CN109954476A - A kind of bivalve layer calcium carbonate hollow microsphere CO of additive Mn2The preparation method of adsorbent - Google Patents
A kind of bivalve layer calcium carbonate hollow microsphere CO of additive Mn2The preparation method of adsorbent Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- 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
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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Abstract
The present invention is a kind of bivalve layer calcium carbonate hollow microsphere CO of additive Mn2The preparation method of adsorbent.This method comprises the following steps: first with sucrose solution hydro-thermal reaction and etc. carbon ball is prepared, then using carbon ball as sacrifice template, it adds it in calcium salt and the mixed solution of manganese salt, then by water-bath, drying, roasting, the bivalve layer calcium carbonate hollow microsphere CO of additive Mn is obtained2Adsorbent.The present invention can accurately realize the regulation of the shell thickness, microballoon size, calcium manganese ratio to the hollow calcium carbonate microspheres of bivalve layer of additive Mn by modulation calcium manganese ratio, carbon ball template, solvent composition.Preparation-obtained adsorbent presents higher adsorption capacity and good stability in adsorption desorption circulation, wherein the initial adsorption capacity upto of the adsorbent of best performance to 0.62g CO2/ g adsorbent remains to maintain 0.53g CO after 25 circulations2/g adsorbent。
Description
Technical field
The present invention relates to a kind of calcium oxide-based CO of the special appearance of inert component doping2The preparation method of adsorbent belongs to
In CO2High temperature trapping and field of material preparation.
Background technique
In recent years, as usage amount of the mankind to fossil fuel increasingly increases, burning produces a large amount of CO2。CO2Make
For one of main greenhouse gases, environmental problem brought by the greenhouse effects of generation is more serious.Currently by mankind's activity
The CO of generation2Most of flue gas in coal-burning power plant, and Ca-base adsorbent can be straight due to its higher operation temperature
It connects to the CO in flue gas2It is trapped, without carrying out cooling processing to flue gas, the energy can be saved, add its adsorption capacity
Greatly, raw material sources are extensive, many merits such as low in cost, become current most application prospect collecting carbonic anhydride technology it
One.
But the current main application difficult point of Ca-base adsorbent is easy sintering deactivation in use, be on the one hand because
For CaCO3Tamman's temperature it is low, be on the other hand because of CaO and CaCO3Molal volume difference it is larger, adsorption desorption circulation in
The mechanical stress generated by volume change generates constant impingement to the structure of adsorbent, and then the collapsing for aggravating sorbent structure is burnt
Knot causes inactivation.For these problems, current technical method is that dystectic inertia group is doped in Ca-base adsorbent
Point, and doping method is mainly more traditional technical method, for example sol-gal process, wet mixing are legal, infusion process etc., these
Method can not achieve through the structure design to adsorbent the sintering for avoiding Ca-base adsorbent, thus can be from Ca-base adsorbent
Structure design on cope with the Sintering Problem of Ca-base adsorbent.
Summary of the invention
It is an object of the present invention to be easy sintering current Ca-base adsorbent aiming at the problem that rapid deactivation, a kind of manganese is provided and is mixed
Miscellaneous bivalve layer calcium carbonate hollow microsphere CO2The preparation method of adsorbent.This method is using more shell hollow microsphere structures
On the basis of, uniqueness introduces manganese inert component, and its role is to by reducing calcium carbonate crystallite dimension, increase shell intensity and mentioning
High adsorbent improves the adsorption capacity and stability of adsorbent at sphericity, the effective physical barrier of formation etc..
Technical scheme is as follows:
A kind of bivalve layer calcium carbonate hollow microsphere CO of additive Mn2The preparation method of adsorbent, includes the following steps:
1) sucrose solution is put in crystallizing kettle, hydrothermal crystallizing reaction 1.5~3 hours is carried out at 160~230 DEG C, so
Products obtained therefrom is filtered afterwards, alternately washing is carried out with second alcohol and water to gained filter cake, then dry 8~16h at 60~120 DEG C,
The carbon ball that diameter is 1~4 μm is obtained after grinding；
Wherein, the concentration of sucrose solution is 0.5M~2M；
2) metal salt is added in solvent, metal salt solution is obtained after stirring and dissolving, then add institute in step 1)
Carbon ball processed, obtains suspension；After suspension ultrasonic disperse 5~30 minutes, then in 25~60 DEG C of water-bath 5~15h of magnetic agitation,
Gained filter cake is after being filtered, washed, dry 8 at 60~120 DEG C~for 24 hours；
Wherein, metal salt is calcium nitrate or calcium nitrate and manganese acetate, molar ratio calcium nitrate: manganese acetate=1:0~
0.01；Solvent is the mixed solution of water or second alcohol and water, volume ratio water: ethyl alcohol=1:0~5；In metal salt solution, nitre
Sour calcium concentration is 1-4M；300~1200mg carbon ball is added in every 30 milliliters of metal salt solutions；
3) it is placed in Muffle furnace after being ground 2) middle gained dry products, in air atmosphere, with the first heating speed
Rate is warming up to 380~420 DEG C, then with the second heating rate temperature to 490~510 DEG C, keeps 1~3h of temperature calcination, obtains manganese
The bivalve layer calcium carbonate hollow microsphere CO of doping2Adsorbent；
The first heating rate in the step 3) is 1~10 DEG C/min, and the second heating rate is the first heating speed
The 25%~75% of rate.
In the step 2), when solvent is the mixed solution of second alcohol and water, volume ratio is preferably water: ethyl alcohol=1:
1~5.
In the step 2), when metal salt is calcium nitrate and manganese acetate, molar ratio is preferably calcium nitrate: manganese acetate=
1:0.01~0.5.
The invention has the benefit that
1. the present invention is successfully prepared a kind of Ca-base adsorbent of novel additive Mn with double layer hollow micro-sphere structure,
Fig. 4 is the scanning electron microscope image of the bivalve layer calcium carbonate tiny balloon of typical additive Mn, is produced as we can see from the figure
It is product uniform particle diameter, good at sphericity.Fig. 1 is the transmission electron microscope image of four kinds of different calcium manganese ratio adsorbents, can from figure
To see that the product of four kinds of different calcium manganese ratios has been respectively formed clearly double layer hollow micro-sphere structure.
2. compared with the absorption property of Most current Ca-base adsorbent reported in the literature, additive Mn prepared by the present invention
Double layer hollow calcium carbonate microspheres adsorbent present higher adsorption capacity and stability, and wherein the incorporation of manganese significantly mentions
The high absorption property of adsorbent, wherein when Microsphere Size is 500nm, calcium manganese molar ratio is 12-1, the initial suction of adsorbent
Attached capacity is up to 0.62g-CO2/ g-adsorbent is higher by 30% than the adsorbent absorption property without additive Mn, at 25
0.53g-CO is still able to maintain after circulation2/ g-adsorbent is higher by 130% than the adsorbent absorption property without additive Mn,
Present more excellent absorption property stability.
3. synthesis technology of the invention is not related to the use of any organic solvent, initiator and surfactant, have green
The advantages that color is nontoxic, simple to operation, products therefrom uniform particle diameter.
4. the present invention can accurately realize the bivalve to additive Mn by modulation solvent composition, carbon ball size, calcium manganese ratio
The regulation of the shell thickness, microballoon size, calcium manganese ratio of the hollow calcium carbonate microspheres of layer.
Detailed description of the invention
Fig. 1 is the transmission electron microscope image of the double layer hollow calcium carbonate microspheres adsorbent of four kinds of different calcium manganese molar ratios
(TEM), wherein Fig. 1 a, Fig. 1 b, Fig. 1 c and Fig. 1 d be respectively pure calcium carbonate, practical calcium manganese molar ratio be 30/1,12/1 and 7/1
Double layer hollow calcium carbonate microspheres transmission electron microscope image (TEM)；
Fig. 2 is the sorption cycle test result of four kinds of different adsorbents of calcium manganese molar ratio；
Fig. 3 is the double layer hollow calcium carbonate microspheres transmission electron microscope figure of the additive Mn of shell layer prepared by embodiment 2
Picture；
Fig. 4 is the double layer hollow calcium carbonate microspheres scanning electron microscope image for the additive Mn that embodiment 3 prepares 500nm
(SEM)；
Fig. 5 is the double layer hollow calcium carbonate microspheres transmission electron microscope image for the additive Mn that embodiment 3 prepares 500nm；
Fig. 6 is the sorption cycle test of the double layer hollow calcium carbonate microspheres adsorbent of 3 kinds of different size of additive Mns；
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
Embodiment 1
(1) preparation of carbon ball template: the aqueous solution for the sucrose that concentration is 1M is fitted into crystallizing kettle, in 200 DEG C of progress water
Products obtained therefrom is filtered after the completion, is carried out to gained filter cake with second alcohol and water by thermal crystallisation reaction, time 120min, crystallization
It alternately washs, by products obtained therefrom, dry 12h, then grinding, gained carbon ball diameter are 2 μm at 80 DEG C.
(2) 20ml dehydrated alcohol and 10ml deionized water are taken, mixed solvent is obtained, by the Ca (NO of 14.169g3)2·4H2O and
Mn (the CH of 0.588g3COO)2·4H2(i.e. the concentration of calcium ion is 2mol/L to O, and the calcium manganese ion molar ratio that feeds intake is 25/1, finally
Obtaining actually measured calcium manganese ion molar ratio in adsorbent is 12/1) to be added in above-mentioned solvent to obtain metal salt solution A, in 1)
Made carbon ball template 600mg is added in this metal salt solution A, obtains suspension B, after carrying out ultrasonic disperse 30 minutes to B, will be hanged
Filter cake is dried 12h by water-bath magnetic agitation 8 hours at 40 DEG C turbid B, rear to filter, washing at 80 DEG C.
(3) gained dry products in (2) are ground, is roasted after grinding, roasting condition is air atmosphere, in horse
400 DEG C first not are warming up to 2 degree every point in furnace, switches heating rate immediately after, 500 DEG C is warming up to 1 degree every point, finally exists
500 DEG C of roastings obtain final products in 2 hours.The practical calcium manganese ratio that products obtained therefrom is measured by ICP is 12:1, therefore is named as
Ca12Mn1。
Embodiment 2
(1) preparation of carbon ball template: the aqueous solution for the sucrose that concentration is 1M is fitted into crystallizing kettle, in 200 DEG C of progress water
Thermal crystallisation reacts 110min, filters products obtained therefrom after the completion of crystallization, is repeatedly handed over second alcohol and water gained filter cake
For washing, then the dry 12h at 80 DEG C, grinding, gained carbon ball diameter are 1 μm.
(2) 20ml dehydrated alcohol and 10ml deionized water are taken, mixed solvent is obtained, by the Ca (NO of 14.169g3)2·4H2O and
Mn (the CH of 0.588g3COO)2·4H2(i.e. the concentration of calcium ion is 2mol/L to O, and the calcium manganese ion molar ratio that feeds intake is 25/1, finally
Obtaining actually measured calcium manganese ion molar ratio in adsorbent is 12/1) to be added in above-mentioned solvent to obtain metal salt solution A, in 1)
Made carbon ball template 600mg is added in this metal salt solution A, obtains suspension B, after carrying out ultrasonic disperse 30 minutes to B, will be hanged
Filter cake is dried 12h by water-bath magnetic agitation 8 hours at 40 DEG C turbid B, rear to filter, washing at 80 DEG C.
3) 2) middle gained dry products are ground, is roasted after grinding, roasting condition is air atmosphere, in Muffle
400 DEG C first are warming up to 2 degree every point in furnace, then switches heating rate, then be warming up to 500 DEG C with 1 degree every point, finally 500
DEG C roasting obtains final products in 2 hours.The practical calcium manganese molar ratio measured according to ICP, products obtained therefrom are named as Ca12Mn1-
500。
Embodiment 3
(1) preparation of carbon ball template: the aqueous solution for the sucrose that concentration is 1M is fitted into crystallizing kettle, in 200 DEG C of progress water
Thermal crystallisation reacts 120min, filters products obtained therefrom after the completion of crystallization, is repeatedly handed over second alcohol and water gained filter cake
For washing, then the dry 12h at 80 DEG C, grinding, gained carbon ball diameter are 2 μm.
(2) 30ml deionized water is taken, mixed solvent is obtained, by the Ca (NO of 14.169g3)2·4H2The Mn of O and 0.588g
(CH3COO)2·4H2(i.e. the concentration of calcium ion is 2mol/L to O, and the calcium manganese ion molar ratio that feeds intake is 25/1, finally obtains adsorbent
In actually measured calcium manganese ion molar ratio be 12/1) to be added in above-mentioned solvent and obtain metal salt solution A, by made carbon ball mould in 1)
Plate 600mg is added in this metal salt solution A, obtains suspension B, after carrying out ultrasonic disperse 30 minutes to B, by suspension B 40
Filter cake is dried 12h by water-bath magnetic agitation 8 hours at DEG C, rear to filter, washing at 80 DEG C.
3) 2) middle gained dry products are ground, is roasted after grinding, roasting condition is air atmosphere, in Muffle
400 DEG C first are warming up to 2 degree every point in furnace, then switches heating rate, 500 DEG C are warming up to 1 degree every point, finally at 500 DEG C
Roasting obtains final products in 2 hours.The practical calcium manganese molar ratio measured according to ICP, products obtained therefrom are the relatively thin Ca12Mn1 of shell
Adsorbent.
Embodiment 4
For other steps with embodiment 1, difference is Mn (CH3COO)2·4H2The additive amount of O is 0.196g, that is, feed intake calcium
Manganese molar ratio is 75:1, and measuring practical calcium manganese molar ratio by ICP is 30:1, is named as Ca30Mn1.
Embodiment 5
For other steps with embodiment 1, difference is Mn (CH3COO)2·4H2The additive amount of O is 1.471g, that is, feed intake calcium
Manganese molar ratio is 10:1, and measuring practical calcium manganese molar ratio by ICP is 7:1, is named as Ca7Mn1.
The calcium manganese ratio of involved adsorbent is the practical calcium manganese molar ratio measured by ICP in attached drawing.
From Fig. 1 it will be seen that the product of four kinds of different calcium manganese ratios has been respectively formed clearly double layer hollow micro-sphere structure.
Fig. 2 is the CO of the double layer hollow microsphere adsorbing agent of four kinds of different calcium manganese molar ratios2Absorption property evaluation result.Evaluation
Process is that (STA449F3) is carried out on thermogravimetric analyzer.When evaluation, the product of about 5mg is placed on crucible, in N2Gas
Under atmosphere, after being warming up to 600 DEG C with the heating rate of 10 DEG C/min, switching atmosphere to 50vol%CO2/ 50vol%N2, inhaled
It is attached, adsorption time 45min.After the completion of absorption, 700 DEG C are warming up to the heating rate of 10 DEG C/min in a nitrogen atmosphere, in nitrogen
20min is desorbed under gas atmosphere.After the completion of desorption, 600 DEG C of progress are cooled to the rate of temperature fall of 10 DEG C/min in a nitrogen atmosphere
Absorption.It loops back and forth like this and completes multiple adsorption desorption performance cycle test.It can be observed from fig. 2 that three kinds of adsorbents of doping manganese
Got well than not carrying out the absorption property of adsorbent of additive Mn.The adsorbent initial adsorption capacity of manganese of wherein undoping is
0.45g-CO2/ g-ads, 25 circulation after drop to 0.23g-CO2/ g-ads, stability are poor.And for calcium manganese ratio be 30-1 when,
Initial adsorption capacity boost is to 0.67g-CO2/ g-ads, however absorption property still less stable.When calcium manganese ratio be reduced to 12-1 and
When 10-1, the initial adsorption capacity of adsorbent respectively reaches 0.56g-CO2/ g-ads and 0.47g-CO2/ g-ads, after 25 recycle
Adsorption capacity slightly decreases, and shows excellent stability.Illustrate that the addition of manganese can not only improve the adsorption capacity of adsorbent,
And the incorporation of enough manganese can significantly improve the absorption stability of adsorbent.
Fig. 3 corresponds to the TEM figure of the product in embodiment 3, it can be seen that after solvent is changed to pure water, can effectively adjust
Shell thickness is saved, can get the hollow calcium carbonate microspheres of bivalve layer of the relatively thin additive Mn of shell.
Fig. 4 corresponds to the SEM figure of the product in embodiment 2, it can be seen that uses the sacrifice template using carbon ball as template
The bivalve layer hollow microsphere adsorbent of the preparation-obtained additive Mn of method has the characteristics that uniform particle diameter, good at sphericity.
Fig. 5 corresponds to the TEM figure of the product in embodiment 2, which is 500nm, it can be seen that is passed through
Using the carbon ball template with smaller diameter, the bivalve layer hollow microsphere absorption of the smaller additive Mn of diameter can be effectively obtained
Agent is realized by using different size of carbon ball template and is adjusted to the size of the bivalve layer hollow microsphere of additive Mn.
Fig. 6 be calcium manganese ratio be 12-1, diameter be respectively 1500,1200,500nm three kinds of additive Mns bivalve layer it is hollow
The CO of microsphere adsorbing agent2Absorption property evaluation result.Evaluation condition is identical as the condition in Fig. 1, it can be seen that microsphere diameter compared with
Hour, that is, Ca12Mn1-500, adsorption capacity will be consistently higher than other the two kinds microballoons being relatively large in diameter and inhale in 25 circulations
Attached dose.Its initial adsorption capacity is 0.62g-CO2/ g-ads, 25 circulation after adsorption capacity remain to maintain 0.53g-CO2/g-
Ads presents more excellent CO2Absorption property.
Unaccomplished matter of the present invention is well-known technique.
Claims (3)
1. a kind of bivalve layer calcium carbonate hollow microsphere CO of additive Mn2The preparation method of adsorbent, it is characterized in that this method includes such as
Lower step:
1) sucrose solution is put in crystallizing kettle, hydrothermal crystallizing is carried out at 160~230 DEG C and is reacted 1.5~3 hours, then will
Products obtained therefrom filters, and carries out alternately washing with second alcohol and water to gained filter cake, then dry 8~16h at 60~120 DEG C, grinding
The carbon ball that diameter is 1~4 μm is obtained afterwards；
Wherein, the concentration of sucrose solution is 0.5M~2M；
2) metal salt is added in solvent, metal salt solution is obtained after stirring and dissolving, then add made carbon in step 1)
Ball obtains suspension；After suspension ultrasonic disperse 5~30 minutes, then in 25~60 DEG C of water-bath 5~15h of magnetic agitation, gained
Filter cake is after being filtered, washed, dry 8 at 60~120 DEG C~for 24 hours；
Wherein, metal salt is calcium nitrate or calcium nitrate and manganese acetate, molar ratio calcium nitrate: manganese acetate=1:0~0.01；
Solvent is the mixed solution of water or second alcohol and water, volume ratio water: ethyl alcohol=1:0~5；In metal salt solution, calcium nitrate is dense
Degree is 1-4M；300~1200mg carbon ball is added in every 30 milliliters of metal salt solutions；
3) it is placed in Muffle furnace after being ground 2) middle gained dry products, in air atmosphere, with the first heating rate liter
Then temperature is warming up to 490~510 DEG C to 380~420 DEG C with the second heating rate, keep 1~3h of temperature calcination, obtain manganese and mix
Miscellaneous bivalve layer calcium carbonate hollow microsphere CO2Adsorbent；
The first heating rate in the step 3) is 1~10 DEG C/min, and the second heating rate is the first heating rate
25%~75%.
2. the bivalve layer calcium carbonate hollow microsphere CO of additive Mn as described in claim 12The preparation method of adsorbent, feature
For in the step 2), when solvent is the mixed solution of second alcohol and water, volume ratio is preferably water: ethyl alcohol=1:1~5.
3. the bivalve layer calcium carbonate hollow microsphere CO of additive Mn as described in claim 12The preparation method of adsorbent, feature
For in the step 2), when metal salt is calcium nitrate and manganese acetate, molar ratio is preferably calcium nitrate: manganese acetate=1:0.01
~0.5.
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| CN113912099A (en) * | 2021-11-23 | 2022-01-11 | 新乡学院 | Multilayer calcium carbonate hollow microsphere for drug loading and preparation method and application thereof |
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| CN103923650A (en) * | 2013-01-11 | 2014-07-16 | 海洋王照明科技股份有限公司 | Metal particle-doped hollow structure calcium stannate luminescence material and preparation method thereof |
| CN104961115A (en) * | 2015-06-24 | 2015-10-07 | 浙江理工大学 | Hollow hydroxyapatite microsphere and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113912099A (en) * | 2021-11-23 | 2022-01-11 | 新乡学院 | Multilayer calcium carbonate hollow microsphere for drug loading and preparation method and application thereof |
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