CN114768753A - Red mud-based CO2Preparation method and application of adsorption and desorption agent - Google Patents
Red mud-based CO2Preparation method and application of adsorption and desorption agent Download PDFInfo
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- CN114768753A CN114768753A CN202210449625.0A CN202210449625A CN114768753A CN 114768753 A CN114768753 A CN 114768753A CN 202210449625 A CN202210449625 A CN 202210449625A CN 114768753 A CN114768753 A CN 114768753A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 64
- 238000003795 desorption Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 61
- 239000007789 gas Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 238000007873 sieving Methods 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 claims abstract 2
- 230000023556 desulfurization Effects 0.000 claims abstract 2
- 239000000428 dust Substances 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims 1
- 239000008187 granular material Substances 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 238000011161 development Methods 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 2
- 238000011269 treatment regimen Methods 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000000292 calcium oxide Substances 0.000 description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000004131 Bayer process Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- 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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- 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
- B01J20/041—Oxides or hydroxides
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
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- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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Abstract
The invention discloses red mud-based CO2The preparation method and application of the adsorption and desorption agent comprise drying and grinding red mud, and sieving the ground red mud with a 60-mesh sieve; uniformly mixing the sieved red mud, CaO powder and MgO powder, and heating and activating the mixed powder to obtain activated red mud, wherein the activated red mud is stored at normal temperature in a dark place in vacuum; grinding and tabletting the activated red mud, granulating, and filling the granules for adsorbing CO2In the reactor, the carbon dioxide gas after desulfurization and dust removal is pressurized and introduced into an adsorption reactor, and after reaching adsorption saturation, the temperature is raised for desorption, and high-concentration CO is enriched2(ii) a The invention realizes the aims of carbon neutralization and carbon emission reduction in industrial development, realizes the synergistic treatment of solid waste and waste gas, conforms to the environmental protection treatment strategy of pollution and carbon reduction synergistic effect, and has good development prospect and environmental significance.
Description
Technical Field
The invention relates to the field of cross-medium pollutant resource treatment, in particular to red mud-based CO2A preparation method and application of an adsorption and desorption agent.
Background
The red mud is strong alkaline industrial solid waste generated in the industrial production process of alumina, the pH value of the red mud is about 10-12, and the specific surface area of the unactivated red mud is 7-10 m2·g-1The specific surface area of the red mud after high-temperature activation can reach 20m2·g-1As described above. The developed pore structure of the red mud is the key of the adsorbent with good adsorption performance, the pore structure, the specific surface area and the pore size of the adsorbent have obvious influence on the adsorption performance, and the abundant pore structure can obtain stronger physical adsorption capacity. It is estimated that, generally, 1 to 1.5 tons of red mud are additionally produced per 1 ton of alumina produced on average; at present, the comprehensive utilization rate of the red mud is low, most of the red mud is piled up by adopting a wet-method open storage dam, a large amount of land is occupied in the piling process, and the high-alkalinity and high-salinity chemical components of the red mud permeate the land to easily cause land alkalization and underground water pollution, so that the ecological environment is damaged. The utilization rate of the red mud is low, and if the red mud is not utilized under the double-carbon background, the red mud is a waste of resources.
Disclosure of Invention
The invention activates industrial solid waste red mud at high temperature, and the activated red mud is pressed into granular CO2Adsorption and desorption of materials, low concentration of CO2Under the pressurizing condition, the red mud is pressurized to promote the low-concentration CO through the adsorption material layer2After the adsorption is saturated, the valve of the air inlet and the air outlet is closed, the temperature in the adsorber is raised, and CO adsorbed in the red mud material is enabled to be adsorbed2Desorption, after which CO is removed2CO is pumped out from the adsorption device for enrichment storage and enrichment storage2Can be used for preparing hydrogen storage material formic acid, and the hydrogen storage energy can replace the traditional fossil energy, thereby realizing the carbon neutralization and carbon peak reaching in the industrial development, the invention provides a new idea of carbon sequestration treatment and disposal,and simultaneously realizes the red mud-based CO2The adsorption and desorption agent provides a brand new technical support for the green and healthy development of the industrial production industry under the aim of 'double carbon'.
The technical scheme of the invention is as follows:
red mud-based CO2The preparation method of the adsorption and desorption agent comprises the following specific steps:
(1) putting the red mud into an oven for drying treatment, putting the dried red mud into a mortar, grinding the red mud into fine particles, putting the fine particles into a screen mesh, and sieving the fine particles with a 60-mesh sieve;
(2) uniformly mixing the sieved red mud, CaO powder and MgO powder, heating and activating the mixed powder to obtain activated red mud, and placing the activated red mud in vacuum condition for normal-temperature dark preservation; grinding, tabletting and granulating the activated red mud to obtain the red mud-based CO2And adsorbing and desorbing the agent.
The red mud in the step (1) comprises the following components in percentage by mass: al (Al)2O3 16～23％，SiO2 9～14％，Fe2O3 23～39％， CaO 13～17％，Na2O 2～7％，TiO21-4%, and the other part is impurities.
The drying temperature of the drying oven in the step (1) is 100-120 ℃ and the temperature is kept for 24 hours.
The mass ratio of the red mud, CaO powder and MgO powder dried in the step (2) is 10 (1-1.2) to (1-1.2).
The heating activation in the step (2) is to heat up to 200 ℃ and 500 ℃ at the heating rate of 3-5 ℃/min under the protection of nitrogen, and keep the temperature for 2-3 h.
And (3) sieving the granules subjected to tabletting and granulating in the step (2) by a 40-60-mesh sieve, namely sieving the granules below the 40-mesh sieve and sieving the granules above the 60-mesh sieve, wherein the particle size of the granules is 0.25-0.425 mm.
The invention also provides the red mud-based CO2An application method of adsorption and desorption agent for adsorbing CO from red mud2Adsorbing CO by filling the particles of adsorbent and desorbent2In the reactor, carbon dioxide-containing gas is introduced into a gas inlet, the flow rate is 400mL/min, the pressurization of the gas inlet is 2bar, the gas is adsorbed after passing through a red mud material layer, after the adsorption material reaches adsorption saturation, a valve of the gas inlet and a valve of a gas outlet are closed, the temperature is raised, and the temperature is increased at 500-600 DEG CKeeping the temperature for 20-30 min so as to ensure that CO is generated2Desorbing from the material, and then removing CO in the reactor2The pressure in the reactor is reduced and the desorption efficiency is increased in the process of pumping out and storing.
The invention has the beneficial effects that:
(1) the invention utilizes industrial solid waste red mud to treat low-concentration CO2Adsorbing, desorbing and enriching to obtain high-concentration CO2Enriched CO2The formic acid can be electrochemically and catalytically converted into formic acid according to the existing method, the economic value is created while the waste is treated by waste and the waste is utilized, and the method is an energy-saving and environment-friendly treatment method and has certain development prospect and significance for environmental protection.
(2) The invention provides a new idea of low-cost treatment and disposal of red mud, alkaline substances are added into dried red mud for modification and then high-temperature activation is carried out, and compared with the original red mud, the modified and activated red mud can be used for treating CO2The adsorption capacity of the red mud is greatly increased, the efficient and directional resource utilization of the red mud is realized, and a brand new technical support is provided for the industrial green and healthy development under the aims of carbon neutralization and carbon peak-to-peak.
(3) The invention realizes CO2The method has the advantages of collecting and processing, reducing the stock quantity of the red mud, realizing 'treatment of waste by waste and utilization of waste', and having great significance. In the large background of carbon neutralization and carbon peak, CO is generated in the industrial production process2The pollution treatment is very important.
Drawings
FIG. 1 shows red mud as received N2Adsorption-desorption isotherm plot;
FIG. 2 shows the activated red mud N of example 22Adsorption-desorption isotherm diagram;
fig. 3 is an SEM image of activated red mud of example 2.
Detailed Description
The present invention is further illustrated by the following specific examples.
CO in examples of the invention2The detection method of the volume fraction comprises the following steps: adopting ECOM flue gas analyzer (ECOM-J2 KN) as the model, and detecting CO2The gas flow rate is 400mL/min, the gas outlet is communicated with a flue gas analyzer, and one gas is measured every 5minCO at the secondary outlet2Gas volume fraction.
Example 1
Red mud-based CO2The preparation method and the application of the adsorption and desorption agent comprise the following specific steps:
(1) the method comprises the following steps of collecting Bayer process massive red mud, wherein the red mud comprises the following components in percentage by mass: al (Al)2O3 16～23％，SiO2 9～14％，Fe2O3 23～39％，CaO 13～17％，Na2O 2～7％，TiO21-4 percent of the red mud, and the balance of inevitable impurities, putting the blocky red mud into an oven, and keeping the temperature for 24 hours at the temperature of 120 ℃ to carry out drying treatment;
(2) putting the dried red mud into a mortar, grinding the red mud into fine particles, and sieving the fine particles with a 60-mesh sieve;
(3) grinding CaO into powder in a mortar, and uniformly mixing the powder with MgO powder and dried and sieved red mud according to the mass ratio of 1:1:10, namely adding 1g of CaO powder and 1g of MgO powder into 10g of red mud;
(4) heating the mixed powder to 200 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 3 hours, heating and activating to obtain activated red mud, and placing the activated red mud in a vacuum condition for normal-temperature dark storage;
(5) grinding activated red mud by a mortar, tabletting to prepare a granular material, sieving the granules by a 40-60-mesh sieve, namely sieving the granules below the 40-mesh sieve and sieving the granules above the 60-mesh sieve, wherein the grain diameter of the granules is 0.25-0.425mm, and preparing the red mud-based CO2Adding the adsorption and desorption agent particle material into the adsorption device, wherein the gas flow rate of a gas inlet is 400mL/min, and CO2Is 1.2%, low concentration CO2Introducing CO at 2bar from the bottom through a gas pressurizer2Passes through the adsorption material layer and is then treated by red mud-based CO2Adsorbing with adsorbent and desorbent, when adsorption saturation is reached (the concentration of carbon dioxide in the gas inlet and the gas outlet is almost unchanged, namely adsorption saturation), closing the valves of the gas inlet and the gas outlet, raising the temperature in the reactor to 500 ℃, keeping the temperature for 25min, vacuumizing while keeping the temperature, and carrying out CO desorption2Pumping out for storage, reducing pressure in the reactor, and enhancing desorption efficiency to make CO2Adsorbing material from red mudDesorbing in the material; the enriched high-concentration CO is treated2Storing, detecting with gas analyzer, desorbing to obtain CO229.3% by volume;
(6) enriched stored CO2And after being dried by calcium oxide, the mixture is introduced into a cathode pool of an H-shaped reaction device of an electrochemical workstation according to a conventional method, and finally the formic acid is produced by electrocatalysis in the cathode pool.
Example 2
Red mud-based CO2The preparation method and the application of the adsorption and desorption agent comprise the following specific steps:
(1) the method comprises the following steps of collecting Bayer process massive red mud, wherein the red mud comprises the following components in percentage by mass: al (Al)2O3 16～23％，SiO2 9～14％，Fe2O3 23～39％，CaO 13～17％，Na2O 2～7％，TiO21-4 percent of the red mud, and the balance of inevitable impurities, and putting the blocky red mud into an oven, and keeping the temperature for 24 hours at the temperature of 120 ℃ for drying treatment;
(2) putting the dried red mud into a mortar, grinding the red mud into fine particles, and sieving the fine particles with a 60-mesh sieve;
(3) grinding CaO into powder in a mortar, and uniformly mixing the powder with MgO powder and dried and sieved red mud according to the mass ratio of 1.1:1.1:10, namely adding 1.1g of CaO powder and 1.1g of MgO powder into 10g of red mud;
(4) heating the mixed powder to 300 ℃ at a heating rate of 4 ℃/min under the protection of nitrogen, preserving heat for 2.5 hours, heating and activating to obtain activated red mud, and placing the activated red mud in a vacuum condition for normal-temperature dark storage;
(5) grinding activated red mud with mortar, tabletting to obtain granular material, sieving with 40-60 mesh sieve (below 40 mesh sieve and above 60 mesh sieve) to obtain granules with particle diameter of 0.25-0.425mm, and making into red mud-based CO2Adding the adsorption and desorption agent particle material into the adsorption device, wherein the gas flow rate of a gas inlet is 400mL/min, and CO is2Is 1.2% by volume, low concentration of CO2Introducing CO at 2bar from the bottom through a gas pressurizer2Passes through the adsorption material layer and is then treated by red mud-based CO2Adsorbing with adsorbent, and adsorbing to saturation(the adsorption saturation is the condition that the carbon dioxide concentration at the air inlet and the air outlet is almost unchanged), closing the valves at the air inlet and the air outlet, raising the temperature in the reactor to 600 ℃, keeping the temperature for 20min, vacuumizing while keeping the temperature, and carrying out CO (carbon dioxide) adsorption2Pumping out for storage, reducing pressure in the reactor, and enhancing desorption efficiency to make CO2Desorbing from the red mud adsorbing material, and concentrating the enriched high-concentration CO2Storing, detecting with gas analyzer, desorbing to obtain CO2Is 36.6 percent;
(6) enriched stored CO2And after being dried by calcium oxide, the calcium oxide is introduced into a cathode pool of an H-shaped reaction device of an electrochemical workstation according to a conventional method, and finally the formic acid is produced by electrocatalysis in the cathode pool.
Example 3
Red mud-based CO2The preparation method and the application of the adsorption and desorption agent comprise the following specific steps:
(1) collecting Bayer process massive red mud, wherein the red mud comprises the following components in percentage by mass: al (aluminum)2O3 16～23％，SiO2 9～14％，Fe2O3 23～39％，CaO 13～17％，Na2O 2～7％，TiO21-4 percent of the red mud, and the balance of inevitable impurities, and putting the blocky red mud into an oven, and keeping the temperature for 24 hours at 100 ℃ to carry out drying treatment;
(2) putting the dried red mud into a mortar, grinding the red mud into fine particles, and sieving the fine particles with a 60-mesh sieve;
(3) grinding CaO into powder in a mortar, and uniformly mixing the powder with MgO powder and dried and sieved red mud according to the mass ratio of 1.2:1:10, namely adding 1.2g of CaO powder and 1g of MgO powder into 10g of red mud;
(4) heating the uniformly mixed modified red mud to 400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat for 2.5 hours, heating and activating to obtain activated red mud, and placing the activated red mud in a vacuum condition for normal-temperature dark storage;
(5) grinding activated red mud with mortar, tabletting to obtain granular material, sieving with 40-60 mesh sieve (below 40 mesh sieve and above 60 mesh sieve) to obtain granules with particle diameter of 0.25-0.425mm, and making into red mud-based CO2Adding the adsorption and desorption agent particle material into the adsorption device, wherein the gas flow rate of a gas inlet is 400mL/min, and CO2Is 1.2%, low concentration CO2Introducing CO at 2bar from the bottom through a gas pressurizer2Passes through the adsorption material layer and is then treated by red mud-based CO2Adsorbing with an adsorption and desorption agent. When the adsorption saturation is reached (the adsorption saturation is achieved when the carbon dioxide concentration of the gas inlet and the gas outlet is almost unchanged), the valves of the gas inlet and the gas outlet are closed, the temperature in the reactor is raised to 550 ℃, the heat preservation time is 25min, the vacuum pumping is carried out while the heat preservation is carried out, and CO is subjected to2Pumping out for storage, reducing pressure in the reactor, enhancing desorption efficiency, and making CO2And desorbing from the red mud adsorbing material. The enriched high-concentration CO is treated2Storing, detecting with gas analyzer, desorbing to obtain CO245.6% by volume;
(6) enriched stored CO2After passing through a calcium oxide drying zone, introducing the calcium oxide into a cathode pool of an H-shaped reaction device of an electrochemical workstation according to a conventional method, and finally carrying out electrocatalysis on the cathode pool to produce the formic acid.
Example 4
Red mud-based CO2The preparation method and the application of the adsorption and desorption agent comprise the following specific steps:
(1) the method comprises the following steps of collecting Bayer process massive red mud, wherein the red mud comprises the following components in percentage by mass: al (aluminum)2O3 16～23％，SiO2 9～14％，Fe2O3 23～39％，CaO 13～17％，Na2O 2～7％，TiO21-4 percent of the red mud, and the balance of inevitable impurities, and putting the blocky red mud into an oven, and keeping the temperature for 24 hours at the temperature of 110 ℃ to carry out drying treatment;
(2) putting the dried red mud into a mortar, grinding the red mud into fine particles, and sieving the fine particles with a 60-mesh sieve;
(3) grinding CaO into powder in a mortar, and uniformly mixing the powder with MgO powder and dried and sieved red mud according to the mass ratio of 1:1.2:10, namely adding 1g of CaO powder and 1.2g of MgO powder into 10g of red mud;
(4) heating the mixed powder to 500 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat for 2 hours, heating and activating to obtain activated red mud, and placing the activated red mud in a vacuum condition for normal-temperature dark storage;
(5) grinding activated red mud by a mortar, tabletting to prepare a granular material, sieving the granules by a 40-60-mesh sieve, namely sieving the granules below the 40-mesh sieve and sieving the granules above the 60-mesh sieve, wherein the grain diameter of the granules is 0.25-0.425mm, and preparing the red mud-based CO2Adding the adsorption and desorption agent particle material into the adsorption device, wherein the gas flow rate of a gas inlet is 400mL/min, and CO is2Is 1.2%, low concentration CO2Introducing CO from the bottom through a gas pressurizer under the pressure of 2bar2Passes through the adsorption material layer and then is treated by red mud-based CO2Adsorbing with desorption agent, closing the valves of the gas inlet and the gas outlet when the adsorption saturation is reached (the adsorption saturation is obtained when the carbon dioxide concentration of the gas inlet and the gas outlet is almost unchanged), raising the temperature in the reactor to 500 ℃, keeping the temperature for 30min, vacuumizing while keeping the temperature, and carrying out CO desorption2Pumping out for storage, reducing pressure in the reactor, enhancing desorption efficiency, and making CO2Desorbing from the red mud adsorbing material; the enriched high-concentration CO is treated2Storing, detecting with gas analyzer, desorbing to obtain CO2Is 41.2%;
(6) enriched stored CO2And after being dried by calcium oxide, the mixture is introduced into a cathode pool of an H-shaped reaction device of an electrochemical workstation according to a conventional method, and finally the formic acid is produced by electrocatalysis in the cathode pool.
FIG. 1 shows the original form of red mud N2Adsorption-desorption isotherm diagram, FIG. 2 is the activated red mud N of example 22The adsorption-desorption isotherm diagram shows that the specific surface area of the original red mud is calculated to be 11.6592m2·g-1The specific surface area of the powder after activation at 300 ℃ was 19.062m2·g-1The specific surface area is obviously increased after activation, and the red mud can improve CO (carbon monoxide) reaction2The amount of adsorption of (3).
FIG. 3 is an SEM image of the activated red mud of example 2, which shows that the activated red mud has a rough surface and many pore structures for promoting CO2The amount of adsorption of (3).
Table 1 shows the same mass (12g) of the original red mud CThe adsorption and desorption performances of the aO, the MgO and the product in the example 1 are summarized, and the table shows that the total adsorption capacity of the red mud is low, the adsorption saturation time is short, the red mud belongs to industrial solid waste, and the material cost is low; the CaO has large adsorption quantity, but in the concrete implementation process, the flue gas has low moisture content, longer adsorption saturation time and CO2Reacts with CaO surface layer to generate CaCO3Will block CO2The reaction is further carried out towards the interior of the CaO material, the adsorption capacity is greatly reduced, and the reaction is blocked by the mutual agglomeration of the materials; the adsorption amount of MgO is large, but the cost of MgO material is high, and CO is simultaneously2Can only react with the surface layer, and the material utilization rate is low; example 1 the product is red mud-based CO obtained by mixing and activating red mud, CaO and MgO2Absorbing and desorbing agent, CaO powder and MgO powder are dispersed and mixed in the red mud pores and can react with CO2The full contact reaction, and can not agglomerate after the reaction and block up the reactor, simultaneously, adsorb saturation time and compare and also significantly reduce, the powdery carbonate that forms in the material after the reaction is under high temperature, desorption efficiency can greatly increased, has increased on the whole to CO2The ability to enrich.
TABLE 1
| Kind of material | Adsorption saturation time min | Adsorption amount mmol/g | Desorption temperature C | Desorption time period min |
| Red mud | 70-80 | 0.11-0.16 | 500 | 15-20 |
| CaO | 220-240 | 0.73-0.96 | 600 | Can not be completely desorbed |
| MgO | 130-135 | 0.27-0.38 | 450 | 40-45 |
| Example 1 product | 90-100 | 0.37-0.51 | 500 | 20-30 |
Claims (8)
1. Red mud-based CO2The preparation method of the adsorption and desorption agent is characterized by comprising the following specific steps:
(1) drying and grinding the red mud, and then sieving the ground red mud with a 60-mesh sieve;
(2) uniformly mixing the sieved red mud, CaO powder and MgO powder, and heating and activating the mixed powder to obtain activated red mud, wherein the activated red mud is stored at normal temperature in a dark place in vacuum; grinding, tabletting and granulating the activated red mud to obtain the red mud-based CO2And adsorbing and desorbing the agent.
2. The red mud-based CO of claim 12The preparation method of the adsorption and desorption agent is characterized in thatIn the step (1), the red mud comprises the following components in percentage by mass: al (Al)2O3 16～23％，SiO2 9～14％，Fe2O3 23～39％，CaO 13～17％，Na2O 2～7％，TiO21-4%, and the other part is impurities.
3. The red mud-based CO according to claim 12The preparation method of the adsorption and desorption agent is characterized in that the drying treatment in the step (1) is heat preservation for 24 hours under the condition of 100-120 ℃.
4. The red mud-based CO according to claim 12The preparation method of the adsorption and desorption agent is characterized in that the mass ratio of the red mud, CaO powder and MgO powder dried in the step (2) is 10: 1-1.2.
5. The red mud-based CO according to claim 12The preparation method of the adsorption and desorption agent is characterized in that the heating activation in the step (2) is to heat up to 200-500 ℃ at the heating rate of 3-5 ℃/min under the protection of nitrogen and keep the temperature for 2-3 h.
6. The red mud-based CO of claim 12The preparation method of the adsorption and desorption agent is characterized in that the particle size of the particles after tabletting and granulating in the step (2) is 0.25-0.425 mm.
7. The red mud-based CO of claim 12The application of the adsorption and desorption agent is characterized in that red mud-based CO is used2Adsorbing CO by filling the particles of adsorbent and desorbent2In the reactor, the carbon dioxide gas after desulfurization and dust removal is pressurized and introduced into an adsorption reactor, and after the adsorption is saturated, the temperature is raised for desorption, and the high-concentration CO is enriched2。
8. The red mud-based CO of claim 12The application of the adsorption-desorption agent is characterized in that the temperature rise desorption is carried out at 500-600 ℃ for 20-30 min.
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|---|---|---|---|---|
| CN104971690A (en) * | 2015-06-15 | 2015-10-14 | 昆明理工大学 | Method for preparing high-temperature CO2 calcium-based adsorbent from papermaking white mud |
| 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 |
| CN110655342A (en) * | 2019-09-03 | 2020-01-07 | 浙江大学 | Modified red mud capable of absorbing, curing and sealing carbon dioxide and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971690A (en) * | 2015-06-15 | 2015-10-14 | 昆明理工大学 | Method for preparing high-temperature CO2 calcium-based adsorbent from papermaking white mud |
| 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 |
| CN110655342A (en) * | 2019-09-03 | 2020-01-07 | 浙江大学 | Modified red mud capable of absorbing, curing and sealing carbon dioxide and preparation method thereof |
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| ZHU, XF，ET AL.: "Calcification-Carbonation Method for Bayer Red Mud Treatment: Carbonation Performance of Hydrogarnets", 《BULLETIN OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY》, pages 68 - 75 * |
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