CN115569630A - Calcium-based CO 2 Adsorbing material and preparation method thereof - Google Patents

Calcium-based CO 2 Adsorbing material and preparation method thereof Download PDF

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CN115569630A
CN115569630A CN202211198545.9A CN202211198545A CN115569630A CN 115569630 A CN115569630 A CN 115569630A CN 202211198545 A CN202211198545 A CN 202211198545A CN 115569630 A CN115569630 A CN 115569630A
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孙健
李和雯
栗珂珂
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Nanjing Normal University
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    • B01J20/28002—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 physical properties
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01J2220/00—Aspects relating to sorbent materials
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • B01J2220/4831—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton having been subjected to further processing, e.g. paper, cellulose pulp
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Abstract

The invention discloses a calcium-based CO 2 The preparation method of the adsorbing material comprises the following steps: dissolving calcium salt and zirconium salt to prepare a mixed solution; (2) Putting the cigarette butts into the mixed solution, and enabling the mixed solution to be absorbed by the cigarette butts to obtain wet fibers; (3) Calcining the wet cigarette butt obtained in the step (2) to obtain the calcium-based CO 2 Adsorbing the material. The method utilizes the cigarette butt as a template for assisting combustion, optimizes the micro-pore structure of the calcium-based material, improves the adsorption capacity of the calcium-based material, removes the drying step in the common synthetic method, and reduces the energy consumption in the synthetic processThe synthesis rate is accelerated.

Description

Calcium-based CO 2 Adsorbing material and preparation method thereof
Technical Field
The invention relates to an adsorbing material and a preparation method thereof, in particular to calcium-based CO 2 An adsorbing material and a preparation method thereof.
Background
Existing CO 2 The trapping technology mainly comprises the trapping before combustion, the trapping after combustion and the trapping of CO by oxygen-enriched combustion 2 Sealing three types of blocksThe method is carried out. Calcium looping (CaL) is a post-combustion capture technology that is of great interest because of its environmentally friendly and low cost characteristics. CaL based on CaO and CaCO 3 The principle of reversible carbonation and decomposition reaction, separation of CO from industrial fumes 2 Realization of CO 2 High efficiency of trapping.
CaO is a common inorganic compound, has low price and wide source, and has theoretical CO 2 The adsorption capacity is strong and is about 0.786g of CO 2 Per gram of CaO. However, due to CaCO 3 The severe sintering phenomenon exists in the high-temperature cyclic reaction process, which causes the serious reduction of the adsorption capacity of the CaO-based adsorbent. Therefore, researchers have proposed a modification method for improving the cyclic reaction performance of the adsorbent by adding an inert carrier. Generally, inert carriers such as Al, mg, ti, and Zr are candidate materials effective for improving the stability of CaO-based adsorbents.
It has been found that doping of the CaO-based sorbent material with an inert carrier can be achieved by wet mixing, impregnation and sol-gel methods. Most synthesis methods require drying a mixture of CaO and an inert carrier precursor to obtain the target CaO-based sorbent. However, the drying process has high energy consumption and is slow, which results in the decrease of the synthesis efficiency of the inert carrier doped CaO-based adsorbent and cannot meet the requirement of industrial mass production.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide calcium-based CO for removing a drying step to reduce energy consumption in a synthesis process 2 Adsorbing material;
it is a second object of the present invention to provide the above calcium-based CO 2 A preparation method of the adsorbing material.
The technical scheme is as follows: the calcium-based CO of the invention 2 The preparation method of the adsorbing material comprises the following steps:
(1) Dissolving calcium salt and zirconium salt to prepare a mixed solution;
(2) Putting the cigarette butts into the mixed solution, and enabling the mixed solution to be absorbed by the cigarette butts to obtain wet fibers;
(3) Calcining the wet cigarette butts obtained in the step (2) to obtain the calciumRadical CO 2 Adsorbing the material.
Wherein, in the step (2), the cigarette stub is broken into small segments and is placed in the mixed solution.
Wherein in the step (2), the cigarette butts are made of cellulose acetate.
Wherein in the step (1), the mass ratio of the calcium salt to the zirconium salt is 3. The calcium salt is calcium nitrate and the zirconium salt is zirconium nitrate.
Wherein in the step (1), the dissolving condition is water bath heating at 40-80 ℃.
Wherein, in the step (3), when the acetate fiber absorbs the mixed solution, the solid-to-liquid ratio is 1 g.
Wherein the calcining temperature in the step (3) is 600-900 ℃, and the time is 60-120 min.
Wherein the temperature rise rate of the calcination in the step (3) is 5-10 ℃/min.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) The invention utilizes the cigarette butts as templates to assist combustion, optimizes the micro-pore structure of the calcium-based material, not only improves the adsorption capacity of the calcium-based material, but also removes the drying step in the common synthetic method, reduces the energy consumption in the synthetic process and accelerates the synthetic speed. (2) By doping the inert carrier zirconium nitrate in the calcium-based material, the sintering resistance and the cycling stability of the calcium-based material are improved, and the calcium-based material CO is realized 2 The conversion rate is greatly improved. (3) The preparation method is simple and suitable for large-scale industrial production.
Drawings
FIG. 1 shows the amounts of CO per unit mass of comparative examples 1 to 3 and example 1 2 Adsorption capacity;
FIG. 2 is SEM images of adsorbents prepared at different temperatures after 17 cycles;
FIG. 3 shows the CO per unit mass of comparative example 1 and examples 2 to 5 2 Adsorption capacity.
Detailed Description
The present invention is described in further detail below.
Example 1
A preparation process of a Ca/Zr15-CAC calcium-based adsorption material based on a cigarette butt template auxiliary combustion method for a zirconium-doped calcium-based adsorption material comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 17.92g and Zr (NO) 3 ) 4 ·5H 2 O sample 2.61g, 50ml deionized water was added. The mixed solution is stirred under the condition of heating in a water bath at 60 ℃ until the sample is completely dissolved.
Step 2, the dried butts were skinned and cut into small pieces approximately 10mm long, and 7.69g of the cut butts were weighed.
And 3, placing the cut cigarette butts in a mixed solution of calcium nitrate and zirconium nitrate, and setting a solid-liquid ratio of 1g to 7ml so as to ensure that the cigarette butts can completely absorb the mixed solution, thereby obtaining wet cigarette butts.
And 4, calcining the wet cigarette butts in a muffle furnace at the heating rate of 10 ℃/min to 900 ℃, and keeping the temperature for 120min at constant temperature to obtain the Ca/Zr15-CAC calcium-based adsorption material based on the cigarette butt template auxiliary combustion method.
Example 2
A preparation method of a Ca/Zr5-CAC calcium-based adsorption material based on a cigarette butt template auxiliary combustion method for a zirconium-doped calcium-based adsorbent material comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 20.03g and Zr (NO) 3 ) 4 ·5H 2 O sample 0.87g, and 50ml of deionized water was added. The mixed solution is stirred under the condition of heating in a water bath at 60 ℃ until the sample is completely dissolved.
Step 2, the dried butts were skinned and cut into small pieces approximately 10mm long, and 7.69g of the cut butts were weighed.
And 3, placing the cut cigarette butts into a mixed solution of calcium nitrate and zirconium nitrate, and setting a solid-to-liquid ratio of 1g to 7ml so as to ensure that the cigarette butts can completely absorb the mixed solution, thereby obtaining the wet cigarette butts.
And 4, calcining the wet cigarette butts in a muffle furnace at the heating rate of 10 ℃/min to 750 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr5-CAC calcium-based adsorption material based on the cigarette butt template auxiliary combustion method.
Example 3
A preparation method of a Ca/Zr10-CAC calcium-based adsorption material based on a cigarette butt template auxiliary combustion method for a zirconium-doped calcium-based adsorbent material comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 18.98g and Zr (NO) 3 ) 4 ·5H 2 O sample 1.74g, and 50ml of deionized water was added. And stirring the mixed solution under the heating condition of water bath at 60 ℃ until the sample is completely dissolved.
Step 2, the dried butts were skinned and cut into small pieces approximately 10mm long, and 7.69g of the cut butts were weighed.
And 3, placing the cut cigarette butts in a mixed solution of calcium nitrate and zirconium nitrate, and setting a solid-liquid ratio of 1g to 7ml so as to ensure that the cigarette butts can completely absorb the mixed solution, thereby obtaining wet cigarette butts.
And 4, calcining the wet cigarette butts in a muffle furnace at the heating rate of 10 ℃/min to 750 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr10-CAC calcium-based adsorption material based on the cigarette butt template auxiliary combustion method.
Example 4
A Ca/Zr15-CAC calcium-based adsorbing material, a preparation method of a zirconium-doped calcium-based adsorbing material based on a cigarette butt template auxiliary combustion method, comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 17.92g and Zr (NO) 3 ) 4 ·5H 2 O sample 2.61g, and 50ml of deionized water was added. The mixed solution is stirred under the heating condition of water bath at 60 ℃ until the sample is completely dissolved.
Step 2, the dried butts were skinned and cut into small pieces approximately 10mm long, and 7.69g of the cut butts were weighed.
And 3, placing the cut cigarette butts in a mixed solution of calcium nitrate and zirconium nitrate, and setting a solid-liquid ratio of 1g to 7ml so as to ensure that the cigarette butts can completely absorb the mixed solution, thereby obtaining wet cigarette butts.
And 4, calcining the wet cigarette butts in a muffle furnace at the heating rate of 10 ℃/min to 750 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr15-CAC calcium-based adsorption material based on the cigarette butt template auxiliary combustion method.
Example 5
A Ca/Zr25-CAC calcium-based adsorbing material, a preparation method of a zirconium-doped calcium-based adsorbing material based on a cigarette butt template auxiliary combustion method, comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 15.81g and Zr (NO) 3 ) 4 ·5H 2 O sample 4.36g, and 50ml of deionized water was added. And stirring the mixed solution under the heating condition of water bath at 60 ℃ until the sample is completely dissolved.
Step 2, the dried butts were skinned and cut into small pieces approximately 10mm long, and 7.69g of the cut butts were weighed.
And 3, placing the cut cigarette butts into a mixed solution of calcium nitrate and zirconium nitrate, and setting a solid-to-liquid ratio of 1g to 7ml so as to ensure that the cigarette butts can completely absorb the mixed solution, thereby obtaining the wet cigarette butts.
And 4, calcining the wet cigarette butts in a muffle furnace at the heating rate of 10 ℃/min to 750 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr25-CAC calcium-based adsorption material based on the cigarette butt template auxiliary combustion method.
Example 6
A preparation process of a Ca/Zr15-CAC calcium-based adsorption material based on a cigarette butt template auxiliary combustion method for a zirconium-doped calcium-based adsorbent material comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 17.92g and Zr (NO) 3 ) 4 ·5H 2 2.61g of O sample, 50ml of deionized water was added. The mixed solution is stirred under the condition of heating in a water bath at 60 ℃ until the sample is completely dissolved.
Step 2, the dried butts are skinned and cut into small pieces approximately 10mm long, and 7.69g of the cut butts are weighed.
And 3, placing the cut cigarette butts in a mixed solution of calcium nitrate and zirconium nitrate, and setting a solid-liquid ratio of 1g to 7ml so as to ensure that the cigarette butts can completely absorb the mixed solution, thereby obtaining wet cigarette butts.
And 4, calcining the wet cigarette butts in a muffle furnace at the heating rate of 10 ℃/min to 600 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr15-CAC calcium-based adsorption material based on the cigarette butt template auxiliary combustion method.
Comparative example 1
Pure calcium hydroxide was used in place of the calcium-based sorbent material.
Comparative example 2
A preparation method of a Ca/Zr15-SG calcium-based adsorption material, namely a zirconium-doped calcium-based adsorbent material based on a sol-gel method, comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 17.92g and Zr (NO) 3 ) 4 ·5H 2 2.61g of O sample, and 50ml of deionized water, and equimolar citric acid were added to obtain a mixed solution.
And 2, stirring the mixed solution in a constant-temperature heating stirrer to be viscous under the water bath heating condition of 80 ℃.
And 3, putting the viscous object into a drying box, and drying for 24 hours at 110 ℃ to obtain the solid precursor material.
And 4, calcining the solid precursor material in a muffle furnace at a heating rate of 10 ℃/min to 900 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr15-SG calcium-based adsorbing material.
Comparative example 3
A preparation method of a Ca/Zr15-WM calcium-based adsorption material based on a wet mixing method for a zirconium-doped calcium-based adsorption material comprises the following specific steps:
step 1, weighing Ca (NO) 3 ) 2 ·4H 2 O sample 17.92g and Zr (NO) 3 ) 4 ·5H 2 O sample 2.61g, and 50ml of deionized water was added to obtain a mixed solution. The mixed solution is stirred in a constant temperature heating stirrer under the heating condition of water bath at 60 ℃ until the sample is completely dissolved.
And 2, putting the mixed solution into a drying box, and drying for 24 hours at 110 ℃ to obtain the solid precursor material.
And 3, calcining the solid precursor material in a muffle furnace at a heating rate of 10 ℃/min to 900 ℃, and keeping the constant temperature for 120min to obtain the Ca/Zr15-WM calcium-based adsorbing material.
Test one: samples of example 1 and comparative examples 1-3 were subjected to cyclic CO using a permanent HT-4 thermogravimetric analyzer 2 And (3) adsorption test:
about 10mg of the sample was placed in an alumina crucible and was 15vol% CO 2 And 85vol% of N 2 Under a mixed atmosphere of 2 And (4) performing adsorption experiments. Calcining the target sample at 850 deg.C for 30min, performing cyclic reaction, carbonating at 650 deg.C for 20min, calcining at 850 deg.C for 10min, repeating the above cyclic process for 17 times, and further deeply studying CO of the sample 2 And (4) adsorption performance.
This test will be conducted with CO 2 Adsorption Capacity C n CaO carbonation conversion X n Derivative V of CaO carbonation conversion n Recycle of CO as an evaluation adsorbent 2 An index of adsorption capacity; wherein, C n Has the unit of g CO 2 G/g sample, g/g; x n The unit of (A) is; v n The unit of (b) is%/min.
Figure BDA0003871526750000051
Figure BDA0003871526750000052
Figure BDA0003871526750000053
Wherein n is the number of carbonation/calcination cycles,
Figure BDA0003871526750000054
and
Figure BDA0003871526750000055
represents the mass of the adsorbent during the nth carbonation and calcination, respectively, g; delta is an adsorbentFree CaO content of (C), M CaO And M CO2 Respectively represent CaO and CO 2 The molar mass of (a);
Figure BDA0003871526750000056
is adsorbent CO 2 Adsorption capacity versus carbonation time.
CO based on cigarette butt template assisted Combustion method example 1 and comparative examples 1-3 2 The adsorption capacity is shown in FIG. 1. Of these, comparative example 1 initial CO 2 The adsorption capacity is the strongest and is 0.562g/g, but the cycling stability is poor. In contrast, example 1 exhibited highly stable CO during cycling 2 And (4) adsorption capacity. CO of comparative example 2 after 17 cycles 2 The adsorption capacity was as high as 0.46g/g, which is about 11.5 times that of comparative example 3. In addition, example 1 also exhibited a relatively high CO 2 The adsorption capacity was 0.279g/g. The time and energy saved by example 1 in the process of circulation experiment can be used for compensating the CO of example 1 relative to comparative example 2 in practical application 2 Loss due to reduced adsorption capacity.
And (2) test II: samples of examples 1, 4 and 6 were subjected to cyclic CO using a permanent HT-4 thermogravimetric analyzer 2 And (4) performing an adsorption test. The test conditions were the same as those of test one.
Characteristic SEM images of examples 1, 4 and 6 based on the cigarette butt template assisted combustion method are shown in fig. 2. The adsorbent of example 4 after 17 cycles showed the most developed surface topography and a more fluffy porous structure compared to examples 1 and 6. The surface morphology of example 1 is not developed because the high temperature calcined sample is prone to severe sintering. The porous microstructure helps to promote CO 2 Diffuses into the synthetic sorbent and fully reacts with the internal active CaO. Thus, example 4 is recycling CO 2 The adsorption aspect is optimal.
And (3) test III: samples of examples 2-5 and comparative example 1 were subjected to cyclic CO using a permanent HT-4 thermogravimetric analyzer 2 And (4) performing adsorption test. The test conditions were the same as those of test one.
CO production method based on cigarette end template auxiliary combustion method in examples 2 to 5 and comparative example 1 2 The adsorption capacity is shown in FIG. 3, withAll examples show more stable CO with increasing Zr ratio 2 Adsorption capacity due to inert ZrO in calcium-based materials 2 Indicating that the addition of Zr-based loading helps to increase the CO content of CaO-based sorbents 2 And (4) adsorption stability. Abundant CaZrO present in calcium-based materials 3 The crystal grains make the crystal grains have more excellent pore structure, and CaZrO 3 The high Taman temperature is 1076 ℃, which can effectively improve the structural stability of the calcium-based adsorbent and simultaneously reduce the negative influence of high-temperature sintering on the adsorption performance of the calcium-based material. Of these, the initial recycle CO of examples 2-3 and comparative example 2 The adsorption capacity is high, about 0.56g/g. CO of examples 2-3 during the Cyclic adsorption test 2 The adsorption capacity was slightly decreased as compared with comparative example 1, but its CO was decreased 2 The adsorption capacity is relatively stable. Furthermore, the initial recycle CO of example 5 2 The adsorption capacity was lower than that of comparative example 1, however, after 17 cycles, the adsorption capacity was higher than that of comparative example 1, which was 0.32g/g.

Claims (8)

1. Calcium-based CO 2 The preparation method of the adsorbing material is characterized by comprising the following steps of:
(1) Dissolving calcium salt and zirconium salt to prepare a mixed solution;
(2) Putting the cigarette butts into the mixed solution, and enabling the mixed solution to be absorbed by the cigarette butts to obtain wet fibers;
(3) Calcining the wet cigarette end obtained in the step (2) to obtain the calcium-based CO 2 And (3) adsorbing the material.
2. Calcium-based CO according to claim 1 2 The preparation method of the adsorbing material is characterized in that in the step (2), the cigarette butts are crushed into small pieces and placed in the mixed solution.
3. The calcium-based CO of claim 1 2 The preparation method of the adsorbing material is characterized in that in the step (2), the components of the cigarette butts are acetate fibers.
4. The method of claim 1Calcium-based CO of 2 The preparation method of the adsorbing material is characterized in that in the step (1), the mass ratio of the calcium salt to the zirconium salt is (3).
5. Calcium-based CO according to claim 1 2 The preparation method of the adsorbing material is characterized in that in the step (1), the dissolving condition is water bath heating at 40-80 ℃.
6. The calcium-based CO of claim 1 2 And (3) an adsorbent, wherein when the acetate fibers absorb the mixed solution in step (3), the solid-to-liquid ratio is 1 g.
7. Calcium-based CO according to claim 1 2 The adsorbing material is characterized in that the calcining temperature in the step (3) is 600-900 ℃, and the time is 60-120 min.
8. Calcium-based CO according to claim 1 2 The adsorbing material is characterized in that the temperature rise rate of the calcination in the step (3) is 5-10 ℃/min.
CN202211198545.9A 2022-09-29 2022-09-29 Calcium-based CO 2 Adsorbing material and preparation method thereof Pending CN115569630A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100212495A1 (en) * 2009-02-26 2010-08-26 Kishor Purushottam Gadkaree Sorbent Structure Applicable for Carbon Dioxide Capture
CN107376826A (en) * 2017-08-29 2017-11-24 武汉凯迪工程技术研究总院有限公司 Calcium oxide-based high temperature CO2Adsorbent and preparation method thereof
CN107961757A (en) * 2017-12-04 2018-04-27 山东大学 A kind of high activity composite calcium-base CO2Absorbent and preparation method thereof
RU2659256C1 (en) * 2017-11-28 2018-06-29 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Method for producing co2 high-temperature adsorbents
CN108525637A (en) * 2018-03-21 2018-09-14 中国矿业大学 A kind of carbon template modified calcium-base carbon dioxide absorber and preparation method thereof
CN111632476A (en) * 2020-05-29 2020-09-08 武汉理工大学 Carbon dioxide adsorbent and preparation method thereof
CN113233512A (en) * 2021-06-03 2021-08-10 华中科技大学 Nano metal oxide and preparation method and application thereof
CN114130361A (en) * 2021-12-24 2022-03-04 南京师范大学 Adsorb CO2The nitrogen-doped porous carbon granular material and the preparation method thereof
US20230087232A1 (en) * 2019-10-22 2023-03-23 Julien PAQUE Cleaning and depolluting of fibres originating from used cigarette butts by placing in contact with a supercritical fluid and recycling of the depolluted fibres

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100212495A1 (en) * 2009-02-26 2010-08-26 Kishor Purushottam Gadkaree Sorbent Structure Applicable for Carbon Dioxide Capture
CN107376826A (en) * 2017-08-29 2017-11-24 武汉凯迪工程技术研究总院有限公司 Calcium oxide-based high temperature CO2Adsorbent and preparation method thereof
RU2659256C1 (en) * 2017-11-28 2018-06-29 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Method for producing co2 high-temperature adsorbents
CN107961757A (en) * 2017-12-04 2018-04-27 山东大学 A kind of high activity composite calcium-base CO2Absorbent and preparation method thereof
CN108525637A (en) * 2018-03-21 2018-09-14 中国矿业大学 A kind of carbon template modified calcium-base carbon dioxide absorber and preparation method thereof
US20230087232A1 (en) * 2019-10-22 2023-03-23 Julien PAQUE Cleaning and depolluting of fibres originating from used cigarette butts by placing in contact with a supercritical fluid and recycling of the depolluted fibres
CN111632476A (en) * 2020-05-29 2020-09-08 武汉理工大学 Carbon dioxide adsorbent and preparation method thereof
CN113233512A (en) * 2021-06-03 2021-08-10 华中科技大学 Nano metal oxide and preparation method and application thereof
CN114130361A (en) * 2021-12-24 2022-03-04 南京师范大学 Adsorb CO2The nitrogen-doped porous carbon granular material and the preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HASHEMI, SM ET AL.: ""Solution combustion synthesis of zirconia-stabilized calcium oxide sorbents for CO2 capture"", 《FUEL》, vol. 269, pages 2 *
HEWEN LI ET AL: ""Facile, time-saving cigarette butt-assisted combustion synthesis of modified CaO-based sorbents for high-temperature CO2 capture"", 《FUEL》, vol. 337, pages 1 - 13 *
李成璞: ""醋酸纤维燃烧辅助合成纳米金属氧化物及其脱硝性能研究"", 《万方数据库》, pages 1 *

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