CN103611490B - A kind of carbon dioxide absorber and preparation method - Google Patents

A kind of carbon dioxide absorber and preparation method Download PDF

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CN103611490B
CN103611490B CN201310660976.7A CN201310660976A CN103611490B CN 103611490 B CN103611490 B CN 103611490B CN 201310660976 A CN201310660976 A CN 201310660976A CN 103611490 B CN103611490 B CN 103611490B
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carbon dioxide
tio
butyl titanate
lithium
sodium
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CN103611490A (en
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刘峙嵘
张寰
占鑫星
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East China Institute of Technology
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/151Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention discloses a kind of carbon dioxide absorber and preparation method, adopt metatitanic acid lithium, chemical formula Li 2tiO 3, or mix sodium metatitanic acid lithium, chemical formula Li 2 (1-x)na 2xtiO 3for under 500 DEG C of-700 DEG C of high temperature to the adsorbent that carbon dioxide adsorbs.Metatitanic acid lithium, using butyl titanate, lithium acetate, absolute ethyl alcohol, glacial acetic acid and water as raw material, adopts hydrolysis of alkoxide sol-gal process to synthesize; Sodium product Li is mixed in preparation 2 (1-x)na 2xtiO 3time add sodium acetate.When temperature is higher than 500 DEG C, adsorbent starts to react with carbon dioxide, and absorption starts to carry out, and when temperature is higher than 700 DEG C, reaction starts counter movement, discharges carbon dioxide, adsorbent reactivation.Adsorb the carbon dioxide in high-temperature flue gas, simple process, product is easily separated, and material easily regenerates, and can recycle.Preparation method's system chemical uniformity of the present invention is stronger; Course of reaction is easy to control; Calcining forming temperature is low, low for equipment requirements; Be easy to modification; Component is even, and purity is high.

Description

A kind of carbon dioxide absorber and preparation method
Technical field
The invention belongs to field of material technology, relate to a kind of Novel carbon dioxide adsorbent and preparation method, particularly relate to a kind of metatitanic acid lithium or natrium doping metatitanic acid lithium of adopting as the new technology of Novel carbon dioxide adsorbent.
Background technology
One of current most important environmental problem discharges by great amount of carbon dioxide the greenhouse effects caused exactly, for the CO2 emission of coal-burning power plant, mainly through firing rear Trapping ways process, it is the conventional means trapped after combustion that solution absorbs, namely by using solvent (organic amine or cold ammonia) to be separated from flue gas by carbon dioxide, the carbon dioxide up to 90% flue gas that can produce from burning, is separated.Although the method absorptive capacity is large, is swift in response, inevitably faces poor heat stability, separation difficulty, corrosive equipment, toxic and volatile, easily cause secondary pollution problems.And use solid adsorption material to carry out adsorption treatment to carbon dioxide, just can overcome the shortcoming of solvent absorption to a certain extent.
Metatitanic acid lithium is as a kind of compound and be of little use, even seldom use, Li 2tiO 3there are three kinds of crystal structures: α-Li 2tiO 3, β-Li 2tiO 3, γ-Li 2tiO 3.α-Li 2tiO 3a kind of metastable state form, when temperature can change β-Li into higher than when 300 DEG C 2tiO 3.β-Li 2tiO 3belong to monoclinic system, the γ-Li of cubic system can be changed into more than 1200 DEG C 2tiO 3, that research is more at present is monoclinic system Li 2tiO 3.β-Li 2tiO 3the related data of character can see the following form 1, data from the article published.
Table 1 β-Li 2tiO 3character sum up
In addition, also for metatitanic acid lithium Li 2tiO 3radiation effect also have a lot of researcher to do a few thing, in HCSB(solid multiplication/He type of cooling) under pattern at 900K time residual He almost can ignore, tritium is residual with release behavior and Li 2zrO 3similar.
At present about Li 2tiO 3the prior art of the preparation method of powder is more limited, and more preparation method is about lithium titanate (Li 4ti 5o 12), because it can have a wide range of applications particularly in lithium battery as battery electrode.Such as: utilize TiO 2with a kind of compound containing elemental lithium as Li 2cO 3, LiOH, LiNO 3, Li 2o etc. are mixed sintering in specific proportions; Maybe will containing lithium source (as LiCl solution) or titanium source (TiOCl 2) mixture heating evaporation after calcine.Preparation Li 2tiO 3method can use for reference from above method.Because inherently lithium titanate (Li 4ti 5o 12) and Li 2tiO 3two kinds of compounds are Li 2o and TiO 2proportioning value different.
The application in the prior art of metatitanic acid lithium is also very limited, and reported have skewness acid lithium as presoma, prepares metatitanic acid type Lithium, for the Li in adsorption aqueous solution +ion, this adsorbent is to Li +ion selectivity is high, can preferably by Li +ion is separated with otheralkali metal or alkaline-earth metal ions, is expected to for salt lake bittern or Extracting Lithium from Seawater.
From the prior art, not yet find that metatitanic acid lithium is as solid adsorption material absorbing carbon dioxide, particularly as the carbon dioxide of solid adsorption material absorption coal-burning power plant's discharge.
Summary of the invention
Directly adsorb carbon dioxide in high-temperature flue gas for reaching, reduce the object because of the energy consumption caused of lowering the temperature, the object of the invention is to provide a kind of pressed powder carbon dioxide absorber metatitanic acid lithium (Li 2tiO 3) mix sodium metatitanic acid lithium (Li with its doping vario-property product 2 (1-x)na 2xtiO 3), can adsorb selectively carbon dioxide in higher temperature range, and adsorbent energy regeneration cycle uses.Meanwhile, metatitanic acid lithium (Li is provided 2tiO 3) mix sodium metatitanic acid lithium (Li with its doping vario-property product 2 (1-x)na 2xtiO 3) preparation method.
One of technical solution of the present invention:
A kind of Novel carbon dioxide adsorbent, adopts metatitanic acid lithium, chemical formula Li 2tiO 3, at high temperature to the adsorbent that carbon dioxide adsorbs.
A kind of Novel carbon dioxide adsorbent, employing metatitanic acid lithium doping modified product-mix sodium metatitanic acid lithium, chemical formula Li 2 (1-x)na 2xtiO 3(wherein x represents the molar fraction that sodium accounts for lithium sodium total amount), at high temperature to the adsorbent that carbon dioxide adsorbs.
Above-mentioned Novel carbon dioxide adsorbent, described high temperature is 500 DEG C-700 DEG C, when temperature is higher than 500 DEG C, adsorbent starts to react with carbon dioxide, and absorption starts to carry out, when temperature is higher than 700 DEG C, reaction starts counter movement, discharges carbon dioxide, adsorbent reactivation.
Metatitanic acid lithium and doping vario-property product thereof at high temperature can occur to react as follows with carbon dioxide:
Li 2 TiO 3 + CO 2 ? Li 2 CO 3 + TiO 2
Li 2(1-x) Na 2x TiO 3 + CO 2 ? (1-x)Li 2 CO 3 + xNa 2 CO 3 + TiO 2
(wherein x represents the molar fraction that sodium accounts for lithium sodium total amount)
Thus reach the effect of absorbing carbon dioxide, use the method easy to the carbon dioxide process in high-temperature flue gas, product is easily separated, and material easily regenerates, and can recycle.
Technical solution of the present invention two:
A preparation technology for metatitanic acid lithium, using butyl titanate, lithium acetate, absolute ethyl alcohol, glacial acetic acid and water as raw material, adopts hydrolysis of alkoxide sol-gal process to synthesize.
Described sol-gal process prepares metatitanic acid lithium, chemical formula Li 2tiO 3process in each pulp furnish:
Mol ratio=the 2:1 of lithium acetate and butyl titanate;
Volume ratio=4:1-the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=20:1-the 30:1 of water and butyl titanate;
Mol ratio=4:1-the 7:1 of acetic acid and butyl titanate;
By described each raw material dosage, first by butyl titanate and 3 times of mixing of the absolute ethyl alcohol to butyl titanate volume, stir and be mixed with mixed liquor A, then lithium acetate, remaining absolute ethyl alcohol, glacial acetic acid and water are mixed, stirring is mixed with mixed liquid B, then is mixed by AB two mixed liquor; Be stirred to System forming homogeneous transparent colloidal sol, at room temperature 20-30 DEG C, ageing 6-10 days, obtain wet gel, under the condition of 80-100 DEG C, wet gel is dried and becomes cullet shape xerogel, subsequently this xerogel is incubated roasting in 8-10 hours at 600 ± 10 DEG C, can Li be obtained 2tiO 3product.
Mix a preparation technology for sodium metatitanic acid lithium, using butyl titanate, lithium acetate, sodium acetate, absolute ethyl alcohol, glacial acetic acid and water as raw material, adopt hydrolysis of alkoxide sol-gal process to synthesize.
Sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=49:1-the 24:1 of lithium acetate and sodium acetate;
Volume ratio=4:1-the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=20:1-the 40:1 of water and butyl titanate;
Mol ratio=4:1-the 7:1 of acetic acid and butyl titanate;
By described each raw material dosage, first by butyl titanate and 3 times of mixing of the absolute ethyl alcohol to butyl titanate volume, stir and be mixed with mixed liquor A, then lithium acetate, sodium acetate, remaining absolute ethyl alcohol, glacial acetic acid and water are mixed, stirring is mixed with mixed liquid B, then is mixed by AB two mixed liquor; Be stirred to System forming homogeneous transparent colloidal sol, at room temperature 20-30 DEG C, ageing 6-10 days, obtain wet gel, under the condition of 80-100 DEG C, wet gel is dried and becomes cullet shape xerogel, subsequently this xerogel is incubated roasting in 8-10 hours at 600 ± 10 DEG C, can Li be obtained 2 (1-x)na 2xtiO 3product.
The present invention adopt sol-gal process prepare metatitanic acid lithium and mix sodium metatitanic acid lithium process aspect comparatively additive method have following advantage: system chemical uniformity is stronger; Course of reaction more easily controls; Calcining forming temperature is low, low for equipment requirements; Stoichiometry is accurate, is easy to modification; Product component is even, and pattern is intact, and purity is high; Be easier to materials processing shaping.
Accompanying drawing explanation
Fig. 1 embodiment of the present invention process chart.
Detailed description of the invention
The present invention is further described by the following examples, but scope of the present invention is not limited to following embodiment.Technical solution of the present invention is also not limited to following cited detailed description of the invention, also comprises any combination between detailed description of the invention.
According to flow process shown in Fig. 1, preparation Li 2tiO 3time do not add sodium acetate, preparation mix sodium product Li 2 (1-x)na 2xtiO 3time add sodium acetate.Preparation Li 2tiO 3time each raw material dosage need meet following ratio (" n " represents amount of substance; " V " represents volume): n (lithium acetate): n (butyl titanate)=2:1; V (absolute ethyl alcohol): V (butyl titanate)=4:1-6:1; N (water): n (butyl titanate)=20:1-40:1; N (acetic acid): n (butyl titanate)=4:1-7:1.Sodium product Li is mixed in preparation 2 (1-x)na 2xtiO 3,time (wherein x represents the molar fraction that sodium accounts for lithium sodium total amount), each raw material dosage need meet following ratio: [n (lithium acetate)+n (sodium acetate)]: n (butyl titanate)=2:1; N (lithium acetate): n (sodium acetate)=49:1-24:1; V (absolute ethyl alcohol): V (butyl titanate)=4:1-6:1; N (water): n (butyl titanate)=20:1-40:1; N (acetic acid): n (butyl titanate)=4:1-7:1.All the other both processes are identical, first by butyl titanate and 3 times of mixing of the absolute ethyl alcohol to butyl titanate volume during mixing, stir and are mixed with mixed liquor A; Again other is mixed, stir and be mixed with mixed liquid B, then AB two mixed liquor is mixed; Mix to System forming homogeneous transparent colloidal sol, ageing 6-10 days under room temperature (20-30 DEG C), obtain wet gel, under the condition of 80-100 DEG C, wet gel is dried and becomes cullet shape xerogel, subsequently this xerogel is incubated roasting in 8-10 hours at about 600 DEG C, can Li be obtained 2tiO 3or Li 2 (1-x)na 2xtiO 3product.
Embodiment 1: described sol-gal process prepares metatitanic acid lithium, chemical formula Li 2tiO 3process in each pulp furnish:
Mol ratio=the 2:1 of lithium acetate and butyl titanate;
Volume ratio=the 4:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 20:1 of water and butyl titanate;
Mol ratio=the 4:1 of acetic acid and butyl titanate.
Embodiment 2: described sol-gal process prepares metatitanic acid lithium, chemical formula Li 2tiO 3process in each pulp furnish:
Mol ratio=the 2:1 of lithium acetate and butyl titanate;
Volume ratio=the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 30:1 of water and butyl titanate;
Mol ratio=the 7:1 of acetic acid and butyl titanate.
Embodiment 3: described sol-gal process prepares metatitanic acid lithium, chemical formula Li 2tiO 3process in each pulp furnish:
Mol ratio=the 2:1 of lithium acetate and butyl titanate;
Volume ratio=the 5:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 25:1 of water and butyl titanate;
Mol ratio=the 5.5:1 of acetic acid and butyl titanate.
Embodiment 4: described sol-gal process prepares metatitanic acid lithium, chemical formula Li 2tiO 3process in each pulp furnish:
Mol ratio=the 2:1 of lithium acetate and butyl titanate;
Volume ratio=the 4:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 30:1 of water and butyl titanate;
Mol ratio=the 4:1 of acetic acid and butyl titanate.
Embodiment 5: described sol-gal process prepares metatitanic acid lithium, chemical formula Li 2tiO 3process in each pulp furnish:
Mol ratio=the 2:1 of lithium acetate and butyl titanate;
Volume ratio=the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 20:1 of water and butyl titanate;
Mol ratio=the 7:1 of acetic acid and butyl titanate.
Embodiment 6: sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=the 49:1 of lithium acetate and sodium acetate;
Volume ratio=the 4:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 20:1 of water and butyl titanate;
Mol ratio=the 4:1 of acetic acid and butyl titanate.
Embodiment 7: sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=the 24:1 of lithium acetate and sodium acetate;
Volume ratio=the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 40:1 of water and butyl titanate;
Mol ratio=the 7:1 of acetic acid and butyl titanate.
Embodiment 8: sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=the 37:1 of lithium acetate and sodium acetate;
Volume ratio=the 5:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 30:1 of water and butyl titanate;
Mol ratio=the 5.5:1 of acetic acid and butyl titanate.
Embodiment 9: sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=the 49:1 of lithium acetate and sodium acetate;
Volume ratio=the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 20:1 of water and butyl titanate;
Mol ratio=the 7:1 of acetic acid and butyl titanate.
Embodiment 10: sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=the 24:1 of lithium acetate and sodium acetate;
Volume ratio=the 4:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=the 40:1 of water and butyl titanate;
Mol ratio=the 4:1 of acetic acid and butyl titanate.
During absorbing carbon dioxide gas, make Li 2tiO 3or Li 2 (1-x)na 2xtiO 3powder is exposed to pure carbon dioxide gas or containing in the gaseous mixture of carbon dioxide, when temperature is higher than 500 DEG C, adsorbent starts to react with carbon dioxide, absorption starts to carry out, and when temperature is higher than 700 DEG C, reaction starts counter movement, discharge carbon dioxide, adsorbent reactivation.This adsorption and desorption experiment carries out in Thermal Synthetic Analysis instrument, and adsorption process, under the atmosphere of pure carbon dioxide or carbon dioxide and nitrogen mixture, investigates Li by example weight variation with temperature 2tiO 3or Li 2 (1-x)na 2xtiO 3to the absorption property of carbon dioxide.Under comparatively suitable condition, Li 2tiO 3sample is maximum weightening finish about 25.3% under pure carbon dioxide atmosphere, calculates, if Li according to chemical equation 2tiO 3with carbon dioxide complete reaction, sample weightening finish about 40.0%, visible Li 2tiO 3better to the absorption property of carbon dioxide.Under comparatively suitable condition, Li 2 (1-x)na 2xtiO 3sample is maximum weightening finish about 30.1% under pure carbon dioxide atmosphere, and the doping vario-property received, enhances Li 2tiO 3to the absorption property of carbon dioxide.Desorption process, under air atmosphere environment, investigates the Li of absorbing carbon dioxide by example weight variation with temperature 2tiO 3or Li 2 (1-x)na 2xtiO 3desorb (regeneration) behavior.Under comparatively suitable condition, Li 2tiO 3sample final mass is about 103.5% of initial incremental amount, namely about has the carbon dioxide being equivalent to sample quality 21.8% to there occurs desorb.Under comparatively suitable condition, Li 2 (1-x)na 2xtiO 3sample final mass is about 102.9% of initial incremental amount, namely about has the carbon dioxide being equivalent to sample quality 27.2% to there occurs desorb.By above experimental data, metatitanic acid lithium (Li is described 2tiO 3) and mix sodium metatitanic acid lithium (Li 2 (1-x)na 2xtiO 3) adsorption-desorption process can be there is under certain condition with carbon dioxide.
Metatitanic acid lithium (Li prepared by described pulp furnish and process conditions 2tiO 3) and metatitanic acid lithium (Li 2 (1-x)na 2xtiO 3) material, its purposes be preserve, fix, the carbon dioxide be separated in pure carbon dioxide gas or Multiple components gaseous mixture.

Claims (3)

1. a carbon dioxide absorber, is characterized in that, employing metatitanic acid lithium doping modified product-mix sodium metatitanic acid lithium, chemical formula Li 2 (1-x)na 2xtiO 3, wherein x represents the molar fraction that sodium accounts for lithium sodium total amount, at high temperature to the adsorbent that carbon dioxide adsorbs; Described high temperature is 500 DEG C-700 DEG C, and when temperature is higher than 500 DEG C, adsorbent starts to react with carbon dioxide, and absorption starts to carry out, and when temperature is higher than 700 DEG C, reaction starts counter movement, discharges carbon dioxide, adsorbent reactivation.
2. the preparation method of a kind of carbon dioxide absorber as claimed in claim 1, is characterized in that, using butyl titanate, lithium acetate, sodium acetate, absolute ethyl alcohol, glacial acetic acid and water as raw material, adopts hydrolysis of alkoxide sol-gal process to synthesize.
3. preparation method as claimed in claim 2, is characterized in that, sodium metatitanic acid lithium, chemical formula Li are mixed in described sol-gal process preparation 2 (1-x)na 2xtiO 3process in each pulp furnish:
Mol ratio=the 1:2 of lithium acetate and sodium acetate sum and butyl titanate;
Mol ratio=49:1-the 24:1 of lithium acetate and sodium acetate;
Volume ratio=4:1-the 6:1 of absolute ethyl alcohol and butyl titanate;
Mol ratio=20:1-the 40:1 of water and butyl titanate;
Mol ratio=4:1-the 7:1 of acetic acid and butyl titanate;
By described each raw material dosage, first by butyl titanate and 3 times of mixing of the absolute ethyl alcohol to butyl titanate volume, stir and be mixed with mixed liquor A, then lithium acetate, sodium acetate, remaining absolute ethyl alcohol, glacial acetic acid and water are mixed, stirring is mixed with mixed liquid B, then is mixed by AB two mixed liquor; Be stirred to System forming homogeneous transparent colloidal sol, at room temperature 20-30 DEG C, ageing 6-10 days, obtain wet gel, under the condition of 80-100 DEG C, wet gel is dried and becomes cullet shape xerogel, subsequently this xerogel is incubated roasting in 8-10 hours at 600 ± 10 DEG C, can Li be obtained 2 (1-x)na 2xtiO 3product, wherein x represents the molar fraction that sodium accounts for lithium sodium total amount.
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CN112023870A (en) * 2020-07-10 2020-12-04 重庆大学 High-temperature CO for reinforcing reforming methane reaction2Method for preparing adsorbent
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