (en) | 2023-07-28 | 2023-10-30 | A preparation method of calcium based adsorbent based on supercritical co2 extraction technology |
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| CN202310940909.4A CN117000197B (en) | 2023-07-28 | 2023-07-28 | A method for preparing calcium-based adsorbents based on supercritical CO2 extraction technology |
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| ZA202310087B (en) | 2024-05-30 |
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