CN103787354A - Method for preparing MCM-41 molecular sieve by utilizing fly ash and application of MCM-41 molecular sieve - Google Patents
Method for preparing MCM-41 molecular sieve by utilizing fly ash and application of MCM-41 molecular sieve Download PDFInfo
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- CN103787354A CN103787354A CN201410039979.3A CN201410039979A CN103787354A CN 103787354 A CN103787354 A CN 103787354A CN 201410039979 A CN201410039979 A CN 201410039979A CN 103787354 A CN103787354 A CN 103787354A
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Abstract
The invention discloses a method for preparing an MCM-41 molecular sieve by utilizing fly ash and application of the MCM-41 molecular sieve and belongs to the technical field of preparation of molecular sieves. The method comprises the following steps of: a, drying fly ash raw powder to constant weight, mixing an HCl solution and the dried fly ash, and stirring, centrifugalizing, washing and drying for later use; b, mixing the fly ash treated in the step a with NaOH, calcining, cooling, then grinding into fine powder, adding a ground calcined substance to deionized water, mixing, stirring and carrying out centrifugal separation to obtain supernatant; c, weighing a template agent CTAB (Cetyltrimethyl Ammonium Bromide), dissolving into the deionized water, continuously stirring under the condition of water bath, dropwise adding the supernatant obtained in the step b, regulating the pH of a solution by using HNO3, carrying out crystallization reaction on an obtained gelatinous substance, then naturally cooling to room temperature; and centrifuging, washing, drying and calcining to obtain the MCM-41 molecular sieve. By sufficiently utilizing the fly ash discharged from a thermal power plant as a silicon-aluminum source, the method disclosed by the invention reduces the synthesis cost of the MCM-41 molecular sieve and the utilization value is high.
Description
Technical field
The present invention relates to molecular sieve technical field, more particularly, relating to a kind of flyash that utilizes power plant emission is method and the application that main silicon and aluminum source is prepared MCM-41 molecular sieve.
Background technology
Mesopore molecular sieve compared with traditional micro porous molecular sieve, have stable skeleton structure, duct be six side's ordered arrangement, size evenly, there are high-specific surface area (600～1200 m
2g
-1), high-adsorption-capacity (>0.7cm
3g
-1), the good characteristic such as larger aperture (2～30nm).Show very large application potential in fields such as selecting absorption, separation and catalysis.But compare micro porous molecular sieve and natural zeolite material, mesopore molecular sieve MCM-41 adopts pure industrial chemicals if silicon-dioxide, water glass, tetraethoxy etc. are as silicon source conventionally, and cost costliness, has limited the application of molecular sieve MCM-41.The Main chemical component of flyash is A1
2o
3, SiO
2deng, be expected to become substituted for silicon, aluminum chemistry pure reagent and come the suitable feedstock of synthesizing Si-Al mesopore molecular sieve.
Through retrieval, by utilizing the flyash of power plant emission as silicon and aluminum source synthesis of molecular sieve, have open to reduce the technical scheme of molecular sieve cost, as Chinese Patent Application No. 200810231810.2, the applying date is on October 20th, 2008, and invention and created name is: a kind of preparation method of SI-MCM-41 mesopore molecular sieve; The disclosed preparation method of this application case utilizes flyash for main raw material, by using again alkali Tianjin after the removal of impurities of sour Tianjin, obtain water glass, then take sodium silicate solution as raw material, by adding template, sulphur acid for adjusting pH value can generate mesopore molecular sieve in sodium silicate solution, then burn template, obtain Si-MCM-41 mesopore molecular sieve.Si-MCM-41 mesopore molecular sieve prepared by this application case has mesopore and microvoid structure, there is higher specific surface area, and good absorption property, but this application case in to the treating processes of flyash by adding sulfuric acid to remove the metal ion such as Fe, Ca in flyash, this kind of method easily introduced the sulfate ion that is not easy removal, the silicate ion producing is below exerted an influence, and this technical scheme still needs further improvement.
Summary of the invention
1. the technical problem that invention will solve
The object of the invention is to overcome the high deficiency of preparation cost of MCM-41 molecular sieves in prior art, a kind of method and the application of coal ash for manufacturing for MCM-41 molecular sieve that utilize is provided, the present invention selects the hydrochloric acid of easily removing as acid dip solution, metallic impurity ion in not only can more effective removal flyash, improve the activity of powdered coal ash, while is due to the easy volatile of chlorion, can not impact pretreated raw material, the MCM-41 molecular sieve performance excellence preparing, and preparation cost is low.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
A kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing of the present invention, the steps include:
A, former flyash powder is dried to constant weight, mix with xeraphium coal ash with HCl solution, stirring, centrifugal, washing, dry for standby;
B, by flyash after treatment step a and NaOH mixed calcining, grind to form fine powder after cooling, calcined material after the grinding obtaining is joined in deionized water, mix, stir, centrifugation obtains supernatant liquor;
C, take template CTAB and be dissolved in deionized water, under water bath condition, continue to stir, dropwise drip the supernatant liquor obtaining in step b, use HNO
3regulator solution pH, continues to stir obtaining spawn, and the spawn obtaining is carried out to crystallization, naturally cools to room temperature after crystallization, and centrifugal, washing, oven dry, roasting obtain MCM-41 molecular sieve.
Further, in step a, the mass percent concentration of HCl solution used is 20%-30%, and the solid-liquid proportioning of xeraphium coal ash and HCl solution is 1:20; In centrifugally operated, centrifugal speed is 4000-6000rpm, and centrifugation time is 30-40min; In washing operation with deionized water wash to washings pH be 6 ~ 7.
Further, the contained SiO of flyash in calcination process described in step b
2with the mass ratio of NaOH be 1:2.2, calcining temperature is 500-600 ℃, calcination time 3-4 h.
Further, in step b, cooling gained rear calcined material is ground to form to fine powder and cross 200-300 mesh sieve; After grinding, the mass ratio of calcined material and deionized water is 1:20; In stirring operation, churning time is 24 hours; In centrifugally operated, centrifugal speed is 4000-6000rpm, and centrifugation time is 20-30min.
Further, SiO in template CTAB, supernatant liquor in step c
2and H
2the mol ratio of O is 0.15: 1:100; Bath temperature is 35 ℃, and the rate of addition of the supernatant liquor obtaining in step b is 1 ~ 2/s; HNO
3the mass percent concentration of solution is 10%-15%, uses HNO
3regulator solution pH is 10 ~ 11.
Further, in step c, crystallization temperature is 100 ℃, in roasting process, is warming up to 550 ℃ of roastings with the speed of 1 ℃/min.
A kind of application of coal ash for manufacturing for MCM-41 molecular sieve that utilize of the present invention, described MCM-41 molecular sieve is for the absorption of Cr (VI) ion.
Preferably, controlling adsorption temp is 25 ℃, Cr (VI) solion pH value is 6, Cr in solution (VI) ionic concn is 10mg/L, adsorption time is 60min, the solid-to-liquid ratio of the dosage of MCM-41 molecular sieve and Cr (VI) solion is 1:50, Cr in adsorbent solution (VI) ion.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following unusual effect:
(1) a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing of the present invention, make full use of the flyash of power plant emission as silicon and aluminum source, reduce the synthetic cost of molecular sieve, make full use of acidity and the easy volatile of hydrochloric acid soln, in flyash treating processes, not only can improve the activity of powdered coal ash, more can not introduce new impurity;
(2) a kind of application of coal ash for manufacturing for MCM-41 molecular sieve that utilize of the present invention, this MCM-41 molecular sieve has good adsorptive power to Cr (VI) ion, under 25 ℃, the condition of pH=6, to reaching 96.73% containing the clearance of Cr (VI) ion in the standardized solution of Cr (VI) ion.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the MCM-41 molecular sieve for preparing of the present invention;
Fig. 2 is the N of the MCM-41 molecular sieve for preparing of the present invention
2adsorption-desorption isothermal map;
Fig. 3 is the dosage of the MCM-41 molecular sieve for preparing of the present invention adsorption rate influence curve figure to Cr (VI) ion.
Embodiment
For further understanding content of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
By reference to the accompanying drawings, a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing of the present embodiment, flyash used is provided by Datang Luo He fuel-burning power plant, Huainan, and its main chemical compositions is in table 1.Other chemical reagent mainly comprise cetyl trimethylammonium bromide (CTAB, analytical pure), NaOH (analytical pure), HNO
3common reagent such as (analytical pure).
The chemical composition of table 1 flyash
As can be seen from Table 1, in the present embodiment former powder of flyash used, except Si, Al composition, also have the Fe element of high level, the concrete operations of the synthetic MCM-41 molecular sieve of the present embodiment are:
A, take the former powder of 200g fly ash in electric power plant, at l00 ℃, dry to constant weight, then the hydrochloric acid soln that is 20% by it with mass percent concentration mixes take solid-liquid proportioning (g/mL) as the ratio of 1:20, the hydrochloric acid soln that the present embodiment functional quality percentage concentration is 20% had both guaranteed to have enough HCl concentration to remove foreign ion, can make again solid and solution have more suitable solid-to-liquid ratio simultaneously.Stir 12h at 80 ℃ of lower magnetic forces, with the centrifugal speed centrifugation 40min of 4000rpm, with deionized water washing leaching cake remove residual hydrochloric acid to washings pH be 7, filter cake oven dry is placed in vacuum drier for subsequent use.What deserves to be explained is, in the process of synthetic MCM-41 molecular sieve, the existence meeting of the elements such as Fe is reacted and is generated precipitation in NaOH solution system, or decomposes in the time of high temperature roast, cause synthetic product whiteness and degree of crystallinity to reduce, thereby affect the performance of synthesis of molecular sieve product.Therefore, before synthetic MCM-41 molecular sieve, need flyash to carry out pre-treatment.The pretreatment process that the present embodiment adopts makes full use of acidity and the easy volatile of hydrochloric acid soln, select the hydrochloric acid of easily removing as acid dip solution, metallic impurity ion in not only can more effective removal flyash, clearance exceedes 99.6%, remaining Si after Impurity removal, Al composition can replace the synthesis material of pure chemistry composition completely, the activity of powdered coal ash improves greatly, while is due to the easy volatile of chlorion, can not impact pretreated raw material, remove the Fe in flyash than using sulfuric acid, the metal ions such as Ca, the clearance of the present embodiment metallic impurity ion is higher, the MCM-41 molecular sieve performance preparing is more excellent.
B, take respectively the pretreated flyash 20g of step a and 44gNaOH, mix, and under 500 ℃ of conditions, calcine 4 h in retort furnace, taking-up naturally cools to 30 ℃ of room temperatures, because solid particulate is thinner, larger with the contact area of liquid, more be easy to the Si in solid, the stripping of Al composition extracts, the present embodiment first grinds to form fine powder by calcining after product and crosses 200 mesh sieves, after grinding, calcined material is mixed with deionized water by solid-liquid mass ratio (g/mL) 1:20 again, stir 24h, centrifugation 30min under the rotating speed of 4000rpm, get supernatant liquor, as synthetic MCM-41 molecular sieve silicon source.
C, take CTAB(cetyl trimethylammonium bromide) be template, take CTAB and be dissolved in deionized water, bath temperature is made as 35 ℃, is stirred to solution and is the light blue of homogeneous clarification.Utilize magnetic stirring apparatus in continuous whipping process, dropwise drip (1 ~ 2/s) supernatant liquor of step b acquisition, SiO in template CTAB, supernatant liquor
2and H
2the mol ratio of O is 0.15: 1:100, the HNO that is 10% with mass percent concentration
3the pH value of regulator solution is 10, continues to stir aging 2h, obtains white gels.The white gels obtaining is proceeded in tetrafluoroethylene reactor after 100 ℃ of crystallization 48h, naturally cool to room temperature, it is centrifugal that (the MCM-41 particle of the cooling rear generation of crystallization is very thin, except a large amount of precipitations of reunion are arranged at bottom, solution is also suspension liquid, the centrifugal solid that can make is fully reclaimed), washing, dry, in retort furnace, be warming up to 550 ℃ of roastings with 1 ℃/min speed, the present embodiment can make by temperature rise rate slowly that template is relatively mild to be removed, prevent the defect of the crystalline structure comparatively fast causing because of template removal, then constant temperature calcining 6h, obtain mesoporous MCM-41 sieve sample.
The specific surface area of the MCM-41 molecular sieve that the present embodiment prepares is 596.7m
2/ g, mean pore size is 5.19nm, hole wall is thick is 0.96nm, has the characteristic of typical mesopore molecular sieve MCM-41.As shown in Figure 1, as seen from Figure 1, there is a significant diffraction peak at (100) face in sample to the XRD figure of MCM-41 molecular sieve, and this is the characteristic peak of mesopore molecular sieve MCM-41, can have hexagonal mesoporous arrangement architecture by confirmatory sample.In addition, also can observe obvious diffraction peak at (110) face and (200) face, illustrate that the prepared mesopore molecular sieve MCM-41 sample of the present embodiment has good long-range order and degree of crystallinity.In Fig. 1, X-coordinate represents 2 θ angle of diffraction, and ordinate zou represents diffracted intensity.
The N of the MCM-41 molecular sieve that the present embodiment prepares
2adsorption-desorption thermoisopleth as shown in Figure 2, as can be seen from Figure 2, along with adsorbed gas N
2with the increase of the relative pressure of carrier gas He, having there is a large hysteresis loop in thermoisopleth, shows that this thermoisopleth meets Lang Gemiaoer IV type, is typical mesoporous material adsorption curve.In Fig. 2, X-coordinate represents relative pressure, and ordinate zou represents adsorptive capacity.
The MCM-41 molecular sieve that the present embodiment prepares has good adsorptive power to Cr (VI) ion, wherein, controlling adsorption temp is 25 ℃, the pH of solution is 6, Cr in solution (VI) ionic concn is 10mg/L, adsorption time is 60min, when the solid-to-liquid ratio (g/ml) of the dosage of MCM-41 molecular sieve and Cr (VI) solion is 1:50, MCM-41 molecular sieve adsorptive power the best to Cr (VI) ion, can reach 96.73% to the clearance of Cr (VI) ion.
What deserves to be explained is, because mesopore molecular sieve MCM-41 is mainly by the ion exchange of its surface-Si-OH group to the adsorption of Cr (VI) ion, when pH too large (being generally greater than 8), molecular sieve can be partly dissolved, and pH is less, the H in solution
+the Competition of ion pair adsorption potential is greater than ion exchange, causes adsorption rate on the low side, therefore the pH value of solution removal effect in the time of neutrality acidity on the weak side is a little best.And generally, industry occupies the majority containing Cr (VI) ion waste water acidity, can increase again processing cost if added in advance into a large amount of alkali in waste water, therefore, contriver finally determines that by test of many times the pH of control solution is 6 the bests.In addition, contriver draws by theoretical analysis and verification experimental verification, in the situation that other conditions are identical, when Cr in solution (VI) ionic concn is 10mg/L, guarantee that the dosage of MCM-41 molecular sieve and the solid-to-liquid ratio (g/ml) of Cr (VI) solion can obtain best adsorption effect for 1:50.
As shown in Figure 3, under 25 ℃ of conditions, take respectively 0.5,1.0,1.5,2.0,2.5, MCM-41 sieve sample prepared by 3.0g the present embodiment adds in Cr (VI) solion of 100 mL10mg/L, regulator solution pH=6, constant temperature oscillator vibration absorption 60min, after centrifugation, get supernatant liquor, adopt Cr (VI) ionic concn after the two hydrazine spectrophotometry absorption of phenylbenzene phosphinylidyne.The clearance of Cr (VI) ion is along with increase tendency appears in the increase of MCM-41 dosage, at the beginning because sorbent material consumption is very few, it is saturated that Cr in solution (VI) ion reaches absorption very soon, clearance is less, along with the increase of MCM-41 molecular sieve dosage, it is more and more that Cr in solution (VI) ion is adsorbed, clearance increases sharply, in the time that dosage reaches 2g, the clearance of Cr (VI) ion can reach 96.73%, continue to increase dosage, clearance changes and slows down gradually, until substantially remain unchanged again.
The present embodiment a kind of utilizes method and the application of coal ash for manufacturing for MCM-41 molecular sieve, substantially with embodiment 1, existing preparation process is summarized as follows:
Take 200g coal ash of power plant, at l00 ℃, dry to constant weight, then the hydrochloric acid soln that is 30% by it with mass percent concentration take solid-to-liquid ratio (g/mL) after 1:20 proportioning is mixed, stir 12h at 80 ℃ of lower magnetic forces, with the centrifugal speed centrifugation 30min of 6000rpm, with deionized water washing leaching cake to filtrate pH be 6, dry be placed in vacuum drier for subsequent use.
Take respectively pre-treating fly ash 20g and 44gNaOH, mix, and in retort furnace 600 ℃ calcining 3 h, taking-up naturally cools to room temperature, grinds to form fine powder and crosses 300 mesh sieves, and after grinding, calcined material is mixed with deionized water by solid-liquid mass ratio 1:20, stir 24h, under the rotating speed of 6000rpm, centrifugation 20min, gets supernatant liquor, as synthetic MCM-41 molecular sieve silicon source.
Take CTAB as template, according to n (CTAB): n (SiO
2): n (H
2o)=0.15: the mol ratio of 1:100, take CTAB and be dissolved in deionized water, bath temperature is made as 35 ℃, is stirred to solution and is the light blue of homogeneous clarification.Utilize magnetic stirring apparatus in continuous whipping process, dropwise drip (1 ~ 2/the silicon source solution s) prepared in step b, the HNO that is 15% by concentration
3the pH value of regulator solution is 10 ~ 11, continues to stir aging 2h, obtains white gels.Proceeded in tetrafluoroethylene reactor after 100 ℃ of crystallization 48h, naturally cool to room temperature, centrifugal, washing, dries, and in retort furnace, is warming up to 550 ℃ of roastings with 1 ℃/min speed, and then constant temperature calcining 6h, obtains mesopore molecular sieve MCM-41 sample.
The present embodiment a kind of utilizes method and the application of coal ash for manufacturing for MCM-41 molecular sieve, substantially with embodiment 1, existing preparation process is summarized as follows:
Take 200g coal ash of power plant, at l00 ℃, dry to constant weight, then the hydrochloric acid soln that is 25% by it with mass percent concentration take solid-to-liquid ratio (g/mL) after 1:20 proportioning is mixed, stir 12h at 80 ℃ of lower magnetic forces, with the centrifugal speed centrifugation 40min of 5000rpm, with deionized water washing leaching cake to filtrate pH be 6.5, dry be placed in vacuum drier for subsequent use.
According to m (SiO
2): m (NaOH)=1:2.2 proportioning, take respectively pre-treating fly ash and NaOH, mix, and in retort furnace 500 ℃ of calcining 3.5 h, take out and naturally cool to room temperature, grind to form fine powder and cross 300 mesh sieves, press solid-liquid mass ratio 1:20 and mix with deionized water, stir 24h, centrifugation 30min under 5000rpm, get supernatant liquor, as synthetic MCM-41 silicon source.
Take CTAB as template, according to n (CTAB): n (SiO
2): n (H2O)=0.15: the mol ratio of 1:100, take CTAB and be dissolved in deionized water, bath temperature is made as 35 ℃, is stirred to solution and is the light blue of homogeneous clarification.Utilize magnetic stirring apparatus in continuous whipping process, dropwise drip (1 ~ 2/the silicon source solution s) prepared in step b, the HNO that is 10% by concentration
3the pH value of regulator solution is 11, continues to stir aging 2h, obtains white gels.Proceeded in tetrafluoroethylene reactor after 100 ℃ of crystallization 48h, naturally cool to room temperature, centrifugal, washing, dries, and in retort furnace, is warming up to 550 ℃ of roastings with 1 ℃/min speed, and then constant temperature 6h, obtains mesopore molecular sieve MCM-41 sample.
A kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing described in embodiment 1 ~ 3, make full use of the flyash of power plant emission as silicon and aluminum source, extract silicon source by pre-treatment, then adopt hydro-thermal sol-gel method to prepare mesopore molecular sieve MCM-41 sample, for the comprehensive regulation and the deep processing of flyash have proposed new road.Be under the condition that 25 ℃, pH are 6, ionic concn is 10mg/L at solution temperature, maximum material removal rate to Cr (VI) ion can reach 97.86%, provide certain theoretical basis for MCM-41 molecular sieve is applied to sewage treatment area, using value is high.
Claims (8)
1. utilize the method for coal ash for manufacturing for MCM-41 molecular sieve, the steps include:
A, former flyash powder is dried to constant weight, mix with xeraphium coal ash with HCl solution, stirring, centrifugal, washing, dry for standby;
B, by flyash after treatment step a and NaOH mixed calcining, grind to form fine powder after cooling, calcined material after the grinding obtaining is joined in deionized water, mix, stir, centrifugation obtains supernatant liquor;
C, take template CTAB and be dissolved in deionized water, under water bath condition, continue to stir, dropwise drip the supernatant liquor obtaining in step b, use HNO
3regulator solution pH, continues to stir obtaining spawn, and the spawn obtaining is carried out to crystallization, naturally cools to room temperature after crystallization, and centrifugal, washing, oven dry, roasting obtain MCM-41 molecular sieve.
2. a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing according to claim 1, is characterized in that: in step a, the mass percent concentration of HCl solution used is 20%-30%, and the solid-liquid proportioning of xeraphium coal ash and HCl solution is 1:20; In centrifugally operated, centrifugal speed is 4000-6000rpm, and centrifugation time is 30-40min; In washing operation with deionized water wash to washings pH be 6 ~ 7.
3. a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing according to claim 2, is characterized in that: the contained SiO of flyash in calcination process described in step b
2with the mass ratio of NaOH be 1:2.2, calcining temperature is 500-600 ℃, calcination time 3-4 h.
4. according to a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing described in claim 2 or 3, it is characterized in that: in step b, cooling gained rear calcined material is ground to form to fine powder and cross 200-300 mesh sieve; After grinding, the mass ratio of calcined material and deionized water is 1:20; In stirring operation, churning time is 24 hours; In centrifugally operated, centrifugal speed is 4000-6000rpm, and centrifugation time is 20-30min.
5. a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing according to claim 4, is characterized in that: SiO in template CTAB, supernatant liquor in step c
2and H
2the mol ratio of O is 0.15: 1:100; Bath temperature is 35 ℃, and the rate of addition of the supernatant liquor obtaining in step b is 1 ~ 2/s; HNO
3the mass percent concentration of solution is 10%-15%, uses HNO
3regulator solution pH is 10 ~ 11.
6. a kind of method of coal ash for manufacturing for MCM-41 molecular sieve of utilizing according to claim 5, is characterized in that: in step c, crystallization temperature is 100 ℃, in roasting process, is warming up to 550 ℃ of roastings with the speed of 1 ℃/min.
7. utilize an application for MCM-41 molecular sieve prepared by the method for claim 1, it is characterized in that: described MCM-41 molecular sieve is for the absorption of Cr (VI) ion.
8. a kind of application of coal ash for manufacturing for MCM-41 molecular sieve that utilize according to claim 7, it is characterized in that: controlling adsorption temp is 25 ℃, be 6 containing Cr (VI) solion pH value, Cr in solution (VI) ionic concn is 10mg/L, the dosage of MCM-41 molecular sieve is 1:50 with the solid-to-liquid ratio containing Cr (VI) solion, Cr in adsorbent solution (VI) ion.
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| CN109704363A (en) * | 2018-12-27 | 2019-05-03 | 中国神华能源股份有限公司 | A kind of method that white clay prepares Al-MCM-41 molecular sieve |
| CN112387299A (en) * | 2020-11-30 | 2021-02-23 | 江南大学 | Method for preparing L-furan serine by biomass chemical-enzymatic method |
| TWI723352B (en) * | 2019-03-13 | 2021-04-01 | 逢甲大學 | Method of incineration ash reused for synthesis of porous materials |
| CN115818658A (en) * | 2021-09-17 | 2023-03-21 | 淮南师范学院 | Method for preparing zeolite molecular sieve by using fly ash as raw material |
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