CN103738961A - Method for preparing hollow and solid spherical active carbon by humus - Google Patents
Method for preparing hollow and solid spherical active carbon by humus Download PDFInfo
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- CN103738961A CN103738961A CN201310673086.XA CN201310673086A CN103738961A CN 103738961 A CN103738961 A CN 103738961A CN 201310673086 A CN201310673086 A CN 201310673086A CN 103738961 A CN103738961 A CN 103738961A
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Abstract
The invention discloses a method for preparing hollow and solid spherical active carbon by humus, and belongs to the technical field of active carbon. The method comprises the following steps: washing commercial humus with water to obtain water-soluble humus, performing alkali washing to obtain alkali-soluble humus; preparing a solution by the obtained humus, deionized water or ammonia aqueous solution, performing spray granulation at different temperature conditions to obtain hollow or solid carbon balls, and then performing carbonization and activation to obtain hollow or solid spherical active carbon. The advantages of the method of the invention are that: the adopted raw materials are low in price and wide in source; no addition of any organic solvent or balling auxiliary agent is necessary in the balling process; the preparation process is simple; the hollow or solid carbon balls are controllable; the ball size distribution is controllable; and the method is easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of by the controlled method of preparing hollow and solid ball shape active carbon of soil ulmin.Belong to activated carbon technology field.
Background technology
Ball shape active carbon is except having the height similar to conventional gac than table, and good sphericity, packing density is even, intensity is high, the series of advantages such as wear-resistant, corrosion-resistant, is widely used in the fields such as environmental protection, medicine, military affairs, energy storage.But the selection of presoma and preparation technology have very important impact for performance and the application of ball shape active carbon.At present commercial ball shape active carbon is mainly divided three classes by raw material difference: coal-based, resin base and asphalt-base spherical activated carbon; Pelletizing method mainly contains suspension method [Preparation of carbonaceous spheres from suspensions of pitch matericals], emulsion process [CN101792678A], disc granulation method [US4273675] and spray granulation [US7781370]; Nodularization, the oxidation that preparation technology generally comprises raw material do not melted, charing and activation.
Such as, although the nature of these traditional materials (density, softening temperature etc.) has larger difference, but pelletizing method exists common ground, be all to make raw material be molten state or liquid state, then solidify balling-up.Conventionally before balling-up, the technique such as need to carry out fragmentation to raw material, sieve, and in raw material, sneak into naphthalene etc. with reduce its softening temperature or by material dissolution in organic solvent, therefore in preparation process, raw material micro mist and volatilely have thing (naphthalene etc.) or organic solvent to be easily diffused into cause environmental pollution in air.In order to keep its spherical morphology, to use the ball shape active carbon prepared by traditional Carbon Materials must be through not melt processed of peroxidation, just can carry out charing and activation.
Summary of the invention
The object of the present invention is to provide a kind of method of being prepared hollow and solid ball shape active carbon by soil ulmin, the method process is simple, without being oxidized not melt processed, environmental pollution is little, yield is high, good sphericity, hollow or solid charcoal ball controlled and be easy to realize suitability for industrialized production.
The present invention implements by the following technical programs, and a kind of method of being prepared hollow sphere gac by soil ulmin, is characterized in that comprising the following steps:
(1) by commercial soil ulmin process deionized water dissolving, collect supernatant liquor, dry, obtain water humus (xanthohumic acid); Get its throw out; after dissolving with ammoniacal liquor, sodium hydroxide or the potassium hydroxide of pH>9 again; sedimentation and filtration obtains supernatant liquor; in clear liquid, drip the hydrochloric acid soln of 0.1M thereon; until pH<3; after standing 10-24h, form charcoal-aero gel, charcoal-aero gel is dry with deionized water wash, obtain caustic solubility soil ulmin (humic acids);
(2) water humus step (1) being made and deionized water are mixed with mass ratio for (0.01-0.2): solution (0.8-0.99); The caustic solubility soil ulmin that step (1) is made and the ammonia soln of pH>9 are hybridly prepared into mass ratio for (0.01-0.2): alkaline solution (0.8-0.99);
(3) step (2) is made water miscible and alkaline solution soil ulmin solution at feeding temperature, be 80-120 ℃, temperature out is 70-110 ℃, sample introduction flow velocity is 200-800L/h, operating pressure is 0.2-0.5MPa, blower fan frequency is 40-60Hz, nozzle diameter is to use sponging granulator to carry out mist projection granulating under the condition of 0.5-1mm, and obtaining particle diameter is the Carbon Hollow ball of 0.75 ~ 15 μ m;
(4) Carbon Hollow ball step (3) being made rises to 500 ~ 900 ℃ with the heat-up rate of 1 ~ 10 ℃/min under nitrogen protection atmosphere, and insulation 1 ~ 10h, cools to room temperature naturally, obtains the Carbon Hollow ball of charing;
(5) Carbon Hollow ball potassium hydroxide being made with step (4) is take alkali charcoal mass ratio as (0.5 ~ 3): 1 evenly mixes; under nitrogen protection atmosphere; with the heat-up rate of 1 ~ 10 ℃/min, rise to 750 ~ 950 ℃; insulation 1 ~ 5h; naturally cool to room temperature, obtain the hollow sphere gac of high-ratio surface.
By soil ulmin, prepared a method for solid ball shape active carbon, it is characterized in that comprising the following steps:
(1) by commercial soil ulmin process deionized water dissolving, collect supernatant liquor, dry, obtain water humus (xanthohumic acid); Get its throw out; after dissolving with ammoniacal liquor, sodium hydroxide or the potassium hydroxide of pH>9 again; filtering-depositing; in clear liquid, drip the hydrochloric acid soln of 0.1M thereon; until pH<3; after standing 10-24h, form charcoal-aero gel, charcoal-aero gel is dry with deionized water wash, obtain caustic solubility soil ulmin (humic acids);
(2) water humus step (1) being made and deionized water are mixed with mass ratio for (0.01-0.2): solution (0.8-0.99); The caustic solubility soil ulmin that step (1) is made and the ammonia soln of pH>9 are hybridly prepared into mass ratio for (0.01-0.2): alkaline solution (0.8-0.99);
(3) step (2) is made water miscible and alkaline solution soil ulmin solution at feeding temperature, be 30-75 ℃, temperature out is 20-63 ℃, sample introduction flow velocity is 200-800L/h, operating pressure is 0.2-0.5MPa, blower fan frequency is 40-60Hz, nozzle diameter is to carry out mist projection granulating under the condition of 0.5-1mm, and obtaining particle diameter is the solid charcoal ball of 0.5 ~ 10 μ m;
(4) solid charcoal ball step (3) being made rises to 500 ~ 900 ℃ with the heat-up rate of 1 ~ 10 ℃/min under nitrogen protection atmosphere, and insulation 1 ~ 10h, cools to room temperature naturally, obtains the solid charcoal ball of charing;
(5) solid charcoal ball potassium hydroxide being made with step (4) is take alkali charcoal mass ratio as (0.5 ~ 3): 1 evenly mixes; under nitrogen protection atmosphere; with the heat-up rate of 1 ~ 10 ℃/min, rise to 750 ~ 950 ℃; insulation 1 ~ 5h; naturally cool to room temperature, obtain the solid ball shape active carbon of high-ratio surface.
Tool of the present invention has the following advantages: the cost of material that 1) the present invention adopts is cheap, is extensively present in occurring in nature, and such as soil, water body and weathered coal etc. also can obtain by microbiological deterioration organic matter simultaneously; 2) in balling-up process without adding any organic solvent and balling-up auxiliary agent; 3) its preparation technology is simple, hollow/solid charcoal ball is controlled, ball size distribution is controlled and be easy to realize suitability for industrialized production; 4) this technology has avoided being oxidized not melting process, and directly charing, activation two steps obtain the gac of Gao Bibiao.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the prepared hollow sphere gac of embodiment 1.
Fig. 2 is the electron scanning micrograph of the hollow sphere gac after the prepared fragmentation of embodiment 1.
Fig. 3 is the electron scanning micrograph of embodiment 1 prepared solid ball shape active carbon.
Fig. 4 is the electron scanning micrograph of the solid ball shape active carbon after the prepared fragmentation of embodiment 1.
Embodiment
Embodiment 1
1, the soil ulmin of 50g commercialization is placed in to the deionized water of 2L, under the condition that is 400r/min at rotating speed, stirs 1h.Centrifugation after it fully dissolves, collects supernatant liquor 1.8L and is placed in after the dry 60h of 90 ℃ of baking ovens, obtains 12g water humus;
2,, under the condition that is 100r/min in room temperature and stir speed (S.S.), to the water humus 10g that adds step 1 to obtain in 90g deionized water, constant temperature stirs after 1h standby;
3, by the 100g soil ulmin aqueous solution in step 2, at feeding temperature, be that 90 ℃, temperature out are 77 ℃, sample introduction flow velocity is that under the condition of 400L/h, to adopt nozzle diameter be 0.75mm, operating pressure is 0.2MPa, blower fan frequency is that (Shanghai is along instrument experimental installation company limited for the experiment press spray tablets press of 40Hz, model: SP-1500) carry out mist projection granulating, make Carbon Hollow ball;
4, the Carbon Hollow ball of step 3 is risen to 600 ℃ with the heat-up rate of 1 ℃/min under nitrogen atmosphere, and at 600 ℃ of insulation 1h, naturally cool to room temperature, take out, obtain the Carbon Hollow spherolite of charing;
5, charing Carbon Hollow ball potassium hydroxide being made with step 4 evenly mixes as 3 take alkali charcoal mass ratio, and under nitrogen protection atmosphere, the heat-up rate of 2 ℃/min rises to 800 ℃; and at 800 ℃ of insulation 1h; naturally cool to room temperature, take out, obtain hollow sphere gac.By scanning electronic microscope (seeing Fig. 1), observe, the spherical morphology of ball shape active carbon remains intact, and size distribution is between 3-11 μ m, and its specific surface area is 2720 m
2/ g; Fig. 2 is the scanning electron microscope diagram of hollow sphere gac after 150 MPa pressure.
Embodiment 2
The present embodiment process is identical with embodiment 1, and difference is: by 90 ℃, changing the feeding temperature in step (3) into 60 ℃, temperature out is 45 ℃, and the specific surface area that finally obtains the solid ball shape active carbon of size distribution between 1-10 μ m is 2387 m
2/ g; Fig. 3 and 4 is respectively solid ball shape active carbon and the scanning electron microscope diagram after 150 MPa pressure thereof
Embodiment 3
1, by commercial 60g soil ulmin process deionized water dissolving, get the sodium hydroxide solution (PH=10) that its throw out is placed in 2L, under the condition that is 200r/min at rotating speed, stir 1h.Centrifugation after it fully dissolves, collects upper strata soluble part, drips the hydrochloric acid soln of 0.1M, until solution PH=2.3, standing 15h forms charcoal-aero gel.With deionized water, gel is repeatedly washed, is filtered to filtrate and show after neutrality, gel is placed in to the dry 24h of 80 ℃ of baking ovens, obtain 43g caustic solubility soil ulmin (humic acids);
2, under the condition that is 150r/min in room temperature and stir speed (S.S.), to the caustic solubility soil ulmin 20g that adds step 1 to obtain in 80g ammonia soln (PH=10), standby after stirring at normal temperature 2h;
3, by the alkaline solution of the 100g soil ulmin in step 2, at feeding temperature, be that 80 ℃, temperature out are 71 ℃, sample introduction flow velocity is that under the condition of 500L/h, to adopt nozzle diameter be 0.60mm, operating pressure is 0.4MPa, blower fan frequency is that the experiment press spray tablets press of 45Hz carries out mist projection granulating, makes solid charcoal ball;
4, the charcoal ball of step 3 is risen to 500 ℃ with the heat-up rate of 5 ℃/min under nitrogen atmosphere, and at 500 ℃ of insulation 3h, naturally cool to room temperature, take out, obtain the charcoal ball of charing;
5, charing charcoal ball potassium hydroxide being made with step 4 mixes take alkali charcoal mass ratio as 2; under nitrogen protection atmosphere; the heat-up rate of 4 ℃/min rises to 850 ℃; and at 850 ℃ of insulation 2h; naturally cool to room temperature; take out, obtain size distribution hollow sphere gac between 0.8-14 μ m.The spherical morphology of hollow sphere gac still remains intact, and its specific surface area is 2480m
2/ g;
Embodiment 4
The present embodiment process is identical with embodiment 3, and difference is: by 80 ℃, changing the feeding temperature in step (3) into 60 ℃, temperature out is 50 ℃, and the specific surface area that finally obtains the solid ball shape active carbon of size distribution between 0.80-9 μ m is 2050m
2/ g.
Embodiment 5
1, the soil ulmin of 45g commercialization is placed in to the deionized water of 1L, under the condition that is 350r/min at rotating speed, stirs 3h.Centrifugation after it fully dissolves, collects supernatant liquor 0.9L and is placed in after the dry 40h of 90 ℃ of baking ovens, obtains 10g water humus;
2,, under the condition that is 250r/min in room temperature and stir speed (S.S.), to the water humus 10g that adds step 1 to obtain in 190g deionized water, constant temperature stirs after 1h standby;
3, by the 200g soil ulmin aqueous solution in step 2, at feeding temperature, be that 110 ℃, temperature out are 105 ℃, sample introduction flow velocity is that under the condition of 700L/h, to adopt nozzle diameter be 1mm, operating pressure is 0.35MPa, blower fan frequency is that the experiment press spray tablets press of 55Hz carries out mist projection granulating, makes Carbon Hollow ball;
4, the Carbon Hollow ball of step 3 is risen to 800 ℃ with the heat-up rate of 10 ℃/min under nitrogen atmosphere, and at 800 ℃ of insulation 6h, naturally cool to room temperature, take out, obtain the Carbon Hollow spherolite of charing;
5, charing Carbon Hollow ball potassium hydroxide being made with step 4 carries out evenly mixing take alkali charcoal mass ratio as 0.5; under nitrogen protection atmosphere; the heat-up rate of 5 ℃/min rises to 800 ℃; and at 800 ℃ of insulation 1h; naturally cool to room temperature; take out, obtain the hollow sphere gac of size distribution between 1-13 μ m, its specific surface area is 1507 m
2/ g.
Embodiment 6
1, by commercial 80g soil ulmin process deionized water dissolving, get the potassium hydroxide solution (PH=11.3) that its throw out is placed in 2.5L, under the condition that is 500r/min at rotating speed, stir 2h.Centrifugation after it fully dissolves, collects upper strata soluble part, drips the hydrochloric acid soln of 0.1M, until solution PH=1.5 form charcoal-aero gel after standing 24h.With deionized water, gel is repeatedly washed, is filtered to filtrate and show after neutrality, gel is placed in to the dry 30h of 80 ℃ of baking ovens, obtain 60g caustic solubility soil ulmin (humic acids);
2, under the condition that is 300r/min in room temperature and stir speed (S.S.), to the caustic solubility soil ulmin 20g that adds step 1 to obtain in 380g ammonia soln (PH=12), standby after stirring at normal temperature 1h;
3, by the alkaline solution of the 400g soil ulmin in step 2, at feeding temperature, be that 50 ℃, temperature out are 45 ℃, sample introduction flow velocity is that under the condition of 450L/h, to adopt nozzle diameter be 0.70mm, operating pressure is 0.5MPa, blower fan frequency is that the experiment press spray tablets press of 60Hz carries out mist projection granulating, makes charcoal ball;
4, the charcoal ball of step 3 is risen to 900 ℃ with the heat-up rate of 10 ℃/min under nitrogen atmosphere, and at 900 ℃ of insulation 2h, naturally cool to room temperature, take out, obtain the charcoal ball of charing;
5, charing charcoal ball potassium hydroxide being made with step 4 mixes take alkali charcoal mass ratio as 1; under nitrogen protection atmosphere; the heat-up rate of 5 ℃/min rises to 900 ℃; and at 900 ℃ of insulation 3h; naturally cool to room temperature; take out, obtain the solid ball shape active carbon of size distribution between 0.6-10 μ m, its specific surface area is 1659 m
2/ g.
Claims (2)
1. the method for kind being prepared hollow sphere gac by soil ulmin, is characterized in that comprising the following steps:
(1) by commercial soil ulmin process deionized water dissolving, collect supernatant liquor, dry, obtain water humus; Get its throw out; after dissolving with ammoniacal liquor, sodium hydroxide or the potassium hydroxide of pH>9 again; sedimentation and filtration obtains supernatant liquor; in clear liquid, drip the hydrochloric acid soln of 0.1M thereon; until pH<3; after standing 10-24h, form charcoal-aero gel, charcoal-aero gel is dry with deionized water wash, obtain caustic solubility soil ulmin;
(2) water humus step (1) being made and deionized water are mixed with mass ratio for (0.01-0.2): solution (0.8-0.99); The caustic solubility soil ulmin that step (1) is made and the ammonia soln of pH>9 are hybridly prepared into mass ratio for (0.01-0.2): alkaline solution (0.8-0.99);
(3) step (2) is made water miscible and alkaline solution soil ulmin solution at feeding temperature, be 80-120 ℃, temperature out is 70-110 ℃, sample introduction flow velocity is 200-800L/h, operating pressure is 0.2-0.5MPa, blower fan frequency is 40-60Hz, nozzle diameter is to use sponging granulator to carry out mist projection granulating under the condition of 0.5-1mm, and obtaining particle diameter is the Carbon Hollow ball of 0.75 ~ 15 μ m;
(4) Carbon Hollow ball step (3) being made rises to 500 ~ 900 ℃ with the heat-up rate of 1 ~ 10 ℃/min under nitrogen protection atmosphere, and insulation 1 ~ 10h, cools to room temperature naturally, obtains the Carbon Hollow ball of charing;
(5) Carbon Hollow ball potassium hydroxide being made with step (4) is take alkali charcoal mass ratio as (0.5 ~ 3): 1 evenly mixes; under nitrogen protection atmosphere; with the heat-up rate of 1 ~ 10 ℃/min, rise to 750 ~ 950 ℃; insulation 1 ~ 5h; naturally cool to room temperature, obtain the hollow sphere gac of high-ratio surface.
2. a method of being prepared solid ball shape active carbon by soil ulmin, is characterized in that comprising the following steps:
(1) by commercial soil ulmin process deionized water dissolving, collect supernatant liquor, dry, obtain water humus; Get its throw out; after dissolving with ammoniacal liquor, sodium hydroxide or the potassium hydroxide of pH>9 again; filtering-depositing; in clear liquid, drip the hydrochloric acid soln of 0.1M thereon; until pH<3; after standing 10-24h, form charcoal-aero gel, charcoal-aero gel is dry with deionized water wash, obtain caustic solubility soil ulmin;
(2) water humus step (1) being made and deionized water are mixed with mass ratio for (0.01-0.2): solution (0.8-0.99); The caustic solubility soil ulmin that step (1) is made and the ammonia soln of pH>9 are hybridly prepared into mass ratio for (0.01-0.2): alkaline solution (0.8-0.99);
(3) step (2) is made water miscible and alkaline solution soil ulmin solution at feeding temperature, be 30-75 ℃, temperature out is 20-63 ℃, sample introduction flow velocity is 200-800L/h, operating pressure is 0.2-0.5MPa, blower fan frequency is 40-60Hz, nozzle diameter is to carry out mist projection granulating under the condition of 0.5-1mm, and obtaining particle diameter is the solid charcoal ball of 0.5 ~ 10 μ m;
(4) solid charcoal ball step (3) being made rises to 500 ~ 900 ℃ with the heat-up rate of 1 ~ 10 ℃/min under nitrogen protection atmosphere, and insulation 1 ~ 10h, cools to room temperature naturally, obtains the solid charcoal ball of charing;
(5) solid charcoal ball potassium hydroxide being made with step (4) is take alkali charcoal mass ratio as (0.5 ~ 3): 1 evenly mixes; under nitrogen protection atmosphere; with the heat-up rate of 1 ~ 10 ℃/min, rise to 750 ~ 950 ℃; insulation 1 ~ 5h; naturally cool to room temperature, obtain the solid ball shape active carbon of high-ratio surface.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106075442A (en) * | 2016-07-04 | 2016-11-09 | 同济大学 | There is preparation method and the purposes of the medicine carrying hollow carbon sphere of photothermal conversion effect |
| CN108946721A (en) * | 2018-07-16 | 2018-12-07 | 深圳市环球绿地新材料有限公司 | Spherical activated charcoal of high compressive strength and its preparation method and application |
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| CN1607174A (en) * | 2003-09-25 | 2005-04-20 | 吴羽化学工业株式会社 | Process for producing spherical activated carbon |
| JP2005132696A (en) * | 2003-10-31 | 2005-05-26 | Japan Organo Co Ltd | Activated carbon precursor and activated carbon |
| CN101143720A (en) * | 2006-09-29 | 2008-03-19 | 北京化工大学 | Active carbon micro-sphere absorption material and preparation method thereof |
| CN101343060A (en) * | 2008-08-01 | 2009-01-14 | 王德福 | Organic absorbent charcoal and preparing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607174A (en) * | 2003-09-25 | 2005-04-20 | 吴羽化学工业株式会社 | Process for producing spherical activated carbon |
| JP2005132696A (en) * | 2003-10-31 | 2005-05-26 | Japan Organo Co Ltd | Activated carbon precursor and activated carbon |
| CN101143720A (en) * | 2006-09-29 | 2008-03-19 | 北京化工大学 | Active carbon micro-sphere absorption material and preparation method thereof |
| CN101343060A (en) * | 2008-08-01 | 2009-01-14 | 王德福 | Organic absorbent charcoal and preparing method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106075442A (en) * | 2016-07-04 | 2016-11-09 | 同济大学 | There is preparation method and the purposes of the medicine carrying hollow carbon sphere of photothermal conversion effect |
| CN106075442B (en) * | 2016-07-04 | 2022-08-19 | 同济大学 | Preparation method and application of drug-loaded hollow carbon sphere with photo-thermal conversion effect |
| CN108946721A (en) * | 2018-07-16 | 2018-12-07 | 深圳市环球绿地新材料有限公司 | Spherical activated charcoal of high compressive strength and its preparation method and application |
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