CN104959132A - Preparation method of carbon dioxide calcium-based adsorbent - Google Patents
Preparation method of carbon dioxide calcium-based adsorbent Download PDFInfo
- Publication number
- CN104959132A CN104959132A CN201510331984.6A CN201510331984A CN104959132A CN 104959132 A CN104959132 A CN 104959132A CN 201510331984 A CN201510331984 A CN 201510331984A CN 104959132 A CN104959132 A CN 104959132A
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- China
- Prior art keywords
- calcium
- adsorbent
- preparation
- alginic acid
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NVDORESINSWXKC-UHFFFAOYSA-N [Ca].O=C=O Chemical compound [Ca].O=C=O NVDORESINSWXKC-UHFFFAOYSA-N 0.000 title abstract 5
- 239000011575 calcium Substances 0.000 claims abstract description 48
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 aluminum ions Chemical class 0.000 claims abstract description 7
- 235000010443 alginic acid Nutrition 0.000 claims description 23
- 229920000615 alginic acid Polymers 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000783 alginic acid Substances 0.000 claims description 17
- 229960001126 alginic acid Drugs 0.000 claims description 17
- 150000004781 alginic acids Chemical class 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 235000010408 potassium alginate Nutrition 0.000 claims description 3
- 239000000737 potassium alginate Substances 0.000 claims description 3
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 238000003795 desorption Methods 0.000 abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 11
- 125000004122 cyclic group Chemical group 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 7
- 235000010410 calcium alginate Nutrition 0.000 abstract description 5
- 239000000648 calcium alginate Substances 0.000 abstract description 5
- 229960002681 calcium alginate Drugs 0.000 abstract description 5
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 abstract description 5
- LCWAOCHOPBSGMU-UHFFFAOYSA-J aluminum;magnesium;sodium;hydrogen carbonate;oxygen(2-);silicon;trihydroxide Chemical compound [OH-].[OH-].[OH-].[O-2].[Na+].[Mg+2].[Al+3].[Si].OC([O-])=O LCWAOCHOPBSGMU-UHFFFAOYSA-J 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000005431 greenhouse gas Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229960005069 calcium Drugs 0.000 description 41
- 238000010521 absorption reaction Methods 0.000 description 36
- 239000012298 atmosphere Substances 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 6
- 229940072056 alginate Drugs 0.000 description 6
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 239000004330 calcium propionate Substances 0.000 description 1
- 235000010331 calcium propionate Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a preparation method of a carbon dioxide calcium-based adsorbent and belongs to the field of high-temperature adsorption and separation of CO2. The preparation method includes: taking an alginic acid compound as a substrate; subjecting the alginic acid compound to compound cross-linking with a calcium source and an aluminum source to form calcium alginate; performing high-temperature calcining on the calcium alginate to obtain the porous calcium-based CO2 adsorbent. The carbon dioxide calcium-based adsorbent is high in CO2 adsorption efficiency and simple in high-temperature desorption, and obvious lowering of efficiency after repeated use is avoided. A cross-linking mechanism is adopted to directly fix calcium ions and aluminum ions on an alginic acid compound framework uniformly, so that the preparation method is simple and high in operability; CO2 adsorption efficiency and cyclic adsorption performance of the carbon dioxide calcium-based adsorbent can be improved remarkably, and the carbon dioxide calcium-based adsorbent can be widely applied to capture and storage of greenhouse gas CO2.
Description
Technical field
The present invention relates to a kind of preparation method of carbon dioxide Ca-base adsorbent, belong to CO
2high temperature adsorption and separation field.
Background technology
Industrial expansion, causes CO
2discharge capacity increase year by year, the thing followed is global environmental problem-greenhouse effects.For present situation, researcher is to CO
2separation and trapping carried out systematic research, considering that the gas temperature that factory's actual discharge goes out is higher, is improve the utilization rate of heat energy, and this patent is then mainly in CO
2separating at high temperature trapping.
Cheap and easy to get and its CO of CaO
2adsorption capacity is the highest, and its theoretical adsorbance is 78.6wt% (gCO
2/ g CaO).Therefore, Ca-base adsorbent (CaO) is used to carry out high temperature trapping CO
2application potential is larger.The method adopting Ca-base adsorbent Cyclic Carbonation/calcining to be separated then is considered to the cheapest and effective CO at present
2one of separation and collection mode.But Ca-base adsorbent also exists a lot of deficiency, on the one hand, Ca-base adsorbent causes specific area to decline through repeatedly calcining generation sintering phenomenon, and circulation absorption performance reduces; On the other hand, a certain amount of SO is contained in industrial waste gas
2, CaO and SO
2the CaSO that reaction generates
4cannot regenerate under the condition that carbonating/calcining is separated, CaO effective content be reduced, CO
2circulation absorption hydraulic performance decline.
The preparation method of Ca-base adsorbent is various, and for the defect of Ca-base adsorbent easy-sintering, this patent then mainly prepares porous type calcium base CO
2adsorbent, has the hole communicated in a large number in this adsorbent, flourishing pore structure can increase CO
2adsorbance is improved with the contact area of CaO.Pore structure will have the skeletal support of better heat stability that adsorbent just can be made still to keep higher adsorbance through repeatedly circulating.Aluminium source in this patent and calcium source can form Ca through high-temperature calcination
3al
2o
6and Ca
12al
14o
33deng material, this type of material better heat stability, can be used as the skeletal support loose structure of Ca-base adsorbent and then hinders the generation of sintering phenomenon.
Calcium source category is various, and there are CaO, CaCO in common inorganic calcium source
3deng, there are calcium gluconae, calcium lactate and calcium propionate etc. in organic calcium source, and in recent years, a lot of researcher uses waste residue discarded object as calcium source as egg shell, carbide slag and slag etc.Sorbent structure prepared by use inorganic calcium source is primarily of CaO, CaCO
3the structures shape of itself, comparatively organic calcium source is poor for structure plasticity; Waste residue discarded object needs when doing calcium source to consider impurities removal, and in waste residue, contained material is complicated, needs to consider the unfavorable factor of various impurity to equipment in factory's practical application; And organic calcium source organic moiety after calcining forms gas, for adsorbent leaves a large amount of holes, increase the specific area of adsorbent.And common organic calcium source cannot make calcium ion and aluminium ion be evenly distributed in adsorbent skeleton, therefore, this patent uses marine alga acid and calcium source and aluminium source to be cross-linked to form the mechanism of corresponding alginate, calcium aluminium ion is made to be evenly distributed in alginic acid skeleton, alginic acid is a kind of polysaccharide material extracted from algae, form primarily of beta-D-mannuronic acid (being called for short M unit) and α-L-guluronic acid (being called for short G unit) 2 kinds of components, in the marine alga acids structure of matter containing a large amount of group can with calcium, aluminium ion is cross-linked, calcium alginate is common in pharmaceutical carrier, many-sided research such as skeleton and resistance fire material, add the Fire resistances that aluminium alginate then can strengthen calcium alginate, do not find at present to use alginate to make the composite calcium-base CO in calcium/aluminium source
2adsorbent.
The common preparation method of calcium alginate is by sodium alginate and CaCl
2be cross-linked to form, because the content of sodium, potassium ion is to CO
2circulation adsorption desorption performance impact is comparatively large, therefore adopts different calcium/aluminium source and marine alga acid to prepare alginate in this patent.Alginic acid is utilized to be dissolved in this characteristic of highly basic, alginic acid is dissolved in calcium hydroxide suspension, under differential responses time and temperature, make calcium aluminium ion and alginic acid full cross-linked, obtained alginate, by the alginate of synthesis, drying, calcining can make alginic acid decomposed release CO again
2and H
2o forms final porous type calcium base CO
2adsorbent.
Summary of the invention
The present invention utilizes groups a large amount of in alginic acid compound structure to be combined with calcium, aluminium ion homogeneous cross-link, defines a large amount of pores through calcining, thus increases adsorbent specific area, improves its circulation absorption performance.This invention exploits the high temperature calcium base CO that a kind of technique is simple, be easy to operation
2sorbent preparation method, specifically comprises the following steps:
(1) in molar ratio for the ratio of 1:5 ~ 10:1 is by adding in distilled water after calcium source, the mixing of aluminium source, mixture after stirring, is obtained;
(2), after the temperature of mixture is adjusted to-25 ~ 50 DEG C, the ratio being 1:1 ~ 1:100 in the mass ratio of calcium source, aluminium source mixture gross mass and alginic acid compounds adds alginic acid compounds stirring reaction 1 ~ 120 h in the mixture;
(3) react after washing 2 ~ 3 times with acid solution after afterproduct is dried to constant weight and be washed with distilled water to neutrality, desciccate is to constant weight;
(4) CO is obtained after step (3) dried product being calcined 30min ~ 10h at 700 ~ 1200 DEG C
2ca-base adsorbent.
Calcium source of the present invention is the one in calcium oxide, calcium hydroxide; Aluminium source is the one in aluminium chloride, aluminum nitrate; Alginic acid compounds is the one in alginic acid, sodium alginate, potassium alginate.
Acid solution of the present invention is the one in 1 ~ 10 wt % nitric acid, 1 ~ 10wt % hydrochloric acid, 1 ~ 10wt % acetic acid.
Beneficial effect of the present invention:
(1) the present invention is mainly for CO such as power plant
2the industry that discharge capacity is large, at high temperature directly can absorb CO
2, economize energy; Reclaim carbon resource simultaneously, reduce CO
2discharge, thus play the effect of protection of the environment.
(2) the present invention adopts simple composite crosslinking react and calcine and obtain target product, and preparation technology is simple, be easy to operation, cost is low, and can achieve large-scale industrial and apply, gained adsorbent is porous material, and it is to CO
2adsorption efficiency can reach 89%.
Accompanying drawing explanation
Fig. 1 is gained calcium base CO in embodiment 1
2the scanning electron microscope (SEM) photograph of adsorbent;
Fig. 2 be in embodiment 1 gained Ca-base adsorbent to CO
2circulation absorption curve.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1
Be dissolved in the distilled water of 100ml after taking 0.74g calcium hydroxide and 3.75g aluminum nitrate (mol ratio 1:1) mixing, stir; 4.49g alginic acid (mass ratio 1:1) is added, constant temperature vigorous stirring reaction 120h after mixeding liquid temperature being modulated 50 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with 1 wt % salpeter solution, desciccate is to permanent again; Product is calcined at 900 DEG C 10h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 89%, after cyclic absorption 20 times, adsorption efficiency is 79.6%.
Can find out that the high temperature carbon dioxide Ca-base adsorbent of synthesis exists a large amount of macropore duct by Fig. 1,2, therefore through the Posterior circle conversion ratio that repeatedly circulates still up to 79.6%.
Embodiment 2
Be dissolved in the distilled water of 100ml after taking 5.6g calcium oxide and 1.33g aluminium chloride (mol ratio 10:1) mixing, stir; 6.93g alginic acid (mass ratio 1:1) is added, constant temperature vigorous stirring reaction 48h after mixeding liquid temperature being modulated 0 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with 5 wt % hydrochloric acid solutions, desciccate is to permanent again; Product is calcined at 1200 DEG C 1h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 82.5%, after cyclic absorption 20 times, adsorption efficiency is 73.7%.
Embodiment 3
Be dissolved in the distilled water of 1000ml after taking 5.6g calcium oxide and 3.75g aluminum nitrate (mol ratio 10:1) mixing, stir; 93.5g alginic acid (mass ratio 1:10) is added, constant temperature vigorous stirring reaction 120h after mixeding liquid temperature being modulated 0 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with 10wt % acetum, desciccate is to permanent again; Product is calcined at 900 DEG C 1h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 87.4%, after cyclic absorption 20 times, adsorption efficiency is 75.1%.
Embodiment 4
Be dissolved in the distilled water of 100ml after taking 0.74g calcium hydroxide and 1.33g aluminium chloride (mol ratio 1:1) mixing, stir; 2.03g alginic acid (mass ratio 1:1) is added, constant temperature vigorous stirring reaction 1h by after mixeding liquid temperature modulation-25 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with 5 wt % salpeter solutions, desciccate is to permanent again; Product is calcined at 900 DEG C 1h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 84%, after cyclic absorption 20 times, adsorption efficiency is 72.6%.
Embodiment 5
Be dissolved in the distilled water of 100ml after taking 5.6g calcium oxide and 1.33g aluminium chloride (mol ratio 10:1) mixing, stir; 6.93g sodium alginate (mass ratio 1:1) is added, constant temperature vigorous stirring reaction 48h by after mixeding liquid temperature modulation-25 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with the acetum of 5 wt %, desciccate is to permanent again; Product is calcined at 700 DEG C 1h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 74.5%, after cyclic absorption 20 times, adsorption efficiency is 60.9%.
Embodiment 6
Be dissolved in the alkaline aqueous solution of 100ml after taking 0.74g calcium hydroxide and 6.65g aluminium chloride (mol ratio 1:5) mixing, stir; 7.39g sodium alginate (mass ratio 1:1) is added, constant temperature vigorous stirring reaction 10h by after mixeding liquid temperature modulation-25 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with the acetum of 10wt %, desciccate is to permanent again; Product is calcined at 900 DEG C 30min and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 80.2%, after cyclic absorption 20 times, adsorption efficiency is 67.1%.
Embodiment 7
Be dissolved in the distilled water of 1000ml after taking 0.074g calcium hydroxide and 0.665g aluminum nitrate (mol ratio 1:5) mixing, stir; 73.9g sodium alginate (mass ratio 1:100) is added, constant temperature vigorous stirring reaction 120h after mixeding liquid temperature being modulated 50 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with 10 wt % salpeter solutions, desciccate is to permanent again; Product is calcined at 900 DEG C 10h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 84.8%, after cyclic absorption 20 times, adsorption efficiency is 76.8%.
Embodiment 8
Be dissolved in the distilled water of 1000ml after taking 5.6g calcium oxide and 3.75g aluminum nitrate (mol ratio 10:1) mixing, stir; 93.5g potassium alginate (mass ratio 1:10) is added, constant temperature vigorous stirring reaction 72h after mixeding liquid temperature being modulated 0 DEG C; Reacted rear products therefrom dry 8h at 120 DEG C, be again washed with distilled water to neutrality after washing 3 times with 1 wt % salpeter solution, desciccate is to permanent again; Product is calcined at 900 DEG C 1h and namely obtain white calcium base CO
2adsorbent.
The calcium base CO that the present embodiment prepares
2adsorbent is used for CO
2circulation absorption, adsorption temp is 700 DEG C, adsorption time is 30min, absorption atmosphere be 1/1 CO
2and N
2atmosphere; Desorption temperature is 860 DEG C, desorption time 10min, desorption atmosphere 100%N
2atmosphere, it is to CO
2absorption efficiency be 84.2%, after cyclic absorption 20 times, adsorption efficiency is 76.3%.
Claims (3)
1. a CO
2the preparation method of Ca-base adsorbent, is characterized in that: specifically comprise the following steps:
(1) in molar ratio for the ratio of 1:5 ~ 10:1 is by adding in distilled water after calcium source, the mixing of aluminium source, mixture after stirring, is obtained;
(2), after the temperature of mixture is adjusted to-25 ~ 50 DEG C, the ratio being 1:1 ~ 1:100 in the mass ratio of calcium source, aluminium source mixture gross mass and alginic acid compounds adds alginic acid compounds stirring reaction 1 ~ 120 h in the mixture;
(3) react after washing 2 ~ 3 times with acid solution after afterproduct is dried to constant weight and be washed with distilled water to neutrality, desciccate is to constant weight;
(4) CO is obtained after step (3) dried product being calcined 30min ~ 10h at 700 ~ 1200 DEG C
2ca-base adsorbent.
2. CO according to claim 1
2the preparation method of Ca-base adsorbent, is characterized in that: described calcium source is the one in calcium oxide, calcium hydroxide; Aluminium source is the one in aluminium chloride, aluminum nitrate; Alginic acid compounds is the one in alginic acid, sodium alginate, potassium alginate.
3. CO according to claim 1
2the preparation method of Ca-base adsorbent, is characterized in that: described acid solution is the one in 1 ~ 10 wt % nitric acid, 1 ~ 10wt % hydrochloric acid, 1 ~ 10wt % acetic acid.
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| CN105498710A (en) * | 2015-12-20 | 2016-04-20 | 高大元 | Preparation method for preparing modified compound calcium-based carbon dioxide adsorbent through fishbone |
| CN105727882A (en) * | 2016-02-04 | 2016-07-06 | 华中科技大学 | Calcium-based CO2 adsorbent and preparing method thereof |
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| CN105498710A (en) * | 2015-12-20 | 2016-04-20 | 高大元 | Preparation method for preparing modified compound calcium-based carbon dioxide adsorbent through fishbone |
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| CN106000301A (en) * | 2016-05-30 | 2016-10-12 | 华中科技大学 | Preparation method of spherical calcium-based CO2 adsorbent |
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| CN107445160A (en) * | 2017-08-08 | 2017-12-08 | 中国林业科学研究院林产化学工业研究所 | A kind of insolubility alginic acid alkali super capacitor active carbon and one step charing preparation method of adjustable aperture |
| CN107572517A (en) * | 2017-09-01 | 2018-01-12 | 中国林业科学研究院林产化学工业研究所 | Alginic acid alkali three-dimensional network layered activated carbon and one step charing preparation method |
| CN116251595A (en) * | 2023-02-09 | 2023-06-13 | 中国石油大学(华东) | Calcium aluminate-based multi-metal composite material and preparation method and application thereof |
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