CN101204646A - Process for sorbing material using soot - Google Patents
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- CN101204646A CN101204646A CNA2007100028647A CN200710002864A CN101204646A CN 101204646 A CN101204646 A CN 101204646A CN A2007100028647 A CNA2007100028647 A CN A2007100028647A CN 200710002864 A CN200710002864 A CN 200710002864A CN 101204646 A CN101204646 A CN 101204646A
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Abstract
A method of preparing a sorbing material by coal ash is provided by the invention, which mainly utilizes the screening technique to separate unburned carbon from coal ash; the unburned carbon is then processed by vapor or carbon dioxide to cause a plurality of micro-holes forming on surface of the unburned carbon and becoming absorbing space that can contain micro-substance; the sorbing material thus prepared has high porosity, large adsorbance, high adsorbance efficiency and low cost, and can be used as a sorbing material for processing wastewater.
Description
Technical field
The present invention relates to a kind of method of making sorbing material with coal ash, utilize triage techniques specifically, unburned carbon in the sorting coal ash, utilize the steam activation technology again, carry out the unburned carbon surface treatment, and then prepare that adsorbance is big, adsorption efficiency is good, and and it is with low cost, be used to handle the sorbing material of waste water.
Background technology
The generating capacity of coal ash is huge, has approximately every year about 2,100,000 tons, and it utilizes mode mainly is as cement additive, utilization rate is about 60% again, and remaining part need be carried out offal treatment, because quantity reaches about more than 1,000,000 tons, carry out the difficulty height of handling, become environmental issue.
Utilize outside the present situation above-mentioned, other possible purposes of coal ash was also once proposed in the correlative study document both at home and abroad, have abilities such as Adsorption of Heavy Metal Ions and organic matter as coal ash, it can supply to handle heavy metal wastewater therebies such as Cr VI, divalence cadmium, cupric, divalence mercury, divalent zinc, ferric iron, and general organic dye waste water.This is that these oxides have surface charge in water, adsorbable different charge ion owing to contain oxides (as table 1) such as the silicon of having an appointment more than 70%, aluminium, iron in the composition of coal ash.Contain a spot of unburned carbon in addition in the coal ash, the surperficial adsorb organic compound matter of Fan Dewaerli that can be faint (Vander Wall force).But generally speaking, the adsorbance of coal ash is low, far below commercially available wastewater treatment sorbing material, need a large amount of interpolations just can reach pollution emission standard, therefore a large amount of coal ash is added in the waste water reluctantly, the usefulness in the hope of for the absorption heavy metal just causes the sludge quantity in the waste water to heighten.
In view of this, the present invention researches and develops the method for making high adsorption capacity, sorbing material that cost is low with coal ash then, and then invent out with material sieving technology and sub-elect the unburned carbon composition, utilize high-temperature activation technical finesse unburned carbon again, make the surface of unburned carbon form numerous fine holes, become the space that can hold a large amount of adsorbents; The adsorbent porosity height that the method manufactures, adsorbance is big, and adsorption efficiency is good, and with low cost, not only can be applied to handle waste water, also can achieve the utilization again of coal ash on the other hand, effectively improves the difficult problem of a large amount of pending coal ash.
The chemical composition of table 1 coal ash
| Sample | CS1 | CS2 | SD |
| Physical property | |||
| Appearance color | Light/dark balance | Aterrimus | Brown |
| Meta particle diameter (μ m) | 22.5 | 51.7 | 29.3 |
| Density (g/cm 3) | 2.20 | 2.07 | 2.42 |
| Chemical composition and character | |||
| SiO 2 | 44.4 | 34.0 | 51.8 |
| Al 2O 3 | 18.6 | 14.9 | 19.2 |
| Fe 2O 3 | 2.2 | 8.6 | 6.1 |
| CaO | 0.7 | 3.4 | 3.3 |
| MgO | 0.6 | 0.4 | 1.8 |
| Na 2O | 1.3 | 1.1 | 1.4 |
| K 2O | 0.7 | 0.5 | 0.8 |
| TiO 2 | 0.4 | 1.0 | 1.1 |
| SO 3 | 0.8 | 0.1 | 0.5 |
| C | 23.3 | 31.2 | 6.7 |
| Loss on ignition (%) | 24.5 | 33.4 | 7.4 |
| The pH value | 8.1 | 8.5 | 9.5 |
Summary of the invention
Coal ash is the accessory substance of coal-burning boiler, and the composition of coal ash is made of oxide and a spot of carbon, and wherein oxide ratios is at least more than 70%, the carbon (table 1) that remaining then is about several percentages to 30%.The fine particles of oxide is that carbon is then thicker about several microns, about tens of microns are to hundred microns, can utilize technology such as suitable screening, flotation that aforementioned particulate is carried out sorting in technique of preparing.
In addition, the carbon component in the coal ash is the imperfect combustion remaining particle of coal, utilizes the surface of steam activation carbon, can form numerous small holes, cause bigger serface, absorption property can reach the quality of general commercially available adsorption production, can become high performance sorbing material.
Therefore use technique of preparing, the carbon in the coal ash is concentrated, again carbon is applied surface activation process, the specific area of carbon is increased, produce the sorbing material of high absorption property thus.
The inventor is by result's (by table 2) of coal ash screening, and the distribution of carbon deflection is utilized and screened the coarse component that concentrates out at coarse component as can be known, and preferable carbon grade is about about 50～70% (weight).If utilize the aspect as a result of flotation sorting, show that according to existing document the preferable carbon grade in floating ore deposit is about about 45～70% (weight).Though have separating effect, main with sorbing material for still not high enough for the carbon grade (part by weight) of absorption, can cause the whole adsorption efficiency of sorbing material on the low side.According to microscopical observation, the particle of coal ash unburned carbon contains the hole of several microns sizes, can find to have in the hole existence of oxide particle by microscope, there is the oxide particle in the hole in these, when sorting, concentrate on the screen cloth together or in the floating ore deposit, cause the carbon grade not high along with carbon granules.For breaking through this restriction to improve the carbon grade, the present invention uses ultrasonic wave to handle, place water to import ultrasonic wave again coal ash, oxide is fully disperseed, in the hole of carbon, shift out, reach the good separation of two class particles, carry out sorting with wet type screening or flotation technology again, screening can obtain carbon grade product on the sieve more than 90%, and the carbon grade of float product also reaches more than 85%.
Table 2 flying dust sample dry type results of screening
Aspect activation processing because the chemical stability of carbon is good, with general chemical agent difficulty react, and easily and oxidizing gas such as oxygen, carbon monoxide/carbon dioxide, steam react.Slow, the fast order of carbon and these gas reaction speed is carbon dioxide/carbon monoxide＜steam＜oxygen etc., wherein the reaction with oxygen is exothermic reaction, be difficult to control reaction temperature, therefore the present invention adopts steam, carbon dioxide/carbon monoxide etc. as activated gas, carry out surface activation process, so that the surface of carbon concentration matter can obtain preferable activation effect after reaction.
The present invention proposes the method that coal ash is made sorbing material, can produce the sorbing material of high absorption property, the senior activated carbon product that quality/absorption property and general commercially available wastewater treatment are used is suitable, and because the preparation raw material is taken from discarded object, so can significantly reduce manufacturing cost, the estimation per ton cost below 300 yuan, is about 1/2nd of commercially available senior activated carbon product at U.S. dollar, market advantage height.And the coal ash source is sufficient, raw material is obtained easily, help a large amount of productions, treat disposal concerns and use coal ash not only can solve domestic a large amount of coal ash, low, the high adsorption efficiency of its cost of made sorbing material can significantly reduce expensive cost for wastewater treatment, extensively is supplied in wastewater treatment, safeguard environmental quality, have the double effects of the treatment of wastes with processes of wastes against one another.
Generally speaking, the a kind of of invention makes the method for sorbing material with coal ash, mainly is fire coal ash is sub-elected unburned carbon with triage techniques, again unburned carbon carried out the high-temperature activation processing, make the surface of unburned carbon form numerous fine holes, become for the adsorption space that holds small material; Constituting thus can be for the sorbing material of handling waste water.
Specifically, of the present inventionly a kind ofly make the method for sorbing material, it is characterized in that its concrete implementation step is with coal ash:
(1) separates the coal ash constituent: at first coal ash and water are fully mixed, mixed liquor is imported ultrasonic wave, fully disperse to cause the coal ash constituent;
(2) carry out the carbon processing of concentrating: after step (1) ultrasonic wave is handled, use the wet type screening to carry out the carbon processing of concentrating again;
(3) activation processing: will carry out the high-temperature activation processing by the carbon concentration matter of gained after step (2), and to form numerous holes on carbon surface, promote specific area, becoming can be for the space of absorption.
After the activation processing step of step (3), also can carry out once more the carbon processing of concentrating, with the absorption property of further raising sorbing material.
Description of drawings
Figure 1 shows that the step of the inventive method;
Figure 2 shows that flow rates is to promoting the effect of activation products specific area;
Figure 3 shows that the steam activation temperature is to promoting the effect of activation products specific area;
Figure 4 shows that the carbon dioxide activation temperature is to promoting the effect of activation products specific area.
The specific embodiment
The inventive method mainly comprises ultrasonic wave and handle to separate coal ash constituent, carbon and concentrate and handle and with steps such as high-temperature activation carbon concentration matters.Relevant the present invention reaches the effect of above-mentioned expection and purpose, and the technological means of being used is enumerated embodiment now and is described as follows in detail:
Embodiment one
At first, please cooperate consult shown in Figure 1:
(1) separates the coal ash constituent: at first coal ash and water are mixed (solid-to-liquid ratio=1g: 20ml), mixed liquor is imported ultrasonic wave (20KHz), fully disperse to cause coal ash constituent (oxide particle and carbon granule);
(2) carry out the carbon processing of concentrating: handle through step (1) ultrasonic wave, use the wet type screening again, take out the above part of 400 orders, ultrasonic wave processing its carbon grade after 10 minutes can reach (table 3 is consulted in cooperation) more than 85%, and again after 15 minutes, then can obtain the carbon grade and (as table 3, can find out that ultrasonic wave handles the effect that carbon is concentrated up to 90.5% carbon concentration matter, the preferable time, the carbon grade of concentration matter can be up to 90.5% about about 15 minutes).
Table 3 ultrasonic wave is handled the effect that promotes concentration matter carbon grade
| Ultrasonic treatment time (min) | The part by weight of+400 order concentration matters (%) | The carbon grade (%) of+400 order concentration matters |
| When initial | 30.4 | 56.9 |
| 5 | 24.6 | 70.9 |
| 10 | 20.5 | 85.1 |
| 15 | 19.9 | 90.5 |
| 20 | 19.9 | 90.6 |
(ultrasonic frequency 20KHz, solid-to-liquid ratio=1g: 20ml)
(3) activation processing: will carry out the steam activation processing by gained carbon concentration matter (the carbon grade is 90.5%) after step (2), and to form numerous holes on carbon surface, promote specific area, becoming can be for the space of absorption.By shown in Figure 2, can find out flow rates to promoting the effect of activation products specific area, preferable condition is more than the about 8cm/min of flow rates; Again as seen from Figure 3 temperature and time to promoting the effect of product specific area: when activation temperature be about 3 hours of 900 ℃-soak time, activation temperature be about 1.5 hours of 950 ℃-soak time, when activation temperature be 1, preferable soak time is about 0.5 hour in the time of 000 ℃, and the product specific area of acquisition is at 750～800m
2Between/the g,, can also increase greatly for the space of absorption than improving before the activation processing more than 25 times.
Improve the effect of concentration matter carbon grade to activation processing as can be seen from Table 4 in addition, if the preferable carbon grade of concentration matter at least more than 85%, can obtain the specific area 650m of activation products
2More than/the g, to make the sorbing material of high absorption property.
Table 4 concentration matter high-carbon grade is to the effect of activation processing
*Activation processing condition: 900 ℃ of temperature, 2.5hr, flow rates 8cm/min
Handle effect
As known from the above, the specific area of sorbing material of the present invention is big, can be big for adsorption space, pairing adsorbance is also not little, so select in the general commercially available sorbing material, be references object with the famous activated carbon commodity of big adsorbance, in order to the processing effect of this product to be described.Compare certain industrial powdered activated carbon commodity, the result is as shown in table 5.Can find out the quality of sorbing material of the present invention, on decolorizing ability and ash, all reach the sorbing material standard that commonly industrial wastewaters such as can be applicable to organic wastewater, waste water from dyestuff is handled; Simultaneously also can carry out market price, conclude the business and peddle with reference to the activated carbon products effect.The coal ash that more previous research institute is carried is as the absorption purposes, and processing effect of the present invention surmounts the coal ash absorption affinity that previous research institute is put forward, and has reached the product level of senior waste water treating agent.
The product efficacy of the sorbing material of table 5 the present invention preparation
| Analysis project | The sorbing material of the present invention's preparation * | Certain industrial powdered activated material with carbon element |
| The methylene blue value | 13ml/g | 13ml/g |
| Ash | 13.5％ | 14.5％ |
*The specific area scope is at 750～800m
2Between/the g
Economic benefit
Sorbing material of the present invention has advantages such as high absorption quality, low manufacturing cost, and raw material source can be exempted the disposal costs that coal ash is thrown aside from coal ash simultaneously.Below with regard to the handling of coal ash per ton, the profit that the present invention makes sorbing material,
Carry out assessment of economic benefit:
Treatment of Coal Ash is taken :-30 U.S. dollars/ton coal ash
The productive rate of sorbing material of the present invention: 0.15 ton of sorbing material/ton coal ash
The market value of sorbing material of the present invention: 600 U.S. dollars/ton sorbing material
The manufacturing cost of sorbing material of the present invention :-300 U.S. dollars/ton sorbing material
The profit that the present invention increased: 45 U.S. dollars/ton coal ash
The pending amount of domestic coal ash: 1.26 hundred ten thousand tons/year
The total cost of disposing :-37.8 hundred ten thousand U.S. dollar/years
Be engaged in profit of the present invention: 56.7 hundred ten thousand U.S. dollar/years totally
Embodiment two
The present invention's second possible embodiments comprises ultrasonic wave equally and handles to separate coal ash constituent, carbon and concentrate and handle and with steps such as high-temperature activation carbon concentration matters, see also shown in Figure 1:
(1) separate the coal ash constituent: at first coal ash and water are mixed, its mixed proportion is the same, and mixed liquor is imported ultrasonic wave, fully disperses to cause the coal ash constituent;
(2) carry out the carbon processing of concentrating: handle through step (1) ultrasonic wave, use the wet type screening to carry out the carbon processing of concentrating again;
(3) activation processing: the carbon concentration matter that gets after step (2) utilizes carbon dioxide to carry out activation processing again, please cooperate consult shown in Figure 4, activation processing in carbon dioxide (cm/min) atmosphere, wherein temperature and time is to promoting the effect of product specific area: 950 ℃-soak time of activation temperature be 3 hours, when activation temperature be 1, preferable soak time is about 1.4 hours in the time of 000 ℃, so, can obtain the product specific area at 680～700m
2Between/the g,, can also increase relatively for the space of absorption than improving before the activation processing more than 20 times.
The processing effect of embodiment two
The assay of this product is certain industrial powdered activated carbon commodity relatively, and the result is as shown in table 6.Can find out the quality of sorbing material of the present invention, on decolorizing ability and ash, reach commercialization, still can meet the product of commercial grade, be applied to the sorbing material that commonly industrial wastewaters such as organic wastewater, waste water from dyestuff are handled; Also can fix a price, conclude the business and peddle according to the activated carbon products effect.
The product efficacy of the sorbing material of table 6 the present invention preparation
| Analysis project | The sorbing material of the present invention's preparation | Certain industrial powdered activated material with carbon element |
| The methylene blue value | 12ml/g | 11ml/g |
| Ash | 13％ | 14％ |
In addition, in the embodiment of the invention one, two, wherein the processing method that concentrates of step (two) also can adopt the flotation mode, reclaims carbon from floating ore deposit; Also be can be for the technological means of the carbon that concentrates.
Embodiment three
The present invention's the 3rd possible embodiments comprises constituent, carbon that ultrasonic wave handle to separate coal ash equally and concentrates and handle and step such as high-temperature activation carbon concentration matter, and after above-mentioned steps is finished, to the gained activation products, carry out wet type screening step again, with the absorption property of further raising product, implementation step is:
(1) separates the coal ash constituent: at first coal ash and water are mixed, mixed liquor is imported ultrasonic wave, fully disperse to cause the coal ash constituent;
(2) carry out the carbon processing of concentrating: handle through step (1) ultrasonic wave, use the wet type screening to carry out the carbon processing of concentrating again;
(3) activation processing: the carbon concentration matter through the screening of step (2) wet type carries out the high-temperature activation processing;
(4) the activation products carbon processing of concentrating once more: through the product of step (3) activation processing, use wet type screening to carry out the carbon processing of concentrating again, obtain about 400 mesh sieve tops,, thereby can reach the effect of the whole adsorption efficiency of further raising sorbing material because the carbon grade on sieve top is higher.
The processing effect of embodiment three
The activation products effect that concentrates and handle through carbon once more as seen from Table 7, to activation products 1* through carbon concentrate handle after, specific area is at 790m originally
2Can be promoted to 820m about/g
2/ g, the methylene blue value also increases to 14～15ml/g by 13～14ml/g, and ash is reduced to 9.0% by 13.5%, illustrates to have the further effect of product absorption property.In addition by the activation products in the table 72
*Also can find out through carbon concentrate handle after, because ash surpasses 15%, handle its specific area of back for originally by 673m
2/ g obtains to be promoted to 760m
2/ g, the methylene blue value also increases to 13～14ml/g by 11～12ml/g, and ash is reduced to below 10% by 20%, obviously can promote product hierarchy on the effect.
Table 7 carbon once more concentrates and handles the effect of further product absorption property
| |
|
|
|
|
| Specific area m 2/g | 790 | 820 | 673 | 760 |
| Carbon grade % | 86.5 | 91 | 79.2 | 91.7 |
| Ash % | 13.5 | 9 | 20.8 | 9.3 |
| Methylene blue value ml/g | 13～14 | 14～15 | 11～12 | 13～14 |
*Activation condition: initial concentration matter carbon grade 90.5%, 900 ℃, flow rates 8cm/min, 2.5hr
*Activation condition: initial concentration matter carbon grade 85.5%, 900 ℃, flow rates 8cm/min, 2.5hr
Via above explanation as can be known, the present invention can be had the following advantage and an effect:
1. the present invention uses coal-fired ash for raw material, to be prepared into sorbing material, not only with the discarded object recycling, and can save the huge cost of discarded coal ash disposal costs.
2. the sorbing material for preparing gained according to the inventive method can replace existing goods (activated carbon), is especially providing in the wastewater treatment.
3. the sorbing material for preparing gained according to the inventive method, through the absorption related experiment, has tangible wastewater treatment effect, its adsorbance/efficient has been equivalent to the existing large activated carbon class commodity of adsorbance, that is its adsorbance of the prepared sorbing material of the present invention is greater than other general sorbing material, and its grade is equivalent to activated carbon class commodity.
4. the present invention can effectively reduce the cost of manufacture of sorbing material, and end product quality can reach commercialization, has economic worth.
5. the exercisable coal ash raw material of the present invention is obtained easily, use coal ash not only can solve domestic a large amount of coal ash problem to be disposed, and made sorbing material, its preparation cost is low, adsorption efficiency is high again, and can be supplied in a large number wastewater treatment, and then reduce expensive cost for wastewater treatment, have the double effects of the treatment of wastes with processes of wastes against one another.
Claims (11)
1. method of making sorbing material with coal ash, it is characterized in that it mainly is that burned-coal fly ash is sub-elected unburned carbon with triage techniques, again unburned carbon is carried out high-temperature activation and handle, make the surface of unburned carbon form numerous fine holes, become for the adsorption space that holds small material; Constituting thus can be for the sorbing material of handling waste water.
2. a kind of according to claim 1 coal ash is made the method for sorbing material, it is characterized in that, its concrete implementation step is:
(1) separates the coal ash constituent: at first coal ash and water are fully mixed, mixed liquor is imported ultrasonic wave, fully disperse to cause the coal ash constituent;
(2) carry out the carbon processing of concentrating: after step (1) ultrasonic wave is handled, use the wet type screening to carry out the carbon processing of concentrating again;
(3) activation processing: will carry out the high-temperature activation processing by the carbon concentration matter of gained after step (2), and to form numerous holes on carbon surface, promote specific area, becoming can be for the space of absorption.
3. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that the ultrasonic treatment time of step (1) is more than at least 10 minutes.
4. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that, the screening of step (2) wet type is to take out the above parts of 400 orders, can get the carbon grade up to 90.5% carbon concentration matter.
5. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that, for the carbon grade of the employed carbon concentration matter of step (3) high-temperature activation at least more than 85%.
6. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that, the high-temperature activation of step (3) is handled and can be adopted steam as activated gas.
7. make the method for sorbing material as a kind of coal ash as described in the claim 6, it is characterized in that flow rates is more than the 8cm/min.
8. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that, the high-temperature activation of step (3) is handled can adopt carbon dioxide as activated gas.
9. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that step (3) high-temperature activation preferred temperature is 800～1,000 ℃, soak time was at 3.5～0.5 hours.
10. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that the processing method that concentrates of step (2) also can adopt the flotation mode, from floating ore deposit, reclaim carbon.
11. make the method for sorbing material as a kind of coal ash as described in the claim 2, it is characterized in that, after the activation processing step of step (3), can carry out once more the carbon processing of concentrating, with the absorption property of further raising sorbing material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898107A (en) * | 2010-07-09 | 2010-12-01 | 宁波工程学院 | Method for treating chromium-containing wastewater by using barite adsorbent |
| CN102249630A (en) * | 2011-04-28 | 2011-11-23 | 北京工业大学 | Cement-based material able to adsorb heavy metal ions |
| CN103011367A (en) * | 2012-12-31 | 2013-04-03 | 广东石油化工学院 | Method for resource utilization of fluidized bed combustion ash residues |
| CN105026031A (en) * | 2013-03-15 | 2015-11-04 | 索尼公司 | Adsorbing carbon material |
| CN111099589A (en) * | 2019-12-27 | 2020-05-05 | 肇庆学院 | Preparation of biochar by using coal fly ash as raw material and application of biochar as live bacteria carrier |
-
2007
- 2007-02-08 CN CNA2007100028647A patent/CN101204646A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898107A (en) * | 2010-07-09 | 2010-12-01 | 宁波工程学院 | Method for treating chromium-containing wastewater by using barite adsorbent |
| CN102249630A (en) * | 2011-04-28 | 2011-11-23 | 北京工业大学 | Cement-based material able to adsorb heavy metal ions |
| CN103011367A (en) * | 2012-12-31 | 2013-04-03 | 广东石油化工学院 | Method for resource utilization of fluidized bed combustion ash residues |
| CN103011367B (en) * | 2012-12-31 | 2014-04-16 | 广东石油化工学院 | Method for resource utilization of fluidized bed combustion ash residues |
| CN105026031A (en) * | 2013-03-15 | 2015-11-04 | 索尼公司 | Adsorbing carbon material |
| CN111099589A (en) * | 2019-12-27 | 2020-05-05 | 肇庆学院 | Preparation of biochar by using coal fly ash as raw material and application of biochar as live bacteria carrier |
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Open date: 20080625 |