CN105727882A - Calcium-based CO2 adsorbent and preparing method thereof - Google Patents

Calcium-based CO2 adsorbent and preparing method thereof Download PDF

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CN105727882A
CN105727882A CN201610079081.8A CN201610079081A CN105727882A CN 105727882 A CN105727882 A CN 105727882A CN 201610079081 A CN201610079081 A CN 201610079081A CN 105727882 A CN105727882 A CN 105727882A
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calcio
raw material
adsorbent
algae
calcium
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CN105727882B (en
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刘文强
孙健
徐明厚
陈洪强
杨新伟
胡迎超
王文煜
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Huazhong University of Science and Technology
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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Abstract

The invention discloses calcium-based CO2 adsorbent.The calcium-based CO2 adsorbent is spherical particles with the diameter of 0.3-3.5 mm and are prepared from an alga raw material and a calcium-based raw material which are mixed uniformly by the mass ratio of 0.001:1-0.03:1.The calcium-based raw material is one or more of calcium hydroxide, calcium carbonate or slaked lime.The invention further discloses a preparing method of the calcium-based CO2 adsorbent.0.1-3% of the alga raw material is doped in the calcium-based raw material, a pelleting method is optimized, cycling stability of the calcium-based CO2 adsorbent is improved, and the preparing method is simple and suitable for mass production.

Description

A kind of calcio CO2Adsorbent and preparation method thereof
Technical field
The invention belongs to CO2Absorbent fields, more particularly, to a kind of calcio CO2Adsorbent and preparation method thereof.
Background technology
The CO of a large amount of discharges in Fossil fuel use procedure2It it is considered as the main cause causing global warming.In order to allow the use of Fossil fuel be accepted by environment, a series of CO2Trapping and Plugging Technology Applied are developed.Wherein, calcium circulation CO2Trapping technique is considered as a kind of CO having application prospect most due to its relatively low trapping cost and wide applicability2Trapping technique.
The calcio CO used in prior art2Adsorbent is mainly composed of calcium oxide, but there are two obvious problems when adsorbent is applied to calcium blood circulation: one is that the cyclical stability of calcium oxide adsorbent is poor, secondly because in the process ciculation fluidized between carbonating stove and calcining furnace of calcium oxide adsorbent, granule and granule, the impact of granule and pipeline and thermal stress easily causes the abrasion of adsorbent, causes the loss of active calcium oxide adsorbent.
Prior art is come CO by the method for doping or pelletize2The stability of adsorbent improves.In prilling process, extruded pelletize and the round as a ball pelletize of rotation are two kinds of pelletize modes of most common of which；But, only by the cylindrical fluidisation that is unfavorable for of the absorbent particles of extruded acquisition, and only poor by rotating round as a ball its wear resistance of the absorbent particles obtained.And in doping method, the addition of the material of doping typically requires 5%～20%, so cause the raising of preparation cost.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, the invention provides a kind of calcio CO2Adsorbent, its object is at calcio CO2Adsorbent adds algae raw material, thus improving calcio CO2The fluidization characteristic of adsorbent, antiwear property and cyclical stability.
For achieving the above object, according to one aspect of the present invention, described calcio CO2Adsorbent is spheroidal particle, the diameter of described spheroidal particle is 0.3mm～3.5mm, it includes mixed uniformly algae raw material and calcio raw material, and the mass ratio of described algae raw material and described calcio raw material is 0.001:1～0.03:1, described calcio raw material is calcium hydroxide, calcium carbonate or one or more in Calx.
Preferably, the diameter of described spheroidal particle is 0.9mm～1.25mm.
Preferably, described algae raw material is described algae raw material is algae pyrolysis lime-ash.
As it is further preferred that the preparation method of described algae pyrolysis lime-ash is, by 500 DEG C～900 DEG C heating in inert gas atmosphere of dry algae, until devolatilization therein is complete.
Preferably, described calcio raw material is calcium hydroxide.
Preferably, described algae raw material is 0.005:1～0.02:1 with the mass ratio of described calcio raw material.
It is another aspect of this invention to provide that additionally provide this calcio CO2The preparation method of adsorbent, comprises the following steps:
(1) algae raw material, water and calcio raw material are compared Homogeneous phase mixing with the quality of 0.001:0.1:1～0.03:0.45:1, it is thus achieved that mixed material；Wherein, described calcio raw material is calcium hydroxide, calcium carbonate or one or more in Calx, and its particle diameter is less than 200 μm；
(2) described mixed material extruded, cut and round as a ball, it is thus achieved that the diameter spherical mixed material less than 4mm；
(3) described spherical mixed material is screened out the spheroidal particle that diameter is 0.3mm～3.5mm after drying, it is thus achieved that described calcio CO2Adsorbent.
Preferably, described step (2) specifically, be first squeezed into the cylinder mixed material that diameter is 0.5mm～3.5mm by described mixed material, then is cut and round as a ball by described cylinder mixed material, it is thus achieved that the diameter spherical mixed material less than 4mm.
As it is further preferred that the rotating speed of described extruding is 10r/min～120r/min, the rotating speed of described cutting is 1000r/min～1400r/min, and described round as a ball rotating speed is 600r/min～1200r/min.
Preferably, dry in described step (3) method is air-dry or less than 60 DEG C drying.
In general, by the contemplated above technical scheme of the present invention compared with prior art, due at calcio CO2Preparation process in add algae raw material, it is possible to obtain following beneficial effect:
1,0.1%～3% algae raw material of only adulterating in calcio raw material just can improve CO well2The cyclical stability of adsorbent, does not affect its absorbability simultaneously, reduces CO2The cost of adsorbent doping preparation；
2, the mixed material of preparation structure comparison after extruding is closely knit, the CO of extruding round as a ball acquisition again2Adsorbent and the CO of direct round as a ball acquisition without extruding2Adsorbent is compared, not only epigranular, be prone to fluidized circulation in calcium blood circulation, and there is good CO2Absorbability and antiwear property；And this extruding, cutting round as a ball prilling process are simple, it is suitable for large-scale commercial Application；
3, algae pyrolysis lime-ash is generally the garbage of algae pyrogenation oil refining, it is preferable that using this material as algae raw material, reduce further preparation cost；
4, the present invention need not use high temperature or the exacting terms such as airtight, and preparation method is simple, and production process does not produce toxic waste, it is adaptable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the CO of gained after 25 adsorption-desorption cycle of the sample prepared by embodiment of the present invention 1-3 and comparative example 1-42Absorbability figure line；
Fig. 2 is the CO of gained after 25 adsorption-desorption cycle of the sample prepared by embodiment of the present invention 4-5 and comparative example 12Absorbability figure line.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitute conflict each other.
The invention provides a kind of calcio CO2Adsorbent, described calcio CO2Adsorbent is the spheroidal particle of diameter 0.3mm～3.5mm, and it mass ratio including mixed uniformly algae raw material and calcio raw material, described algae raw material and described calcio raw material is 0.001:1～0.03:1；Wherein, described calcio CO2The diameter of adsorbent is preferably 0.9mm～1.25mm, excessive, easily affect absorption property, too small, it is easily reduced mechanical strength thus affecting cyclical stability, the mass ratio of described algae raw material and described calcio raw material is preferably 0.005:1:1～0.02:1, doping ratio is too high, then easily affecting its absorption property, and improve production cost, doping ratio is too small, improves the DeGrain of cyclical stability；Described algae raw material is the algae powder (powdered substance that namely less than 100 DEG C dehydrations of algae obtain, containing compositions such as fat, protein and polysaccharides) such as microalgae powder, or algae pyrolysis lime-ash (namely dry algae 500 DEG C～900 DEG C heating in inert gas atmosphere, until the coke species that obtains afterwards completely of devolatilization therein) such as microalgae pyrolysis lime-ash；Described calcio raw material is calcium hydroxide, calcium carbonate or Calx, it is also possible to for the mineral containing these compositions, such as industry Calx, limestone or carbide slag garbage.
This calcio CO2The preparation method of adsorbent comprises the following steps:
(1) by algae raw material, water and calcio raw material compare Homogeneous phase mixing with the quality of 0.001:0.1:1～0.03:0.45:1, it is thus achieved that mixed material；Wherein, described calcio raw material is calcium hydroxide, calcium carbonate or one or more in Calx, and its particle diameter is less than 200 μm；
(2) by round as a ball for the extruding of described mixed material, it is thus achieved that the diameter spherical mixed material less than 4mm；
(3) described spherical mixed material is dried (as air-dry or less than 60 DEG C 5h～10h are dried, in order to avoid temperature is too high makes adsorbent and the CO in air2Reaction thus affecting its absorption property) after screen out the spheroidal particle that diameter is 0.3mm～3.5mm, it is thus achieved that described calcio CO2Adsorbent.
Wherein, the flexible normal use squeezing roll circular knitting machine operation of squeezing roll of described step (2), it concretely comprises the following steps, first the rotating speed of described mixed material 10r/min～120r/min is squeezed into the cylinder mixed material that diameter is 0.5mm～3.5mm, described cylinder mixed material is cut under 1000r/min～1400r/min rotating speed 0.5min～2min again, cylinder mixed material is made to be cut into pieces, the cylinder mixed material round as a ball 5min～10min under the rotating speed of 600r/min～1200r/min being finally cut into pieces, it is thus achieved that the diameter spherical mixed material less than 4mm.
Embodiment 1 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae
(1) deionized water of 15ml added in the microalgae powder of the 40g particle diameter calcium hydroxide powder less than 150 μm and 0.2g and stir.
(2) wet stock obtained being passed through single-screw extruder, extrusion die plate aperture is 1mm, and extruding rotating speed is 30r/min, obtains oval column absorbent particles.Then, putting in spheronizator by long cylinder granule, first setting speed is 1400r/min and continues 2min, and long cylinder calcium oxide particle 1400r/min2min is cut into short cylindrical granule, rotating speed is down to 1000r/min again and continues 5min, short cylindrical granule is rolled into calcium oxide bead.
(3) finally being sieved by standard screen by the calcium oxide bead obtained, particle size range bead between 0.9mm～1.25mm is placed in air air-dry 24h, is final calcium oxide-based adsorbent bead CH.
Embodiment 2 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae
Repeating embodiment 1 with described same steps, be distinctive in that, the quality of microalgae powder is 0.4g.
Embodiment 3 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae
Repeating embodiment 1 with described same steps, be distinctive in that, the quality of microalgae powder is 0.8g.
Embodiment 4 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae pyrolysis lime-ash:
Repeat embodiment 1 with described same steps, be distinctive in that, replace the microalgae powder of 0.2g with the microalgae pyrolysis lime-ash of 0.224g.
Embodiment 5 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae pyrolysis lime-ash:
Repeating embodiment 4 with described same steps, be distinctive in that, the quality of microalgae pyrolysis lime-ash doping is 0.9g.
Embodiment 6
Repeating embodiment 4 with described same steps, be distinctive in that, the quality of microalgae pyrolysis lime-ash doping is 0.04g, replaces calcium hydroxide powder with the calcium carbonate powder that particle diameter is 150 μm.
Embodiment 7
Repeating embodiment 4 with described same steps, be distinctive in that, the quality of microalgae pyrolysis lime-ash doping is 1.2g, replaces calcium hydroxide powder with carbide slag garbage powder.
Embodiment 8
Repeating embodiment 4 with described same steps, be distinctive in that, the extrusion die plate aperture chosen in described step (2) is 3.5mm, screens out the particle size range calcium oxide bead at 0.3mm～3.5mm in described step (3).
The preparation of comparative example 1 carbonate-free lime base adsorbent bead
The deionized water of 15ml is added in 40g calcium hydroxide powder and is sufficiently stirred for.The wet stock obtained is passed through single-screw extruder, and extrusion die plate aperture is 1mm, and extruding rotating speed is 30r/min, obtains oval column absorbent particles.Then, putting in spheronizator by long cylinder granule, first setting speed is 1400r/min and continues 2min, and long cylinder calcium oxide particle is cut into short cylindrical granule, then rotating speed is down to 1000r/min and persistently 5min short cylindrical granule is rolled into calcium oxide bead.Finally being sieved by standard screen by the calcium oxide bead obtained, particle size range bead between 0.9mm～1.25mm is placed in air air-dry 24h, is final calcium oxide-based adsorbent bead CH.
Comparative example 2 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae
Repeating embodiment 1 with described same steps, be distinctive in that, the quality of microalgae powder is 2g.
Comparative example 3 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae
Repeating embodiment 1 with described same steps, be distinctive in that, the quality of microalgae powder is 4g.
Comparative example 4 is adulterated the preparation of calcium oxide-based adsorbent bead of microalgae
Repeating embodiment 1 with described same steps, be distinctive in that, the quality of microalgae powder is 8g.
Interpretation
The calcium oxide-based adsorbent bead of non-impurity-doped, doping microalgae and the doping microalgae pyrolysis lime-ash comparative example 1～4 of the present invention and embodiment 1～5 prepared carries out CO on thermogravimetric analyzer (Pyris1)2Absorbability is tested, and sample quality is between 20mg～30mg.Adsorption reaction condition: temperature is 650 DEG C, CO2Concentration is 15vol.%, and gas flow is 100ml/min, and carbonation time is 30min；Desorption reaction condition: temperature is 850 DEG C, 100vol%N2, gas flow is 100ml/min, and desorption time is 2min, the CO recorded2Absorbability is as illustrated in fig. 1 and 2.As can be seen from Figure 1 when the mixing proportion of microalgae and calcium hydroxide is 0.02:1, adsorbent bead shows best absorbability, and after 25 circulations, its absorbability is 0.348gCO2/ g adsorbent is after pure cerium hydroxide calcoglobule 25 times circulation 2.07 times of absorbability.From figure 2 it can be seen that when doping microalgae pyrolysis lime-ash, no matter mixing proportion is 0.0056:1 or 0.0225:1, can both show stable and good absorbability, its absorbability respectively 0.288gCO after 25 circulations2/ g adsorbent and 0.328gCO2/ g adsorbent.But, when the mixing proportion of microalgae and calcium hydroxide is more than 0.05:1, CO can be caused on the contrary2The initial adsorption performance of/g adsorbent reduces.Embodiment 6-8 is analyzed, it is possible to obtain the result similar with embodiment 1-4.
Can be seen that no matter be have only to marginally blend the CO that just can be effectively improved calcium oxide-based adsorbent bead by microalgae or microalgae pyrolysis lime-ash by the test analysis of various embodiments above2Absorbability.Meanwhile, the process that employing extruding-spheronization prepares calcium oxide-based adsorbent bead is simple, and operating cost is low, does not result in environmental pollution.
Those skilled in the art will readily understand; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.

Claims (10)

1. a calcio CO2Adsorbent, it is characterised in that described calcio CO2Adsorbent is spheroidal particle, the diameter of described spheroidal particle is 0.3mm～3.5mm, it includes mixed uniformly algae raw material and calcio raw material, and the mass ratio of described algae raw material and described calcio raw material is 0.001:1～0.03:1, described calcio raw material is calcium hydroxide, calcium carbonate or one or more in Calx.
2. calcio CO as claimed in claim 12Adsorbent, it is characterised in that the diameter of described spheroidal particle is 0.9mm～1.25mm.
3. calcio CO as claimed in claim 12Adsorbent, it is characterised in that described algae raw material is algae pyrolysis lime-ash.
4. calcio CO as claimed in claim 32Adsorbent, it is characterised in that the preparation method of described algae pyrolysis lime-ash is, by 500 DEG C～900 DEG C heating in inert gas atmosphere of dry algae, until devolatilization therein is complete.
5. calcio CO as claimed in claim 12Adsorbent, it is characterised in that described calcio raw material is calcium hydroxide.
6. calcio CO as claimed in claim 12Adsorbent, it is characterised in that the mass ratio of described algae raw material and described calcio raw material is 0.005:1～0.02:1.
7. calcio CO as described in any one in claim 1-62The preparation method of adsorbent, it is characterised in that comprise the following steps:
(1) algae raw material, water and calcio raw material are compared Homogeneous phase mixing with the quality of 0.001:0.1:1～0.03:0.45:1, it is thus achieved that mixed material；Wherein, described calcio raw material is calcium hydroxide, calcium carbonate or one or more in Calx, and its particle diameter is less than 200 μm；
(2) described mixed material extruded, cut and round as a ball, it is thus achieved that the diameter spherical mixed material less than 4mm；
(3) described spherical mixed material is screened out the spheroidal particle that diameter is 0.3mm～3.5mm after drying, it is thus achieved that described calcio CO2Adsorbent.
8. preparation method as claimed in claim 7, it is characterized in that, described step (2) is specially, first described mixed material is squeezed into the cylinder mixed material that diameter is 0.5mm～3.5mm, again described cylinder mixed material is cut and round as a ball, it is thus achieved that the diameter spherical mixed material less than 4mm.
9. preparation method as claimed in claim 8, it is characterised in that the rotating speed of described extruding is 10r/min～120r/min, and the rotating speed of described cutting is 1000r/min～1400r/min, and described round as a ball rotating speed is 600r/min～1200r/min.
10. preparation method as claimed in claim 7, it is characterised in that method dry in described step (3) is air-dry or less than 60 DEG C drying.
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CN108686616A (en) * 2017-04-10 2018-10-23 北京林业大学 A kind of carbon dioxide absorbing material and preparation method thereof
CN108686616B (en) * 2017-04-10 2020-09-11 北京林业大学 Carbon dioxide adsorbing material and preparation method thereof
CN108295802A (en) * 2018-03-30 2018-07-20 南京师范大学 A kind of potassium base CO2Absorbent granules and its preparation method and application
CN109621890A (en) * 2018-12-24 2019-04-16 华中科技大学 A kind of spherical calcium base CO of whole process industrialization2The preparation method of adsorbent
CN110052238A (en) * 2019-04-19 2019-07-26 中南大学 A kind of spherical shape calcium group carbonic anhydride adsorption agent and preparation method thereof
CN110292905A (en) * 2019-07-22 2019-10-01 华中科技大学 A kind of spherical calcium base CO of loaded inert carrier2Adsorbent, its preparation and application
CN110721664A (en) * 2019-10-10 2020-01-24 浙江海洋大学 Preparation method of mussel shell powder/carboxymethyl cellulose composite gel adsorbent
CN110721664B (en) * 2019-10-10 2021-12-17 浙江海洋大学 Preparation method of mussel shell powder/carboxymethyl cellulose composite gel adsorbent
CN112275251A (en) * 2020-10-15 2021-01-29 天津大学 Doped modified calcium-based CO2Batch production method of adsorbent pellets
CN113332948A (en) * 2021-01-28 2021-09-03 华中科技大学 Method for reducing composite molten salt in adsorbent by adding alkaline ion blocking agent

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