CN101912766A - High-strength dry CO2 adsorbent for regeneration by using zeolite as carrier and preparation thereof - Google Patents

Abstract

The invention relates to a high-strength dry CO2 adsorbent for regeneration by using zeolite as a carrier and a preparation method thereof. The adsorbent consists of two parts, namely an active ingredient and a carrier, wherein the active ingredient is hexagonal system potassium carbonate and accounts for 30 to 50 weight percent of the total weight of the adsorbent; and the carrier is the zeolite and accounts for 50 to 70 weight percent of the total weight of the adsorbent. The adsorbent is granular, has the mean particle size of 100 to 200 mu m and the particle size distribution range of 50 to 300 mu m, and is prepared by an excessive impregnating method. The adsorbent has the advantages of large specific surface area, high porosity, high strength, abrasion resistance, and particularly obvious desorption on carbon dioxide; and the preparation method has the advantages of simple and practical preparation method, low cost and suitability for industrial production.

Description

The HIgh strength drying regeneration CO of zeolite as carrier 2Adsorbent and preparation thereof

Technical field

The invention belongs to CO ₂Dry type adsorbent and preparation field thereof particularly relate to a kind of HIgh strength drying regeneration CO of zeolite as carrier ₂Adsorbent and preparation method thereof.

Background technology

Climate change has become the No.1 problem of human kind sustainable development.As everyone knows, CO ₂Be a kind of greenhouse gases of discharge capacity maximum.It is predicted the CO of China ₂Total release will surpass the U.S. and become CO in about the year two thousand twenty ₂No.1 discharging big country, the negative effect that bring more serious weather and ecological environment will certainly for the China and even the whole world like this, therefore, control CO as early as possible as early as possible must adopt an effective measure ₂Discharging, slow down " greenhouse effects ".Consider CO in the power-plant flue gas ₂Branch force down maturity with technical matters, chemical absorption method is to CO in the flue gas ₂To remove be a kind of reasonable selection comparatively speaking.Therefore utilize the dry method adsorbent to remove CO by gas-solid reaction ₂Technology have low, the recycling efficient height of energy consumption of reaction, equipment do not had advantages such as burn into non-secondary pollution and water consumption be little, become present research focus.But that carrier uses in the dry method absorption process at present is AC (active carbon), TiO ₂, MgO, SiO ₂, Al ₂O ₃, NaX, CsNaX, CaO etc., operating cost is higher, is not suitable for using on a large scale in the power plant.

Natural zeolite is that a kind of cost is low, the moisture aluminosilicate mineral of easy exploiting and the frame shape structure that has no side effect, and its chemical composition general formula is: [M2 (I), M (11)] OAl ₂O ₃NSiO ₂MH ₂O, M in the formula (I) and M (II) are respectively monovalence and divalent metal (being generally sodium, potassium, calcium, inscription, barium etc.), and n is the silica alumina ratio of zeolite, and general n=2～10 (containing alkyl can reach more than 20 by the zeolite silica alumina ratio of ion), m=0～9 are water molecule number.

Because the difference of silicon (aluminium) oxygen tetrahedron connected mode forms a lot of holes and duct in zeolite structured, its bug hole volume accounts for the 40%-50% of cumulative volume.Have a large amount of micropores uniformly in the zeolite crystal structure, the aperture is suitable with the molecular size of general material, and its specific area reaches 400-800m ²/ g, the specific area of A type zeolite is more up to 1000m ²/ g, this particular structure and crystal chemistry characteristic make zeolite have good physical and chemical performance, as ion exchangeable, adsorbing separation, catalytic, heat endurance, acid resistance etc.

Big quantity research is also being done aspect the carbon dioxide dry type adsorbent by Southeast China University, applies for a patent: CN101269316A, its adsorbent activity component has remarkable carbonation reaction characteristic for decomposing the hexagonal crystal system potash that makes through saleratus.Therefore, active component is selected the hexagonal crystal system potash that makes through the saleratus decomposition for use among the present invention.

Summary of the invention

Technical problem to be solved by this invention provides a kind of HIgh strength drying regeneration CO of zeolite as carrier ₂Adsorbent and preparation method thereof, this adsorbent specific area is big, porosity good, intensity is high, wear-resistant, and particularly to the adsorbing and removing effect highly significant of carbon dioxide, the preparation method is simple and practical, and cost is low, is suitable for suitability for industrialized production.

The HIgh strength drying regeneration CO of a kind of zeolite as carrier of the present invention ₂Adsorbent, this adsorbent comprise active component and carrier two parts, and described active component is a hexagonal crystal system potash, account for the 30wt%～50wt% of adsorbent gross mass; Described carrier is a zeolite, accounts for the 50wt%～70wt% of adsorbent gross mass; This adsorbent is shaped as graininess, and mean particle size range is 50～300 μ m.

Described zeolite is an active carbon, and possess hydrophilic property, surface area are 400-800m ²/ g.

Described particle size range is 100～200 μ m.

The HIgh strength drying regeneration CO of a kind of zeolite as carrier of the present invention ₂The preparation of adsorbent method comprises:

(1) producing of potassium bicarbonate solution: take by weighing saleratus, the water dissolving obtains potassium bicarbonate solution;

(2) producing of carrier granular: taking by weighing with the saleratus weight ratio is 50～70: 30～50 zeolite, grinds and obtains the carrier granular that particle diameter is 50～300 μ m;

(3) mixing of active component and carrier: the carrier granular that step (2) obtains is put into potassium bicarbonate solution, stir 10～12h;

(4) drying: with the solution left standstill half an hour that step (3) obtains, treat the complete post precipitation of solid particle, remove unnecessary liquid, dry down in 80～100 ℃;

(5) calcining: with dried adsorbent calcining at constant temperature 2～3h under 600～800 ℃ of temperature;

(6) screening: the adsorbent after will calcining sieves according to requirement of engineering.

The HIgh strength drying regeneration CO of zeolite as carrier ₂Adsorbent removes that the method for carbon dioxide is the chemical absorbing dry technique in the flue gas, can adopt fluidized-bed reactor to carry out carbonation reaction in 60～80 ℃ of scopes, thermal regeneration in 100～250 ℃ of scopes, and reactivation heat can be provided by fume afterheat fully.

Beneficial effect

(1) specific area of the present invention is big, porosity good, intensity is high, wear-resistant, particularly the adsorbing and removing effect highly significant regenerability to carbon dioxide is good, but recycled for multiple times has higher economy;

(2) preparation method is simple and practical, and cost is low, is suitable for suitability for industrialized production.

Description of drawings

Fig. 1 is silicon (aluminium) oxygen tetrahedron schematic diagram;

Fig. 2 is silicon (aluminium) oxygen planar structure formula schematic diagram.

The specific embodiment

Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.

Embodiment 1

Take by weighing the 100kg saleratus and pour in the agitator vessel, water filling in container, stirring is simultaneously thoroughly dissolved saleratus; The wooden class active carbon of graininess that takes by weighing the 200kg diameter and be 50～100 μ m is poured into and is stirred 12h in the potassium bicarbonate solution, and it is fully mixed; Adsorbent after mixing is left standstill half an hour, treat the complete post precipitation of solid particle, remove unnecessary liquid, solid mixture is poured in the heating furnace, temperature is set to 80～100 ℃, dry 2h in the stove; Furnace temperature is risen to 600～800 ℃ then, constant temperature 3h calcines; To calcine back sample screening, keep sample between 50～100 μ m.

Embodiment 2

Take by weighing the 100kg saleratus and pour in the agitator vessel, water filling in container, stirring is simultaneously thoroughly dissolved saleratus; The wooden class active carbon of graininess that takes by weighing the 200kg diameter and be 100～200 μ m is poured into and is stirred 12h in the potassium bicarbonate solution, and it is fully mixed; Adsorbent after mixing is left standstill half an hour, treat the complete post precipitation of solid particle, remove unnecessary liquid, solid mixture is poured in the heating furnace, temperature is set to 80～100 ℃, dry 2h in the stove; Furnace temperature is risen to 600～800 ℃ then, constant temperature 3h calcines; To calcine back sample screening, keep sample between 100～200 μ m.

Embodiment 3

Take by weighing the 100kg saleratus and pour in the agitator vessel, water filling in container, stirring is simultaneously thoroughly dissolved saleratus; The wooden class active carbon of graininess that takes by weighing the 200kg diameter and be 200～300 μ m is poured into and is stirred 12h in the potassium bicarbonate solution, and it is fully mixed; Adsorbent after mixing is left standstill half an hour, treat the complete post precipitation of solid particle, remove unnecessary liquid, solid mixture is poured in the heating furnace, temperature is set to 80～100 ℃, dry 2h in the stove; Furnace temperature is risen to 600～800 ℃ then, constant temperature 3h calcines; To calcine back sample screening, keep sample between 200～300 μ m.

Claims (4)

1. the HIgh strength drying regeneration CO of a zeolite as carrier ₂Adsorbent, this adsorbent comprise active component and carrier two parts, and described active component is a hexagonal crystal system potash, account for the 30wt%～50wt% of adsorbent gross mass; Described carrier is a zeolite, accounts for the 50wt%～70wt% of adsorbent gross mass; This adsorbent is shaped as graininess, and mean particle size range is 50～300 μ m.

2. the HIgh strength drying regeneration CO of a kind of zeolite as carrier according to claim 1 ₂Adsorbent is characterized in that: described zeolite is an active carbon, and possess hydrophilic property, surface area are 400-800m ²/ g.

3. the HIgh strength drying regeneration CO of a kind of zeolite as carrier according to claim 1 ₂Adsorbent is characterized in that: described particle size range is 100～200 μ m.

4. the HIgh strength drying regeneration CO of a zeolite as carrier ₂The preparation of adsorbent method comprises:

(1) producing of potassium bicarbonate solution: take by weighing saleratus, the water dissolving obtains potassium bicarbonate solution;

(2) producing of carrier granular: taking by weighing with the saleratus weight ratio is 50～70: 30～50 zeolite, grinds and obtains the carrier granular that particle diameter is 50～300 μ m;

(3) mixing of active component and carrier: the carrier granular that step (2) obtains is put into potassium bicarbonate solution, stir 10～12h;

(4) drying: with the solution left standstill half an hour that step (3) obtains, treat the complete post precipitation of solid particle, remove unnecessary liquid, dry down in 80～100 ℃;

(5) calcining: with dried adsorbent calcining at constant temperature 2～3h under 600～800 ℃ of temperature;

(6) screening.

Images