CN102500310A - High-temperature high-activity calcium-based CO2 adsorbent and preparation method thereof - Google Patents
High-temperature high-activity calcium-based CO2 adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature high-activity calcium-based CO2 adsorbent and a preparation method of the high-temperature high-activity calcium-based CO2 adsorbent. The high-temperature high-activity calcium-based CO2 adsorbent is prepared from calcium citrate, distilled water, dispersant, alcohols, and aluminum salt. The preparation method comprises the following steps: preparing Al(OH)3 by sol-gel method at 55 to 75 DEG C; wrapping calcium citrate particles with Al(OH)3; aging the obtained suspension at room temperature for 8 to 10 hours; suction-filtering and cleaning to remove impurity ions; drying the obtained solid matter at 100 to 120 DEG C for 10 to 12 hours; and calcining at 800 to 950 DEG C for 1 to 2.5 hours. The adsorbent prepared in the invention has high CO2 adsorption activity and high stability at high temperature, and can keep high activity and stability after recycling for multiple times, so that the high-temperature high-activity calcium-based CO2 adsorbent is expected to realize good application prospect in hydrogen making process from methane reformation by adsorbing enhanced methane steam.
Description
Technical field
The present invention relates to a kind of high temperature high active calcium-base CO
2The preparation of adsorbent method, the high temperature calcium base CO that relates in particular to a kind of high activity and high stability and after many circulations, have greater activity
2Adsorbent.
Background technology
High temperature CO commonly used
2Adsorbent has hydrotalcite, dolomite and calcium oxide etc.High temperature calcium base CO wherein
2Adsorbent shows the good adsorption effect, and cheap, the wide material sources of cost of material can be put on display better adsorption effect through it is carried out suitably modification more simultaneously.In petrochemical industry and hydrogen energy source field, high temperature calcium base CO
2Adsorbent can be used for reaction and removes CO
2Adsorption forced methane vapour reforming hydrogen producing new technology process.Its reaction mechanism is in course of reaction, with the CO of Ca-base adsorbent original position absorption reaction generation
2Thereby, break thermodynamics equilibrium limit, reforming reaction is carried out to the product direction.Not only improve methane conversion, and improved the concentration of hydrogen, reduced the cost of after-stage raising density of hydrogen.Because active decline phenomenon appears in general Ca-base adsorbent usually after experience reaction-regeneration cycle repeatedly, therefore seriously hindered adsorption forced methane vapour reforming hydrogen producing The Application of Technology.
In addition, high temperature calcium base CO
2Adsorbent has important application prospects in fields such as energy utilization and conversion, environmental protection and energy-saving and emission-reduction.Utilize calcium oxide and CO
2Exothermic heat of reaction and the branch heat of desorption of calcium carbonate, the chemical heat pump that can be used for energy field is realized the function of thermal energy storage and transformation, it also can be applied to remove contained CO in the flue gas of fossil fuel power generation process generation simultaneously
2
Though Ca-base adsorbent has absorption CO
2Advantages such as ability is strong, with low cost, preparation and production technology are simple and green non-poisonous, but in production application, because device space operation can not be put into a large amount of adsorbents and frequent replacing adsorbent with the restriction of production technology.Thereby, to calcium base CO
2The stability and the reactivity of adsorbent are had higher requirement, through Ca-base adsorbent is suitably modified, to improve repeatedly the active and stable of circulation back adsorbent.
The purpose of this invention is to provide a kind of high temperature calcium base CO with higher adsorption activity and stability
2Adsorbent and preparation method thereof is to overcome the above-mentioned defective that prior art exists.
A kind of high temperature high active calcium-base CO
2Adsorbent is characterized in that: said adsorbent main component is CaO and Ca
9Al
6O
18, mass ratio is 70: 30～80: 20.
A kind of high temperature high activity CO
2The preparation of adsorbent method through the sol-gel process method, is a raw material with calcium citrate, distilled water, dispersant, alcohols, aluminium salt, comprises being prepared as follows step:
(1) take by weighing a certain amount of calcium citrate, be mixed with 15～30% (mass percent) suspension, add an amount of dispersant simultaneously, wherein dispersant is a kind of of calgon and citric acid;
(2) in the suspension that step (1) is prepared, add alcohols and aluminium salt by a certain percentage, stirred 1.5～2.5 hours down in steady temperature (55～75 ℃);
Wherein: alcohols is a kind of of methyl alcohol, ethanol and isopropyl alcohol;
Aluminium salt is a kind of of aluminum nitrate, basic aluminium acetate and aluminium chloride;
(3) step (2) gained solution was at room temperature worn out 8～10 hours, remove foreign ion through the filtering and washing method again;
(4) step (3) gained decorating film was carried out drying 10～12 hours under 100～120 ℃;
(5) step (4) gained sample was calcined 1～2.5 hour down at 800～950 ℃;
(6) step (5) gained sample is ground, be made high temperature high active calcium-base CO
2Adsorbent.
The high temperature high active calcium-base CO of the inventive method preparation
2Adsorbent not only has higher CO
2Adsorption activity, and have higher high-temperature stability, and through repeatedly still having higher CO after carbonating-calcination cycle
2Adsorption activity is expected to be applied to adsorption forced methane vapour reforming hydrogen producing technology.
Description of drawings
Fig. 1 is the SEM figure of the adsorbent of the embodiment of the invention 1.
Fig. 2 for adsorbent among embodiment of the invention 1-4 and the comparative example 1-2 through the result that recycles for 7 times relatively.
Fig. 3 for adsorbent among the embodiment of the invention 1 and the comparative example 1 through the result that recycles for 25 times relatively.
The specific embodiment
The specific embodiment of the invention is described in down, but the invention is not restricted to this.
Under the room temperature, place 56 ml distilled waters to be mixed with the aaerosol solution of 15% (mass percent) 10.01 gram calcium citrates, add calgon 0.001 grams per milliliter.Above-mentioned suspension is added in 75 ℃ of water-bath circulation cups, slowly add 20 milliliters of ethanolic solutions and 1.81 gram aluminum nitrates, add 44 ml distilled waters simultaneously, stirred at room temperature aging 10 hours then 2 hours.Behind aging the end, filtering and washing, following dry 10 hours in 100 ℃ then.At last drying sample is put in the Muffle furnace 850 ℃ of calcinings 1.5 hours.The grinding of sample after the calcining is made adsorbent.
Performance test: on thermogravimetric analyzer, prepared adsorbent is carried out carbonating-calcination cycle experiment, the adsorption capacity of 7 cyclic processes of record.
The method of performance test:
The present invention adopts the adsorption capacity of thermogravimetric analyzer test carbonating-each circulation of calcining.During experiment, a certain amount of adsorbent (about 10 milligrams) is placed thermogravimetric analyzer, in whole test process, keep total gas flow rate constant.The carbonation reaction condition is: CO
2Dividing potential drop 0.20 atmospheric pressure, 600 ℃ of temperature, 30 minutes time, diluent gas is N
2Calcination condition is: pure N
2Atmosphere (stops to feed CO
2), 850 ℃ of temperature, 30 minutes time.According to the adsorbent mass delta data that writes down in the experimentation, calculate the adsorption capacity of adsorbent, it defines as follows:
Under the room temperature, place 24 ml distilled waters to be mixed with the aaerosol solution of 30% (mass percent) 10.02 gram calcium citrates, add calgon 0.001 grams per milliliter.Above-mentioned suspension is added in 55 ℃ of water-bath circulation cups, slowly add 5 milliliters of ethanolic solutions and 2.77 gram aluminum nitrates, add 76 ml distilled waters simultaneously, stirred at room temperature aging 8 hours then 2.5 hours.Behind aging the end, filtering and washing, following dry 12 hours in 120 ℃ then.At last drying sample is put in the Muffle furnace 850 ℃ of calcinings 1 hour.The grinding of sample after the calcining is made adsorbent.
Performance test: on thermogravimetric analyzer, prepared adsorbent is carried out carbonating-calcination cycle experiment, the adsorption capacity of 7 cyclic processes of record.
Under the room temperature, place 56 ml distilled waters to be mixed with the aaerosol solution of 15% (mass percent) 10.02 gram calcium citrates, add citric acid 0.001 grams per milliliter.Above-mentioned suspension is added in 70 ℃ of water-bath circulation cups, slowly add 10 milliliters of ethanolic solutions and 0.96 gram aluminum nitrate, add 44 ml distilled waters simultaneously, stirred at room temperature aging 10 hours then 1.5 hours.Behind aging the end, filtering and washing, following dry 10 hours in 100 ℃ then.At last drying sample is put in the Muffle furnace 800 ℃ of calcinings 2.5 hours.The grinding of sample after the calcining is made adsorbent.
Performance test: on thermogravimetric analyzer, prepared adsorbent is carried out carbonating-calcination cycle experiment, the adsorption capacity of 7 cyclic processes of record.
Under the room temperature, place 56 ml distilled waters to be mixed with the aaerosol solution of 15% (mass percent) 10.01 gram calcium citrates, add citric acid 0.001 grams per milliliter.Above-mentioned suspension is added in 75 ℃ of water-bath circulation cups, slowly add 15 milliliters of aqueous isopropanols and 1.17 gram aluminium chloride, add 44 ml distilled waters simultaneously, stirred at room temperature aging 9 hours then 2 hours.Behind aging the end, filtering and washing, following dry 11 hours in 110 ℃ then.At last drying sample is put in the Muffle furnace 950 ℃ of calcinings 1.5 hours.The grinding of sample after the calcining is made adsorbent.
Performance test: on thermogravimetric analyzer, prepared adsorbent is carried out carbonating-calcination cycle experiment, the adsorption capacity of 7 cyclic processes of record.
The comparative example 1
Under the room temperature, place 56 ml distilled waters to be mixed with the aaerosol solution of 15% (mass percent) 10.20 gram calcium gluconaes, add calgon 0.001 grams per milliliter.Above-mentioned suspension is added in 70 ℃ of water-bath circulation cups, slowly add 5 milliliters of ethanolic solutions and 0.77 gram aluminum nitrate, add 44 ml distilled waters simultaneously, stirred at room temperature aging 8 hours then 2 hours.The aging back evaporate to dryness that finishes, then in 100 ℃ dry 12 hours down.At last drying sample is put in the Muffle furnace 850 ℃ of calcinings 1.5 hours.The grinding of sample after the calcining is made adsorbent.
Performance test: on thermogravimetric analyzer, prepared adsorbent is carried out carbonating-calcination cycle experiment, the adsorption capacity of 7 cyclic processes of record.
The comparative example 2
Under the room temperature, place 56 ml distilled waters to be mixed with the aaerosol solution of 15% (mass percent) in 10.02 gram calcium carbonate, add calgon 0.001 grams per milliliter.Above-mentioned suspension is added in 75 ℃ of water-bath circulation cups, slowly add 20 milliliters of ethanolic solutions and 3.37 gram aluminum nitrates, add 44 ml distilled waters simultaneously, stirred at room temperature aging 10 hours then 2 hours.Behind aging the end, filtering and washing, following dry 10 hours in 110 ℃ then.At last drying sample is put in the Muffle furnace 900 ℃ of calcinings 1.5 hours.The grinding of sample after the calcining is made adsorbent.
Performance test: on thermogravimetric analyzer, prepared adsorbent is carried out carbonating-calcination cycle experiment, the adsorption capacity of 7 cyclic processes of record.
Claims (6)
1. high temperature high active calcium-base CO
2Adsorbent is characterized in that: the composition of said adsorbent is CaO and Ca
9Al
6O
18, its mass ratio is 70: 30～80: 20.
2. high temperature high active calcium-base CO
2The preparation of adsorbent method is characterized in that: said method is a sol-gel process, is raw material with calcium citrate, distilled water, dispersant, alcohols, aluminium salt, comprises being prepared as follows step:
(1) takes by weighing a certain amount of calcium citrate, be mixed with 15～30% (mass percent) suspension, add an amount of dispersant simultaneously;
(2) under 55～75 ℃, in the suspension that step (1) is prepared, add alcohols and aluminium salt by a certain percentage, under steady temperature, stirred 1.5～2.5 hours;
(3) step (2) gained solution was at room temperature worn out 8～10 hours, remove foreign ion through the filtering and washing method again;
(4) step (3) gained decorating film was carried out drying 10～12 hours under 100～120 ℃;
(5) step (4) gained sample was calcined 1～2.5 hour down at 800～950 ℃;
(6) step (5) gained sample is ground, obtain high temperature high active calcium-base CO
2Adsorbent.
3. method according to claim 2 is characterized in that, said dispersant is a kind of of calgon and citric acid.
4. method according to claim 2 is characterized in that, said alcohols is a kind of of methyl alcohol, ethanol and isopropyl alcohol.
5. method according to claim 2 is characterized in that, said aluminium salt is a kind of of aluminum nitrate, basic aluminium acetate and aluminium chloride.
6. method according to claim 2 is characterized in that, the volume ratio of said alcohols and distilled water is 1: 5～1: 20.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784630A (en) * | 2012-07-25 | 2012-11-21 | 华中科技大学 | Preparation method for calcium-based CO2 sorbent |
| CN103657582A (en) * | 2012-09-13 | 2014-03-26 | 华东理工大学 | Improved calcium-oxide-based CO2 adsorbent and preparation method thereof |
| CN105214597A (en) * | 2015-09-21 | 2016-01-06 | 广东电网有限责任公司电力科学研究院 | Middle temperature carbon-dioxide absorbent and forming method thereof |
| US20210339225A1 (en) * | 2018-10-15 | 2021-11-04 | University Court Of The University Of St Andrews | Mixed oxide composite comprising calcium oxide and tricalcium aluminate |
| CN113856617A (en) * | 2021-10-08 | 2021-12-31 | 山西大学 | Preparation method of calcium-based carbon dioxide adsorbent |
| CN114797753A (en) * | 2022-04-29 | 2022-07-29 | 武汉理工大学 | Alumina-based trapping material for efficiently adsorbing carbon dioxide and preparation method and application thereof |
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| CN1762572A (en) * | 2005-09-23 | 2006-04-26 | 浙江大学 | High temperature carbon dioxide adsorbent containing silicon nano calcium oxide, its preparation process and application in hydrogen production process |
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2011
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| CN1762572A (en) * | 2005-09-23 | 2006-04-26 | 浙江大学 | High temperature carbon dioxide adsorbent containing silicon nano calcium oxide, its preparation process and application in hydrogen production process |
| US20110189067A1 (en) * | 2010-02-02 | 2011-08-04 | Retallick William B | Sorbent for carbon dioxide |
Non-Patent Citations (2)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784630A (en) * | 2012-07-25 | 2012-11-21 | 华中科技大学 | Preparation method for calcium-based CO2 sorbent |
| CN103657582A (en) * | 2012-09-13 | 2014-03-26 | 华东理工大学 | Improved calcium-oxide-based CO2 adsorbent and preparation method thereof |
| CN105214597A (en) * | 2015-09-21 | 2016-01-06 | 广东电网有限责任公司电力科学研究院 | Middle temperature carbon-dioxide absorbent and forming method thereof |
| US20210339225A1 (en) * | 2018-10-15 | 2021-11-04 | University Court Of The University Of St Andrews | Mixed oxide composite comprising calcium oxide and tricalcium aluminate |
| CN113856617A (en) * | 2021-10-08 | 2021-12-31 | 山西大学 | Preparation method of calcium-based carbon dioxide adsorbent |
| CN114797753A (en) * | 2022-04-29 | 2022-07-29 | 武汉理工大学 | Alumina-based trapping material for efficiently adsorbing carbon dioxide and preparation method and application thereof |
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Application publication date: 20120620 |