CN100588457C - Shaping method for super absorbent charcoal powder body for adsorbing CO2 - Google Patents

Abstract

The present invention discloses a molding method of powder super activated carbon at the temperature of 0 to 50 DEG C. The present invention is characterized in that when thermosetting phenol-formaldehyde resin is taken as the binding agent and oil pressure molding technique is adopted to prepare the super activated carbon, the super activated carbon can be directly molded at the temperature of 0to 50 DEG C by adding auxiliary binding agents such as carboxymethyl cellulose, methyl cellulose, cellulose, PTFE, PVC, hexamethylene tetramine and tar, etc. The method of the present invention correspondingly reduces the content of the thermosetting phenol-formaldehyde resin binding agent and improves the surface area utilization rate of the super activated carbon; the auxiliary binding agents are cracked in the final carbonization process, thus forming a good gas diffusion channel and improving CO2 molecule dispersion as well as absorption and desorption rate.

Description

A kind of CO absorption 2Forming method with super absorbent charcoal powder body

Technical field:

The present invention relates to a kind of forming method of super absorbent charcoal powder body.Belong to a kind of CO of being used for ₂The preparation method of the moulding super-activated carbon of absorption.

Background technology:

The 4th part of report that the Intergovernmental Panel on Climate Change of UNEP (United Nations Environment Program) (IPCC) delivers at the beginning of 2007 points out that climate warming is the fact of " free from controversy ", and the possibility more than 90% is that mankind's activity has caused climate warming.The CO of a large amount of dischargings of industry such as coal-burning power plant, steel and cement wherein ₂Be one of most important greenhouse gases that cause climate change.China in 2005 is the CO that is only second to the U.S. ₂Discharging big country, expectation may very soon will be above the U.S..As one of United Nations Framework Convention on Climate Change contract party, the minimizing CO that China is faced after this pact comes into force ₂The pressure of discharging is very severe.Reach with energy-saving and cost-reducing, exploitation regenerative resource etc. except employing new technology and to reduce discharging the purpose CO ₂Capturing and seal up for safekeeping technology (CCS) is one of present internationally recognized effective solution route.

Super-activated carbon is a kind of novel carbonaceous porous adsorbing material, has the incomparable ultra-high surface area of other porous material and (reaches as high as 4000m ²/ g), modify by the chemical vapor deposition (CVD) technology in later stage, not only the aperture can be controlled in 0～2nm scope, and can be at CO ₂Molecular characterization modify its surface chemistry environment, thereby when having high-adsorption-capacity, have high selective adsorption capacity.Though super-activated carbon has remarkable characteristics such as adsorption desorption speed is fast, regeneration condition is gentle, serviceability temperature wide spectrum especially to this class linear molecule, but because of it is superfine powder (particle diameter is at 5～50 a μ m) material, at the practical application (CO that produces as industrial process such as coal-burning power plants ₂Gaseous mixture) must be made into type body material, otherwise gas can produce very big pressure drop by bed, even channel or adsorbent such as are blown at unfavorable phenomenon.Thermosetting phenolic resin is a kind of binding agent of routine, when be binding agent the time, must heat-treat super-activated carbon/binder mixtures 180～350 ℃ of elder generations, and then carry out moulding.This method operation easier is big, and the specific area utilization rate of super-activated carbon is low, and has certain energy consumption.To this,, add additional adhesive and directly super-activated carbon is carried out moulding, and the specific area utilization rate is higher, then has very large practical significance if can under normal temperature (0～50 ℃) condition, be binding agent with the thermosetting phenolic resin.

Summary of the invention:

The object of the present invention is to provide a kind of forming technique of the super absorbent charcoal powder body under 0～50 ℃ of condition.This method technology is simple, binder content is low, and the utilization rate of super-activated carbon specific area is high and have a good gas diffusion paths structure.

The present invention realizes by following proposal, it is characterized in that comprising following process:

(1) additional adhesive of easy cracking is dissolved in boiling water and stirring, is mixed and made into slurry with super-activated carbon after being cooled to 20～70 ℃, super-activated carbon accounts for 5～20% of slurry quality;

(2) thermosetting phenolic resin is dissolved in ethanol, and mix with above-mentioned slurry material, roller drives away, wherein thermosetting phenolic resin accounts for 5～60% of super-activated carbon quality;

(3) mixture that step (2) is obtained grinds then in 100～200 ℃ of down dry 1～5h, makes super-activated carbon/additional adhesive/phenolic resins powder material, and making its particle diameter is 3～100 μ m;

(4) with above-mentioned powder material in 0～50 ℃, adopt the oil pressure forming technique, under the pressure of 3～30MPa, make the super-activated carbon formed body of required size;

(5) step (4) gained formed body is placed retort, heating rate with 2～10 ℃/min successively is warming up to 120～250 ℃, 500～1000 ℃ then, and equal constant temperature 1～3h, naturally cool to 20～50 ℃ after, promptly make the super-activated carbon of moulding, be used for CO absorption ₂

Above-mentioned additional adhesive is a kind of in carboxymethyl cellulose and the methylcellulose.

In the above-mentioned technology, be the super-activated carbon/additional adhesive/phenolic resins mixture that will make, making particle diameter earlier is the powder material of 3～100 μ m, carries out moulding then.

Above-mentioned super-activated carbon is that specific area is greater than 2000m ²The active carbon of/g

Beneficial effect

The invention has the advantages that: make binding agent with thermosetting phenolic resin,, realized the straight forming of super-activated carbon under 0～50 ℃ of condition cut down the consumption of energy by the interpolation of additional adhesive; The interpolation of additional adhesive, the corresponding content that reduces the thermosetting phenolic resin binding agent makes the surface area utilization rate of super-activated carbon improve; The cracking of additional adhesive in carbonization process formed good gas diffusion paths, improved CO ₂The diffusion of molecule, adsorption desorption speed.

The specific embodiment

[Comparative Examples one]

(particle diameter is 20 μ m, and specific area is 3000m with 40g thermosetting phenolic resin and 200g super-activated carbon ²/ g) carry out mechanical mixture, take by weighing the 10g mixture then and place the hot-forming container of column (internal diameter 15mm, high 40mm, outer heating) in, again the hot pressing container is placed on the oil pressure former, be warming up to 250 ℃ and constant temperature 3h with the heating rate of 3 ℃/min and be cured heat treatment, after naturally cooling to 30 ℃, get material, obtain column super-activated carbon formed body, but mechanical strength is lower.Again the column super-activated carbon is placed retort, is warming up to 800 ℃ and constant temperature 3h with the heating rate of 5 ℃/min and carries out charing heat treatment, naturally cool to 30 ℃ after, make The column super-activated carbon, its specific area is 1200m ²/ g, compressive strength is 9MPa, under the normal pressure to CO ₂(CO ₂The concentration of gas is 6.5%) equilibrium adsorption capacity be 0.23mmol/g.

[Comparative Examples two]

The 40g thermosetting phenolic resin is dissolved in the 150ml ethanolic solution, and (particle diameter is 20 μ m, and specific area is 3000m with the 200g super-activated carbon ²/ g) mix.The gained mixture placed 100 ℃ vacuum drying oven, dry 2h, take out and be ground to 20 μ m after being cooled to 30 ℃, take by weighing the 10g mixture and place column container molding (internal diameter 15mm, high 40mm) in, again the hot pressing container is placed on the oil pressure former constant voltage 10min under 20MPa, material is got in pressure release, and the gained mixture still is the powder material.As seen, do not add additional adhesive owing to key in, so under 0～50 ℃ of normal temperature, can't obtain the active carbon of moulding.

[embodiment]

Take by weighing the 10g methylcellulose, be dissolved in the boiling water of 150ml and stir 30min, wait solution temperature to reduce to 30 ℃ after, (particle diameter is 20 μ m, and specific area is 3000m with super-activated carbon with 200g ²/ g) progressively add in the made methocel solution, and carry out mechanical mixture.The 40g thermosetting phenolic resin is dissolved in the 150ml ethanolic solution, after stirring 10min, thermosetting phenolic resin solution is added in super-activated carbon/methylcellulose mixture, carry out mechanical mixture once more, to be mixed evenly after, place 100 ℃ vacuum drying oven, dry 2h takes out and is ground to 20 μ m after being cooled to 30 ℃.Take by weighing the 10g mixture and place in the column container molding (internal diameter 15mm, high 40mm), again the hot pressing container is placed on the oil pressure former, under 25 ℃ of room temperatures under 20MPa constant voltage 10min, material is got in pressure release, makes The column super-activated carbon.Column-shaped active carbon is placed retort, successively be warming up to 200 ℃, 800 ℃ with the heating rate of 5 ℃/min, and constant temperature 0.5,1h respectively, naturally cool to 30 ℃ again, get material, promptly making specific area is 2650m ²The column super-activated carbon of/g, its compressive strength is 14MPa, under the normal pressure to CO ₂(CO ₂The concentration of gas is 6.5%) equilibrium adsorption capacity be 0.56mmol/g.

Claims (1)

1, a kind of CO absorption ₂Forming method with super absorbent charcoal powder body is characterized in that, the step of described method is as follows:

(1) additional adhesive of easy cracking is dissolved in boiling water and stirring, is mixed and made into slurry with super-activated carbon after being cooled to 20～70 ℃, super-activated carbon accounts for 5～20% of slurry quality;

(2) thermosetting phenolic resin is dissolved in ethanol, and mix with above-mentioned slurry material, roller drives away, wherein thermosetting phenolic resin accounts for 5～60% of super-activated carbon quality;

(3) mixture that step (2) is obtained grinds then in 100～200 ℃ of down dry 1～5h, makes super-activated carbon/additional adhesive/phenolic resins powder material, and making its particle diameter is 3～100 μ m;

(4) with above-mentioned powder material in 0～50 ℃, adopt the oil pressure forming technique, under the pressure of 3～30MPa, make the super-activated carbon formed body of required size;

(5) step (4) gained formed body is placed retort, heating rate with 2～10 ℃/min successively is warming up to 120～250 ℃, 500～1000 ℃ then, and equal constant temperature 1～3h, naturally cool to 20～50 ℃ after, promptly make the super-activated carbon of moulding, be used for CO absorption ₂

Wherein, described additional adhesive is a kind of in carboxymethyl cellulose and the methylcellulose.