CN103586010A - Method for preparing molecular sieve by using fly ash and mercury removal use of prepared molecular sieve - Google Patents
Method for preparing molecular sieve by using fly ash and mercury removal use of prepared molecular sieve Download PDFInfo
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Abstract
The invention relates to a method for preparing a molecular sieve by using fly ash and a use of the prepared molecular sieve. The preparation method comprises the following steps: mixing the fly ash and an alkali, calcining, cooling to room temperature, grinding to obtain calcined cooked ash; adding water into the calcined cooked ash, heating and stirring in a reactor, heating for static aging and crystallization; filtering, washing, and drying to obtain the molecular sieve. The method adopts the coal-fired waste fly ash as a raw material for synthesis and modification of the molecular sieve to obtain an adsorbent for mercury removal of coal-fired flue gas. The method is simple in preparation process, is low in price of the used fly ash raw material and chemicals, can effectively extract silicon aluminum components in the fly ash for converting into the molecular sieve, has high yield, and can effectively adsorb mercury in the coal-fired flue gas.
Description
Technical field
The present invention relates to a kind of method and purposes of preparing molecular sieve, particularly, relate to a kind of coal ash for manufacturing that utilizes for the method for adsorbent of molecular sieve, gained molecular sieve can be used for coal-fired flue gas mercury removal.
Background technology
Coal is as occupy most important status in modal fossil fuel ， China energy resource structure always.In recent years, along with China's rapid development of economy, especially coal consumption amount of energy-output ratio increases year by year, as the discharge capacity of the flyash of solid waste of fuel coal, also increases year by year.At present, China is to the utilization of flyash still in reduced levels, and flyash more than half still discharges or landfill disposal on the spot, takies tract, and easily cause secondary pollution, only have small part flyash to be utilized for the manufacture of construction materials such as cement, concrete.Flyash main component is alumino-silicate, and molecular sieve is silicate or the alumino-silicate of crystalline state.Therefore flyash can be molecular sieve syntheticly provides required silicon and aluminum source, and it is feasible utilizing technically flyash synthesis of molecular sieve, and to utilize flyash to prepare molecular sieve for raw material be also a kind of effective way that Ash Utilization utilizes.
Meanwhile, coal can give off heavy metal Hg in combustion process, is maximum artificial mercury emissions source, and the coal-fired mercury content of China is higher, and coal consumption amount is large, is the maximum country of Mercury In The Air discharge capacity in the world.Mercury has very big harm to the mankind and ecological environment, and it has high toxicity, persistence, the easy features such as bioconcentration of migration and height, so the mercury emissions in coal-fired flue-gas is in the urgent need to being effectively controlled.The existence form of Mercury In Coal Combustion Flue Gas mainly contains Elemental Mercury (Hg
0), divalence mercury (Hg
2+) and particle mercury (Hg
p) three kinds.Most mercury all exist with Elemental Mercury form, and its volatility is high and be insoluble in water, and in atmosphere, mean residence time is long, and be easy to long-distance transportation and form extensive pollution, be form the most rambunctious.
At present, coal-fired flue gas mercury removal technology is mainly divided three classes: demercuration after demercuration and burning in the front demercuration of burning, burning.Adopting adsorbent to carry out demercuration to flue gas after burning is current topmost mercury control technology, and main adsorbent has active carbon, flying dust, Ca-base adsorbent and mineral substance adsorbent etc.There is the problems such as adsorption capacity is little in flying dust, Ca-base adsorbent and mineral substance adsorbent etc., at present technical can commercial Application be active carbon.Acticarbon is owing to existing required carbon mercury than the shortcoming such as high, expensive, and its actual use is very limited.
Therefore, Development of Novel Cheap highly effective adsorbent is to control at present mercury emissions problem demanding prompt solution.New adsorbent should be able to effectively be removed mercury simple substance, keep flying dust quality, and need to have compared with high-adsorption-capacity, to reduce adsorbent use amount in application process, also should have cheap, operating cost is low, to features such as the applicability of different smoke components and condition are strong, this has brought larger challenge for the developmental research of new adsorbent.
Summary of the invention
The object of the present invention is to provide a kind of coal ash for manufacturing that utilizes for the method for the adsorbent of molecular sieve of demercuration.Take flyash as preparing the primary raw material of adsorbent of molecular sieve, and for the preparation of the adsorbent of molecular sieve of coal-fired flue gas mercury removal, production technology is simple, processing ease, and production cost is low, and can realize the recycling of flyash.
In order to achieve the above object, the present invention adopts following technical scheme:
Utilize coal ash for manufacturing for a method for demercuration molecular sieve, comprise the steps:
(1) flyash and alkali are mixed, calcining, is cooled to after room temperature and grinds and obtain calcining ripe ash;
(2) in step (1) gained is calcined ripe ash, add water, in reactor, heat and stir, lower standing aging, the crystallization of heating;
(3) step (2) gained mixture is filtered, washing, is drying to obtain described molecular sieve.
As optimal technical scheme, preparation method of the present invention, also comprises the steps:
(4) step (3) gained molecular sieve is used to the salt solution impregnation of transition metal, stir load, then filter, dry and obtain modified molecular screen;
Optionally carry out (5) by step (3) gained molecular sieve or the extrusion modling of (4) gained modified molecular screen.
For the present invention, preferably, the described flyash of step (1) grinds to form fine powder after drying.
Preferably, the temperature of described oven dry is 80-130 ℃.
Preferably, the granularity of described grinding was 200 mesh sieves.
Preferably, described alkali grinds to form fine powder.
Preferably, described alkali is hydroxide, is preferably alkali-metal hydroxide, more preferably NaOH.
Preferably, the mass ratio of the described alkali of step (1) and flyash is 0.4-2:1, such as being 0.5,0.7,0.9,1.3,1.5,1.8 etc., is preferably 0.8-1.2:1.
Preferably, the temperature of described calcining is 600-840 ℃, such as being 610 ℃, 640 ℃, 660 ℃, 690 ℃, 730 ℃, 770 ℃, 790 ℃, 820 ℃ etc., is preferably 700-800 ℃.
Preferably, the time of described calcining is 1-3h, is preferably 1.5-2h;
Preferably, described calcining is carried out in Muffle furnace.
For the present invention, preferably, the mass volume ratio of the ripe ash of the described calcining of step (2) and water is 1:2-15g/ml, such as being 1:3g/ml, 1:6g/ml, 1:9g/ml, 1:11g/ml, 1:13g/ml etc., is preferably 1:5-8g/ml.
Preferably, during described stir, the temperature of heating is 40-70 ℃, such as being 44 ℃, 49 ℃, 52 ℃, 56 ℃, 61 ℃, 66 ℃, 69 ℃ etc., is preferably 50-60 ℃.Described heating can be carried out in water-bath.
Preferably, the time of described stirring is 0.5-10h, such as being 0.8h, 1.5h, 2.4h, 4h, 6h, 7.5h, 9h etc., is preferably 1-6h.
Preferably, described standing aging heating-up temperature is 40-70 ℃, such as being 44 ℃, 49 ℃, 52 ℃, 56 ℃, 61 ℃, 66 ℃, 69 ℃ etc., is preferably 50-60 ℃.
Preferably, the described standing aging time is 1-10h, such as being 1.5h, 2.4h, 4h, 6h, 7.5h, 9h etc., is preferably 3-6h.
Preferably, the heating-up temperature of described standing crystallization is 75-100 ℃, such as being 78 ℃, 82 ℃, 86 ℃, 89 ℃, 92 ℃, 95 ℃, 99 ℃ etc., is preferably 90-100 ℃.
Preferably, the time of described standing crystallization is 3-40h, such as being 5h, 9h, 12h, 16h, 19h, 23h, 26h, 28h, 31h, 35h, 38h etc., is preferably 6-24h.
Preferably, described reaction is carried out in the reactor of polytetrafluoroethylene (PTFE).
For the present invention, preferably, the described washing of step (3) is for washing to pH≤10, such as being 8.0,8.5,9.0,9.5,9.8 etc.
Preferably, the temperature of described oven dry is 80-110 ℃.
Preferably, the time of described oven dry is 12-24h.
For the present invention, preferably, the concentration of salt solution of the described transition metal of step (4) is 0.05-0.5mol/L, such as being 0.08mol/L, 0.12mol/L, 0.16mol/L, 0.22mol/L, 0.27mol/L, 0.31mol/L, 0.34mol/L, 0.38mol/L, 0.42mol/L, 0.45mol/L, 0.48mol/L etc., be preferably 0.15-0.3mol/L.
Preferably, the salting liquid of described transition metal is the one kind or two or more mixture in the salting liquid of Cu, Fe, Mn or Co, it is for example the salting liquid of Fe, or the mixture of the salting liquid of Cu and the salting liquid of Fe, or the mixture of the salting liquid of Mn and Co, or the salting liquid mixture of Fe, Mn and Co etc.
Preferably, the salting liquid of described transition metal is the one kind or two or more mixture in the halogen of Cu, Fe, Mn or Co, for example, be CuCl
2solution, or FeBr
3solution, or MnF
3solution, or CoF
2solution, or CuCl
2solution and CoF
2the mixture of solution, or FeBr
3solution, MnF
3solution and CoF
2mixture of solution etc.
Preferably, the volume mass of the salting liquid of described transition metal and step (3) gained molecular sieve, than for 3-20:1ml/g, such as being 4:1ml/g, 6:1ml/g, 9:1ml/g, 12:1ml/g, 15:1ml/g, 18:1ml/g etc., is preferably 6-10:1ml/g.
Preferably, the time of described stirring is more than 1h, such as being 1.5h, 1.9h, 2.2h, 2.5h, 3h, 3.5h, 4.5h, 6h, 8h etc., is preferably 2-4h.
Preferably, the temperature of described oven dry is 100-120 ℃.
Preferably, the time of described oven dry is 12-24h.
For the present invention, preferably, the squeeze pressure of the extrusion modling that step (5) is described is 6-10MPa, such as being 6.5MPa, 7MPa, 8MPa, 9MPa etc.
As optimal technical scheme, the method for the invention comprises the steps:
(1) by grinding to form the flyash of fine powder after drying and grinding to form the alkali of fine powder, in mass ratio for 0.4-2:1 mixes, 600-840 ℃ of calcining, be cooled to room temperature after grinding obtain calcining ripe ash;
(2) take mass volume ratio as 1:2-15g/ml, in calcining ripe ash, step (1) gained adds water, in reactor, at 40-70 ℃, heat and stir after 0.5-10h at 40-70 ℃ standing aging 1-10h, then standing crystallization 3-40h under 75-100 ℃ of heating under heating;
(3) step (2) gained mixture is filtered, wash to pH≤10, dry 12-24h obtains described molecular sieve at 80-110 ℃.
As optimal technical scheme, the method for the invention comprises the steps:
(1) by grinding to form the flyash of fine powder after drying and grinding to form the alkali of fine powder, in mass ratio for 0.4-2:1 mixes, 600-840 ℃ of calcining, be cooled to room temperature after grinding obtain calcining ripe ash;
(2) take mass volume ratio as 1:2-15g/ml, in calcining ripe ash, step (1) gained adds water, in reactor, at 40-70 ℃, heat and stir after 0.5-10h at 40-70 ℃ standing aging 1-10h, then standing crystallization 3-40h under 75-100 ℃ of heating under heating;
(3) step (2) gained mixture is filtered, wash to pH≤10, dry 12-24h obtains described molecular sieve at 80-110 ℃;
(4) salting liquid of the transition metal that is 0.05-0.5mol/L by step (3) gained molecular sieve working concentration, take volume mass ratio as 3-20:1ml/g dipping, stir the above load of 1h, then filtration, dries 12-24h at 100-120 ℃ and obtains modified molecular screen;
Optionally carry out (5) step (4) gained modified molecular screen is used to the moulding of 6-10MPa pressure extrusion, after fragmentation, obtain adsorbent of molecular sieve particle.
One of object of the present invention is also to provide the purposes of the molecular sieve being prepared by flyash of the present invention, described molecular sieve can be used for the control of Mercury In Coal Combustion Flue Gas discharge, is preferred for the control of station boiler, Industrial Boiler or Industrial Stoves coal-fired flue-gas mercury emissions.
Preferably, described adsorbent of molecular sieve is used separately or is used in conjunction with other sorbing materials.
It is raw material that the present invention adopts coal-fired discarded object flyash, carries out the synthetic and modification of molecular sieve, obtain a kind of can be for the adsorbent of coal-fired flue gas mercury removal.The method preparation technology is simple, powdered coal ash used, preparation are cheap, effectively in extract powder coal ash, silane agent is converted into molecular sieve, there is higher productive rate, gained molecular sieve has certain mercury adsorption features, with the adsorbent of molecular sieve that metal halide floods after modification, has very high mercury adsorption features.
It is simple that the method is prepared molecular sieve adsorption agent producing process, processing ease, and production cost is low, for the recycling of flyash provides a new approach, also for coal-fired flue gas mercury removal provides a kind of novel absorption material.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of molecular sieve, is respectively the MnCl through 0.2mol/L
2the XRD spectra of the modified adsorbent after solution load (MnCl2 modification), and the XRD spectra (molecular sieve) of initial molecule sieve;
Fig. 2 is the XRD spectra of molecular sieve, is respectively the CuBr through 0.15mol/L
2the XRD spectra of the modified adsorbent after solution load (CuBr2 modification), and the XRD spectra (molecular sieve) of initial molecule sieve.
Fig. 3 is initial molecule sieve, MnCl
2modification, CuBr
2modification, CuCl
2the mercury adsorption features of modified molecular screen under embodiment condition.
The specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
(1) gather certain fly ash in electric power plant sample, after it is dried at 120 ℃, ground 200 mesh sieves and obtain flyash fine powder.6.4g NaOH is ground to form to fine powder, after fully mixing with 8.0g flyash fine powder, be placed in Muffle furnace high-temperature calcination 90min at 750 ℃, grind after cooling to room temperature with the furnace;
(2) add 80ml water to stir 1h at 50 ℃, pack in polytetrafluoroethylene (PTFE) reactor aging 3h, then standing crystallization 6h under 90 ℃ of water-baths under 60 ℃ of water bath condition into;
(3), by sample suction filtration and wash to pH<10, dry 12h in 110 ℃ of baking ovens, obtains being mixed with the A type molecular sieve product of a certain amount of X-type molecular sieve;
(4) CuCl that compound concentration is 0.2mol/L
2solution, gets step (3) gained molecular sieve 3.0g, adds solution that 30ml joins at room temperature to stir 1h and carries out load, and dry 12h in 110 ℃ of baking ovens, obtains required modified molecular screen adsorbent after filtering;
(5) step (4) gained adsorbent of molecular sieve is ground, at 10MPa lower sheeting, screening 60～80 object particles after pulverizing.
The performance test of gained adsorbent of molecular sieve:
Getting absorbent particles 0.1g packs in fixed bed quartz tube reactor, at N
2under atmosphere, carry out mercury adsorption experiment, wherein mercury concentration is 15 μ g/m
3, reaction temperature is 100 ℃, the about 300000h of air speed
-1, the mercury clearance after operation 2h can reach more than 95%.Its adsorption curve figure is shown in the CuCl in Fig. 3
2modification curve map.
Embodiment 2
(1) gather certain fly ash in electric power plant sample, after it is dried at 100 ℃, ground 200 mesh sieves and obtain flyash fine powder.9.6g NaOH is ground to form to fine powder, after fully mixing with 8.0g flyash fine powder, be placed in Muffle furnace high-temperature calcination 90min at 800 ℃, grind after cooling to room temperature with the furnace;
(2) add 80ml water to stir 6h at 60 ℃, pack in polytetrafluoroethylene (PTFE) reactor aging 4h, then standing crystallization 12h under 90 ℃ of water-baths under 55 ℃ of water bath condition into;
(3) by sample suction filtration and wash to pH<10, dry 12h in 100 ℃ of baking ovens, obtains the mix products of A type molecular sieve and Y zeolite, and its XRD spectra is shown in the initial molecule sieve spectrogram in Fig. 1;
(4) MnCl that compound concentration is 0.2mol/L
2solution, gets step (3) gained molecular sieve 2.0g, adds solution that 20ml joins at room temperature to stir 3h and carries out load, and dry 12h in 120 ℃ of baking ovens, obtains required modified molecular screen adsorbent after filtering, and its XRD spectra is shown in the MnCl in Fig. 1
2spectrogram.In figure, visible this zeolite product is the mixture of A type molecular sieve and Y zeolite, load MnCl
2after, the characteristic peak of molecular sieve reduces, and noncrystalline bag obviously increases, and the MnCl of load is described
2mainly with amorphous state, exist;
(5) step (4) gained adsorbent of molecular sieve is ground, at 8MPa lower sheeting, after pulverizing, screening 60～80 object particles are as adsorbent.
The performance test of gained adsorbent of molecular sieve:
Getting absorbent particles 50mg packs in fixed bed quartz tube reactor, at N
2under atmosphere, carry out mercury adsorption experiment, wherein mercury concentration is 36 μ g/m
3, reaction temperature is 120 ℃, the about 700000h of air speed
-1, the mercury clearance after operation 2h can reach more than 25%.Its adsorption curve figure is shown in the MnCl in Fig. 3
2modification curve map.
Embodiment 3
(1) gather certain fly ash in electric power plant sample, after it is dried at 120 ℃, ground 200 mesh sieves and obtain flyash fine powder.9.6g NaOH is ground to form to fine powder, after fully mixing with 8.0g flyash fine powder, be placed in Muffle furnace high-temperature calcination 120min at 800 ℃, grind after cooling to room temperature with the furnace;
(2) add 80ml water to stir 1h at 50 ℃, pack in polytetrafluoroethylene (PTFE) reactor aging 3h, then standing crystallization 24h under 90 ℃ of water-baths under 60 ℃ of water bath condition into;
(3) by sample suction filtration and wash to pH<10, dry 24h in 110 ℃ of baking ovens, obtains being mixed with the A type molecular sieve product of Y zeolite, and its XRD spectra is shown in the initial molecule sieve spectrogram in Fig. 2;
(4) CuBr that compound concentration is 0.15mol/L
2solution, gets step (3) gained molecular sieve 2.0g, adds solution that 20ml joins at room temperature to stir 2h and carries out load, and dry 24h in 120 ℃ of baking ovens, obtains required modified molecular screen adsorbent after filtering, and its XRD spectra is shown in the CuBr in Fig. 2
2spectrogram.In figure, visible this zeolite product is the mixture of A type molecular sieve and Y zeolite, loaded Cu Br
2after, noncrystalline be surrounded by increase, the CuBr of load
2mainly with amorphous state, exist;
(5) step (4) gained adsorbent of molecular sieve is ground, at 9MPa lower sheeting, after pulverizing, screening 60～80 object particles are as adsorbent.
The performance test of gained adsorbent of molecular sieve:
Getting absorbent particles 50mg packs in fixed bed quartz tube reactor, at N
2under atmosphere, carry out mercury adsorption experiment, wherein mercury concentration is 36 μ g/m
3, reaction temperature is 120 ℃, the about 700000h of air speed
-1, the mercury clearance after operation 2h can remain on more than 98%.Its adsorption curve figure is shown in the CuBr in Fig. 3
2modification curve map.
Embodiment 4
(1) gather certain fly ash in electric power plant sample, after it is dried at 100 ℃, ground 300 mesh sieves and obtain flyash fine powder.9.6g NaOH is ground to form to fine powder, after fully mixing with 5.0g flyash fine powder, is placed in Muffle furnace high-temperature calcination 120min at 600 ℃, grind after cooling to room temperature with the furnace,
(2) add 146ml water to stir 10h at 45 ℃, pack in polytetrafluoroethylene (PTFE) reactor aging 8h, then standing crystallization 20h under 96 ℃ of water-baths under 70 ℃ of water bath condition into.
(3), by sample suction filtration and wash to pH<10, dry 15h in 90 ℃ of baking ovens, obtains the mix products of A type molecular sieve and sodalite.
(4) step (3) gained adsorbent of molecular sieve is ground, at 10MPa lower sheeting, after pulverizing, screening 60～80 object particles are as adsorbent.
The performance test of gained adsorbent of molecular sieve:
Getting absorbent particles 50mg packs in fixed bed quartz tube reactor, at N
2under atmosphere, carry out mercury adsorption experiment, wherein mercury concentration is 36 μ g/m
3, reaction temperature is 120 ℃, the about 700000h of air speed
-1, initial mercury clearance can reach more than 10%.Its adsorption curve figure is shown in the initial molecule sieve curve map in Fig. 3.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. utilize coal ash for manufacturing for a method for demercuration molecular sieve, comprise the steps:
(1) flyash and alkali are mixed, calcining, is cooled to after room temperature and grinds and obtain calcining ripe ash;
(2) in step (1) gained is calcined ripe ash, add water, in reactor, heat and stir, lower standing aging, the crystallization of heating;
(3) step (2) gained mixture is filtered, washing, is drying to obtain described molecular sieve.
2. method according to claim 1, is characterized in that, also comprises the steps:
(4) step (3) gained molecular sieve is used to the salt solution impregnation of transition metal, stir load, then filter, dry and obtain modified molecular screen;
Optionally carry out (5) by step (3) gained molecular sieve or the extrusion modling of (4) gained modified molecular screen.
3. method according to claim 1 and 2, is characterized in that, the described flyash of step (1) grinds to form fine powder after drying;
Preferably, the temperature of described oven dry is 100-120 ℃;
Preferably, the granularity of described grinding was 200 mesh sieves;
Preferably, described alkali grinds to form fine powder;
Preferably, described alkali is hydroxide, is preferably alkali-metal hydroxide, more preferably NaOH.
4. according to the method described in claim 1-3 any one, it is characterized in that, the mass ratio of the described alkali of step (1) and flyash is 0.4-2:1, is preferably 0.8-1.2:1;
Preferably, the temperature of described calcining is 600-840 ℃, is preferably 700-800 ℃;
Preferably, the time of described calcining is 1-3h, is preferably 1.5-2h;
Preferably, described calcining is carried out in Muffle furnace.
5. according to the method described in claim 1-4 any one, it is characterized in that, the mass volume ratio of the ripe ash of the described calcining of step (2) and water is 1:2-15g/ml, is preferably 1:5-8g/ml;
Preferably, during described stirring, the temperature of heating is 40-70 ℃, is preferably 50-60 ℃;
Preferably, the time of described stirring is 0.5-10h, is preferably 1-6h;
Preferably, described standing aging heating-up temperature is 40-70 ℃, is preferably 50-60 ℃;
Preferably, the described standing aging time is 1-10h, is preferably 3-6h;
Preferably, the heating-up temperature of described standing crystallization is 75-100 ℃, is preferably 90-100 ℃;
Preferably, the time of described standing crystallization is 3-40h, is preferably 6-24h;
Preferably, described reaction is carried out in the reactor of polytetrafluoroethylene (PTFE).
6. according to the method described in claim 1-5 any one, it is characterized in that, the described washing of step (3) is for washing to pH≤10;
Preferably, the temperature of described oven dry is 80-110 ℃;
Preferably, the time of described oven dry is 12-24h.
7. according to the method described in claim 2-6 any one, it is characterized in that, the concentration of salt solution of the described transition metal of step (4) is 0.05-0.5mol/L, is preferably 0.15-0.3mol/L;
Preferably, the salting liquid of described transition metal is the one kind or two or more mixture in the salting liquid of Cu, Fe, Mn or Co;
Preferably, the salting liquid of described transition metal is the one kind or two or more mixture in the halogen of Cu, Fe, Mn or Co;
Preferably, the volume mass of the salting liquid of described transition metal and step (3) gained molecular sieve, than for 3-20:1ml/g, is preferably 6-10:1ml/g;
Preferably, the time of described stirring is more than 1h, to be preferably 2-4h;
Preferably, the temperature of described oven dry is 100-120 ℃;
Preferably, the time of described oven dry is 12-24h.
Preferably, the squeeze pressure of the extrusion modling described in step (5) is 6-10MPa.
8. according to the method described in claim 1-7 any one, it is characterized in that, described method comprises the steps:
(1) by grinding to form the flyash of fine powder after drying and grinding to form the alkali of fine powder, in mass ratio for 0.4-2:1 mixes, 600-840 ℃ of calcining, be cooled to room temperature after grinding obtain calcining ripe ash;
(2) take mass volume ratio as 1:2-15g/ml, in calcining ripe ash, step (1) gained adds water, in reactor, at 40-70 ℃, heat and stir after 0.5-10h at 40-70 ℃ standing aging 1-10h, then standing crystallization 3-40h under 75-100 ℃ of heating under heating;
(3) step (2) gained mixture is filtered, wash to pH≤10, dry 12-24h obtains described molecular sieve at 80-110 ℃.
9. according to the method described in claim 1-8 any one, it is characterized in that, described method comprises the steps:
(1) by grinding to form the flyash of fine powder after drying and grinding to form the alkali of fine powder, in mass ratio for 0.4-2:1 mixes, 600-840 ℃ of calcining, be cooled to room temperature after grinding obtain calcining ripe ash;
(2) take mass volume ratio as 1:2-15g/ml, in calcining ripe ash, step (1) gained adds water, in reactor, at 40-70 ℃, heat and stir after 0.5-10h at 40-70 ℃ standing aging 1-10h, then standing crystallization 3-40h under 75-100 ℃ of heating under heating;
(3) step (2) gained mixture is filtered, wash to pH≤10, dry 12-24h obtains described molecular sieve at 80-110 ℃;
(4) salting liquid of the transition metal that is 0.05-0.5mol/L by step (3) gained molecular sieve working concentration, take volume mass ratio as 3-20:1ml/g dipping, stir the above load of 1h, then filtration, dries 12-24h at 100-120 ℃ and obtains modified molecular screen;
Optionally carry out (5) step (3) gained molecular sieve or (4) gained modified molecular screen are used to the moulding of 6-10MPa pressure extrusion, after fragmentation, obtain adsorbent of molecular sieve particle.
10. the purposes of the molecular sieve that claim 1-9 is prepared by flyash, is characterized in that, described molecular sieve can be used for the control of Mercury In Coal Combustion Flue Gas discharge, is preferred for the control of station boiler, Industrial Boiler or Industrial Stoves coal-fired flue-gas mercury emissions;
Preferably, described adsorbent of molecular sieve is used separately or is used in conjunction with other sorbing materials.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106984266A (en) * | 2017-05-27 | 2017-07-28 | 东莞深圳清华大学研究院创新中心 | A kind of method that VOC molecular sieve adsorption materials are prepared by raw material of flyash |
| CN108380173A (en) * | 2018-02-26 | 2018-08-10 | 北京林业大学 | A kind of synthetic zeolite from flyash and its preparation method and application |
| CN108393065A (en) * | 2018-03-06 | 2018-08-14 | 江苏开放大学（江苏城市职业学院） | A kind of fly ash float Compound Heavy Metals sorbing material and its application |
| CN109351326A (en) * | 2018-12-19 | 2019-02-19 | 四川省达科特能源科技股份有限公司 | A kind of renewable mercury removal agent and preparation method thereof for natural gas |
| CN110639599A (en) * | 2019-10-19 | 2020-01-03 | 青岛科技大学 | Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof |
| CN111604031A (en) * | 2020-05-29 | 2020-09-01 | 华中科技大学 | Modified carbon-based/non-carbon-based mercury removal adsorbent and preparation method thereof |
| CN113144818A (en) * | 2021-04-29 | 2021-07-23 | 华电宁夏灵武发电有限公司 | Fly ash-based carbon dioxide absorption system and fly ash recycling method for absorbing carbon dioxide |
| CN115193395A (en) * | 2022-08-05 | 2022-10-18 | 哈尔滨工业大学 | Preparation method and application of mercury removal adsorbent compounded by pyrite and modified fly ash |
| CN115611292A (en) * | 2022-10-18 | 2023-01-17 | 国能(山东)能源环境有限公司 | Copper-based zeolite molecular sieve of fly ash source and preparation method and application thereof |
| CN118161962A (en) * | 2024-04-19 | 2024-06-11 | 上海樱琦干燥剂有限公司 | Calcium molecular sieve drying agent and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492875A (en) * | 2016-10-26 | 2017-03-15 | 东北农业大学 | Prepare the method and the method for processing furfural waste-water of load nano-titanium dioxide/zinc oxide molecular sieves |
| CN106984266A (en) * | 2017-05-27 | 2017-07-28 | 东莞深圳清华大学研究院创新中心 | A kind of method that VOC molecular sieve adsorption materials are prepared by raw material of flyash |
| CN108380173B (en) * | 2018-02-26 | 2021-12-10 | 北京林业大学 | Fly ash synthesized zeolite, preparation method and application thereof |
| CN108380173A (en) * | 2018-02-26 | 2018-08-10 | 北京林业大学 | A kind of synthetic zeolite from flyash and its preparation method and application |
| CN108393065A (en) * | 2018-03-06 | 2018-08-14 | 江苏开放大学（江苏城市职业学院） | A kind of fly ash float Compound Heavy Metals sorbing material and its application |
| CN109351326A (en) * | 2018-12-19 | 2019-02-19 | 四川省达科特能源科技股份有限公司 | A kind of renewable mercury removal agent and preparation method thereof for natural gas |
| CN110639599A (en) * | 2019-10-19 | 2020-01-03 | 青岛科技大学 | Copper-iron bimetal doped modified fly ash-molecular sieve composite catalyst and preparation method and application thereof |
| CN111604031A (en) * | 2020-05-29 | 2020-09-01 | 华中科技大学 | Modified carbon-based/non-carbon-based mercury removal adsorbent and preparation method thereof |
| CN113144818A (en) * | 2021-04-29 | 2021-07-23 | 华电宁夏灵武发电有限公司 | Fly ash-based carbon dioxide absorption system and fly ash recycling method for absorbing carbon dioxide |
| CN113144818B (en) * | 2021-04-29 | 2023-05-02 | 华电宁夏灵武发电有限公司 | Fly ash-based carbon dioxide absorption system and fly ash recycling method for absorbing carbon dioxide |
| CN115193395A (en) * | 2022-08-05 | 2022-10-18 | 哈尔滨工业大学 | Preparation method and application of mercury removal adsorbent compounded by pyrite and modified fly ash |
| CN115611292A (en) * | 2022-10-18 | 2023-01-17 | 国能(山东)能源环境有限公司 | Copper-based zeolite molecular sieve of fly ash source and preparation method and application thereof |
| CN115611292B (en) * | 2022-10-18 | 2024-02-13 | 国能(山东)能源环境有限公司 | Fly ash source copper-based zeolite molecular sieve and preparation method and application thereof |
| CN118161962A (en) * | 2024-04-19 | 2024-06-11 | 上海樱琦干燥剂有限公司 | Calcium molecular sieve drying agent and preparation method thereof |
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