CN103787366A - Preparation method of low-cost ZSM-5 type zeolite molecular sieve, and application thereof - Google Patents
Preparation method of low-cost ZSM-5 type zeolite molecular sieve, and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of low-cost ZSM-5 type zeolite molecular sieve, and application of the low-cost ZSM-5 type zeolite molecular sieve, belonging to the field of a molecular sieve preparation technology. The method comprises the steps of a. drying pulverized fuel ash raw powder to constant weight, mixing HCl solution with the dried pulverized fuel ash, stirring, centrifuging, washing and drying for later use; b. grinding the pulverized fuel ash treated by the step a, mixing the ground pulverized fuel ash with NaOH for melting, cooling, grinding and screening by a molecular sieve; feeding the ground melt into deionized water, mixing, stirring under the condition of water bath, and carrying out centrifugal separation to obtain liquid supernatant; c. taking the liquid supernatant obtained in the step b, taking tetrapropylammonium hydroxide as a template agent and NH4F as a mineralizer, mixing and carrying out crystallization reaction; after that, taking out the product, quenching to the room temperature, washing, drying and roasting to obtain the zeolite molecular sieve. According to the method, the pulverized fuel ash discharged by a thermal power plant is fully utilized as a silicon-alumininm source and is used for replacing pure chemical reagents Si and Al for synthesizing the molecular sieve, so that the synthesis cost of the molecular sieve is lowered, 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 that main silicon and aluminum source is prepared the method for ZSM-5 type zeolite molecular sieve and the application of this molecular sieve.
Background technology
ZSM-5 zeolite molecular sieve, because its unique shape selective catalysis and acid performance make it have very important application in catalysis and separation field, is the focus of chemical scientific research worker research always.At present, existing a large amount of report about ZSM-5 zeolite molecular sieve and performance study thereof, but mainly concentrate on the pure chemistry reagent such as the silica gel higher take cost, water glass, silicon sol, tetraethoxy as silicon source, also will add in addition the aluminium such as aluminum nitrate and Tai-Ace S 150 source, the preparation cost of molecular sieve is very high simultaneously.
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. 201310362950.4, the applying date is on August 20th, 2013, and invention and created name is: a kind of method of coal ash for manufacturing for nano level ZSM-5 molecular sieve of utilizing; This application case discloses a kind of coal ash for manufacturing that utilizes: the pre-treatment of flyash; Utilize pretreated coal ash for manufacturing for aluminium hydroxide and water glass; The aluminium hydroxide and the water glass that after flyash is processed, obtain mix with water, template TPAOH, wherein, water molar fraction is 90%-98%, TPAOH molar fraction is 0.25%-1.0%, aluminium hydroxide molar fraction is 0.025%-0.01%, and water glass molar fraction is 1%-2%; The synthetic 24h-72h of microwave-assisted at 150 ℃-250 ℃; Take out the resultant in reactor, 60-80 ℃ of washing 2-5 time, be dried 12h-24h at 120 ℃; Be dried rear sample roasting 4-8h at 600 ℃-800 ℃, obtain the finished product of nano level ZSM-5 molecular sieve, ZSM-5 molecular sieve particle diameter is 200nm-500nm.This application case has reduced the synthetic cost of ZSM-5 molecular sieve to a certain extent, has realized the recycling of flyash.But this application case is prepared the process complexity of molecular sieve, complicated processing step will cause corresponding the increasing of synthetic cost of molecular sieve undoubtedly, and therefore, this application case still needs further improvement.
Summary of the invention
1. the technical problem that invention will solve
The high deficiency of preparation cost that the object of the invention is to overcome ZSM-5 zeolite molecular sieve in prior art, provides a kind of preparation method and application of low cost ZSM-5 type zeolite molecular sieve; The present invention is using trade waste flyash as raw material, TPAOH (TPAOH) is template, a large amount of Si in extract powder coal ash, Al cycling of elements have been prepared into the ZSM-5 type zeolite molecular sieve that can directly utilize, the present invention's its essential mineral crystalline phase of flyash used is quartz and mullite, also has unformed glassy phase composition, Si, Al content are higher, especially have higher Si/Al ratio, have higher comprehensive utilization value.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve 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, porphyrize step a flyash after treatment, and with NaOH mixed melting, cooling rear porphyrize is crossed molecular sieve, and melts after the porphyrize obtaining is joined in deionized water, after mixing, under water bath condition, stir, centrifugation obtain supernatant liquor;
C, get the supernatant liquor obtaining in step b, take TPAOH as template, NH
4f is mineralizer, by supernatant liquor, TPAOH and NH
4after F hybrid reaction for some time, carry out crystallization, take out quenching to room temperature after crystallization, washing, oven dry, roasting obtain ZSM-5 type zeolite molecular sieve.
Further, in step a, when the former powder of ovendry power coal ash, temperature control is 110-140 ℃, and drying time is 20-24h; The mass percent concentration of HCl solution used is 10%, and the solid-liquid proportioning of xeraphium coal ash and HCl solution is 1:20; In washing operation, requiring the rear washings pH of washing is 6-7.
Further, the contained SiO of flyash in melting process described in step b
2with the mass ratio of NaOH be 1:2.2, melt temperature is 400-500 ℃, fusion time 3-5h.
Further, in step b, before melting operation, by flyash porphyrize after treatment step a, to 300-400 order, after porphyrize, the mass ratio of melts and deionized water is 1:2～4; Bath temperature is 80 ℃, and churning time is 24 hours; Centrifugal speed is 4000-6000rpm, and centrifugation time is 8-10min.
Further, SiO in template TPAOH, supernatant liquor in step c
2and H
2o and mineralizer NH
4the mol ratio of F is 0.2:1:25:0.2, and the hybrid reaction time is 6～12h; Crystallization temperature is 170 ℃; In roasting process, be warming up to 550 ℃ of roasting 6h with the speed of 2 ℃/min.
The preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve of the present invention, step c changes into: get the supernatant liquor obtaining in step b, take TPAOH as template, dehydrated alcohol is directed agents, by supernatant liquor, TPAOH with after dehydrated alcohol hybrid reaction for some time, carry out crystallization, take out quenching to room temperature after crystallization, washing, oven dry, roasting obtain ZSM-5 type zeolite molecular sieve.
Further, SiO in template TPAOH, supernatant liquor in step c
2and H
2the mol ratio of O and directed agents dehydrated alcohol is 1:5:500:20, and the hybrid reaction time is 6～12h; Crystallization temperature is 170 ℃; In roasting process, be warming up to 550 ℃ of roasting 6h with the speed of 2 ℃/min.
The application of a kind of low cost ZSM-5 type zeolite molecular sieve of the present invention, described zeolite molecular sieve is for the absorption of Cr (VI) ion.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following unusual effect:
(1) preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve of the present invention, makes full use of the flyash of power plant emission as silicon and aluminum source, replaces Si, Al pure chemistry reagent synthesis of molecular sieve, has reduced the synthetic cost of molecular sieve;
(2) preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve of the present invention, carries out the pre-treatment of single step to flyash, and more convenient operation, has saved reactions steps; Adopt conventional low price chemical reagent, fully improve the activity of flyash, guarantee in the building-up process of molecular sieve, to there is suitable raw material ratio, and by selecting different auxiliary reagents, make molecular sieve form different shapes, to adapt to different environmental requirements, expanded range of application;
(3) application of a kind of low cost ZSM-5 type zeolite molecular sieve of the present invention, this zeolite molecular sieve has good adsorptive power to Cr (VI) ion, under 25 ℃, the condition of pH=6, to reaching more than 88% containing the clearance of Cr (VI) ion in the standardized solution of Cr (VI) ion.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of the ZSM-5 molecular sieve that (a) in Fig. 1 prepares for synthetic schemes one of the present invention; The scanning electron microscope (SEM) photograph of the ZSM-5 molecular sieve that (b) in Fig. 1 prepares for synthetic schemes two of the present invention;
Fig. 2 is the XRD x ray diffration pattern x of the former powder of flyash that adopts of the present invention;
Fig. 3 is that the present invention uses ZSM-5 molecular sieve that two kinds of synthetic schemess prepare the respectively adsorption curve figure to Cr (VI) ion, in figure, z-1 represents the ZSM-5 molecular sieve that uses synthetic schemes one to prepare, and z-2 represents the ZSM-5 molecular sieve that uses synthetic schemes two to prepare.
Embodiment
For further understanding content of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
By reference to the accompanying drawings, the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve of the present embodiment, flyash used is from fuel-burning power plant, Huainan, and the XRD x ray diffration pattern x of the former powder of flyash is referring to Fig. 2.The former powder essential mineral of flyash crystalline phase is quartz and mullite, also has unformed glassy phase composition.Analyze its main chemical compositions in table 1 through Xray fluorescence spectrometer (XRF).Can obtain the metallic impurity such as Fe, Ca in the flyash that the present embodiment uses by table 1 and occupy a part of ratio, but Si, Al content are higher, especially have higher Si/Al ratio, can separately add silicon source, aluminium source when synthetic, have higher comprehensive utilization value.
The main chemical compositions (wt%) of table 1 flyash
The present embodiment chemical reagent used is as TPAOH (TPAOH), NH
4f, NaOH, HCl etc. are analytical pure.
The concrete preparation process of a kind of low cost ZSM-5 type zeolite molecular sieve of the present embodiment is:
A, former flyash powder 100g is dried to 24h to constant weight at 110 ℃, the HCl solution that is 10% with mass percent concentration by xeraphium coal ash mixes take solid-liquid proportioning (g/mL) as the ratio of 1:20 that (the functional quality percentage concentration HCl concentration enough as 10% hydrochloric acid soln has both guaranteed to have is removed foreign ion, can make again solid and solution have more suitable solid-to-liquid ratio) simultaneously, fully stir 20min, centrifugation 15min under 5000rpm condition, remove after supernatant liquid, with deionized water wash be 7 to washings pH, dry for standby at 100 ℃.
What deserves to be explained is herein, although to enrich silane agent be molecular sieve the synthetic basic substance and may of providing containing in the flyash that the present embodiment adopts, but in flyash, also contain the metallic impurity such as Fe, Ca and the volatilizable organic composition thereof of high level simultaneously, can be to molecular sieve synthetic unfavorable.If directly flyash is reacted for alkali fusion, in flyash, the contained metallic impurity such as Fe, Ca can reduce the transformation efficiency of Si, Al so, traditional treatment process, as the part Fe of physics magnetic method in can only treated coal ash, can not reach good treatment effect for metallic impurity such as Ca.The present embodiment is carrying out before alkali fusion reaction, by the processing of single step chemical acidification, and the correlation parameter in treating processes is optimized to regulation and control, the metallic impurity such as Fe, Ca clearance in flyash can reach more than 99.6%, more convenient operation, has saved reactions steps, simultaneously remaining Si, the synthesis material that Al composition can replace pure chemistry composition completely after Impurity removal, the activity of powdered coal ash improves greatly, is more conducive to the synthetic of molecular sieve.
B, the iron power removing coal ash that accurately takes 20g step a acquisition and 44g NaOH mix, porphyrize evenly to 300 order is placed in retort furnace melting 5h under 400 ℃ of conditions, cooling rear porphyrize is crossed 200 mesh sieves, melts after the porphyrize obtaining is joined in deionized water in the ratio of solid-liquid mass ratio 1:2, be mixed into muddy, under 80 ℃ of water bath condition, stir 24h, make as far as possible particle be uniformly dispersed in solution, make silico-aluminate in flyash at OH
-effect under abundant stripping, then centrifugation 10min under 4000rpm condition, obtain supernatant liquor as silicon and aluminum source.
The synthetic of c, ZSM-5 molecular sieve can adopt two kinds of synthetic schemess, and the present embodiment adopts synthetic schemes one: get the supernatant liquor that a certain amount of step b obtains, take TPAOH (TPAOH) as template, select NH simultaneously
4f is mineralizer, according to n (TPAOH): n (SiO
2): n (H
2o): n (NH
4f) mol ratio of=0.2:1:25:0.2, in there-necked flask, react 12h, be placed in tetrafluoroethylene reactor takes out after crystallization 24h under 170 ℃ of conditions, with the quenching of a large amount of tap water shower fast cooling to 30 ℃ of room temperatures, washing, dry, in retort furnace, with speed temperature programming to the 550 ℃ roasting 6h of 2 ℃/min, obtain white powder ZSM-5 molecular sieve.
Adopt the scanning electron microscope (SEM) photograph of the ZSM-5 molecular sieve for preparing of synthetic schemes one referring to (a) in Fig. 1, the coacervate that its main pattern is slice-type, lamellar spacing can reach nano level, is typical MFI type topological framework.Because hydrophilic group and hydrophobic group under the effect at F-mineralizer have formed laminate structure, thereby make crystal trend towards forming the ZSM-5 molecular sieve of thin layer stratiform pattern.The present embodiment, take TPAOH (TPAOH) as template, is selected NH simultaneously
4f is mineralizer, be conducive to like this generate laminate structure, and produce less macrocrystal defect, in roasting process with 2 ℃/min speed temperature programming to 550 ℃ roasting 6h, can make by slower temperature rise rate that template is relatively mild to be removed, prevent the defect of the crystalline structure comparatively fast causing because of template removal.
The ZSM-5 molecular sieve that the present embodiment prepares has good adsorptive power to Cr (VI) ion, take respectively the ZSM-5 molecular sieve sample that 2g the present embodiment prepares, join in 100mL0.01mol/L Cr (VI) ion standardized solution, under 25 ℃, pH=6 condition in constant temperature water bath with certain rate oscillation absorption 30min, centrifugation, get supernatant liquor, adopt Cr (VI) ionic concn after the two hydrazine spectrophotometry absorption of phenylbenzene phosphinylidyne.
The synthetic ZSM-5 molecular sieve of the present embodiment to Cr (VI) ion standardized solution absorption property change curve referring to Fig. 3, as we can see from the figure, ZSM-5 molecular sieve has good adsorption to Cr (VI), when initial, absorption is very fast, along with the increase adsorption rate of adsorption time slows down, finally be tending towards constant, illustrate reached absorption saturated.The synthetic ZSM-5 molecular sieve of the present embodiment is 88.95% to the clearance that contains Cr (VI) ion in the standardized solution of Cr (VI) ion.
Embodiment 2
The preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve of the present embodiment, substantially with embodiment 1, is now summarized as follows preparation process:
Former flyash powder is dried to 20h to constant weight at 140 ℃, the HCl solution that is 10% with mass percent concentration by xeraphium coal ash mixes take solid-liquid proportioning (g/mL) as 1:20, fully stir 30min, centrifugation 10min under 5000rpm condition, remove after supernatant liquid, with deionized water wash be 6 to pH, dry for standby at 100 ℃.
Accurately taking 20g iron power removing coal ash and 44gNaOH mixes, porphyrize evenly to 400 order is placed in retort furnace melting 3h at 500 ℃, cooling rear porphyrize is crossed 200 mesh sieves, melts after the porphyrize obtaining is joined in deionized water in the ratio of solid-liquid mass ratio 1:4, be mixed into muddy, stirring in water bath 24h at 80 ℃, makes silico-aluminate in flyash at OH
-effect under stripping, then centrifugation 8min under 6000rpm condition, obtain supernatant liquor as silicon and aluminum source.
The present embodiment still selects synthetic schemes one to prepare ZSM-5 molecular sieve, is specially: get a certain amount of above-mentioned supernatant liquor, take TPAOH (TPAOH) as template, select NH simultaneously
4f is mineralizer, according to n (TPAOH): n (SiO
2): n (H
2o): n (NH
4f) mol ratio of=0.2:1:25:0.2, in there-necked flask, react 6h, be placed in after 170 ℃ of crystallization 48h of tetrafluoroethylene reactor, take out with the quenching of a large amount of tap water shower fast cooling to room temperature, washing, dry, in retort furnace, with 2 ℃/min speed temperature programming to 550 ℃ roasting 6h, obtain white powder ZSM-5 molecular sieve.The synthetic ZSM-5 molecular sieve of the present embodiment is to the clearance 91.2% containing Cr (VI) ion in the standardized solution of Cr (VI) ion.
Embodiment 3
The preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve of the present embodiment, substantially with embodiment 1, is now summarized as follows preparation process:
Former flyash powder is dried to 22h to constant weight at 125 ℃, the HCl solution that is 10% with mass percent concentration by xeraphium coal ash mixes take solid-liquid proportioning (g/mL) as 1:20, fully stir 25min, centrifugation 13min under 5000rpm condition, remove after supernatant liquid, with deionized water wash to pH=7, dry for standby at 100 ℃.
Accurately take iron power removing coal ash and NaOH according to mass ratio m (SiO
2): m (NaOH)=1:2.2 proportioning, porphyrize evenly to 200 order is placed in retort furnace melting 4h at 450 ℃, cooling rear porphyrize is crossed 200 mesh sieves, melts after the porphyrize obtaining is joined in deionized water in the ratio of solid-liquid mass ratio 1:3, be mixed into muddy, stirring in water bath 24h at 80 ℃, makes silico-aluminate in flyash at OH
-effect under stripping, then centrifugation 9min under 5000rpm condition, obtain supernatant liquor as silicon and aluminum source.
The present embodiment selects synthetic schemes two to prepare ZSM-5 molecular sieve, is specially: get a certain amount of above-mentioned supernatant liquor, take TPAOH (TPAOH) as template, dehydrated alcohol is directed agents, according to n (TPAOH): n (SiO
2): n (H
2o): the mol ratio of n (EtOH)=1:5:500:20, in there-necked flask, react 8h, be placed in after 170 ℃ of crystallization 36h of tetrafluoroethylene reactor, take out with the quenching of a large amount of tap water shower fast cooling to room temperature, washing, dry, in retort furnace, with 2 ℃/min speed temperature programming to 550 ℃ roasting 6h, obtain white powder ZSM-5 molecular sieve.
Adopt the scanning electron microscope (SEM) photograph of the ZSM-5 molecular sieve for preparing of synthetic schemes two referring to (b) in Fig. 1, the hexagonal structure of length that its main pattern is similar phenyl ring, globule size is very even, and its particle diameter is greatly about 1-2 μ m.In the present embodiment, add ethanol can under weak basic condition, generate the hexagonal infrastructure product of length of high-quality similar phenyl ring, the while is because the present embodiment has increased H
2o/Si ratio, in crystallization process, the concentration of nucleus is lower, makes the nucleus more nutritive substance of enrichment around, grows up thereby crystal grain has enough geometric spaces to be cross-linked with each other.The ZSM-5 molecular sieve that the present embodiment is synthetic, the clearance 82.71% to 100mL0.01mol/L Cr (VI) ion standardized solution Cr (VI) ion under 25 ℃, pH=6 condition.
The preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve described in embodiment 1～3, make full use of the flyash of power plant emission as silicon and aluminum source, replace Si, Al pure chemistry reagent synthesis of molecular sieve, reduce the synthetic cost of molecular sieve, and be conducive to the comprehensive utilization of natural resource and industrial waste.Obtain respectively two kinds of patterns by two kinds of synthetic schemess and had the type ZSM 5 molecular sieve of bigger difference, and the size of zeolite molecular sieve and pattern can directly affect the performances such as catalysis, absorption and the ion-exchange of zeolite molecular sieve, the pattern that it is various and skeleton structure can provide special purpose for aspects such as Industrial Catalysis.In addition, by flyash being carried out to the pre-treatment of single step, make the preparation manipulation of molecular sieve convenient, cost further reduces.The zeolite molecular sieve preparing has good adsorptive power to Cr (VI) ion, provides certain theoretical basis for ZSM-5 molecular sieve is applied to sewage treatment area, and using value is high.
Claims (8)
1. a preparation method for low cost ZSM-5 type zeolite 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, porphyrize step a flyash after treatment, and with NaOH mixed melting, cooling rear porphyrize is crossed molecular sieve, and melts after the porphyrize obtaining is joined in deionized water, after mixing, under water bath condition, stir, centrifugation obtain supernatant liquor;
C, get the supernatant liquor obtaining in step b, take TPAOH as template, NH
4f is mineralizer, by supernatant liquor, TPAOH and NH
4after F hybrid reaction for some time, carry out crystallization, take out quenching to room temperature after crystallization, washing, oven dry, roasting obtain ZSM-5 type zeolite molecular sieve.
2. the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve according to claim 1, is characterized in that: in step a, when the former powder of ovendry power coal ash, temperature control is 110-140 ℃, and drying time is 20-24h; The mass percent concentration of HCl solution used is 10%, and the solid-liquid proportioning of xeraphium coal ash and HCl solution is 1:20; In washing operation, requiring the rear washings pH of washing is 6-7.
3. the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve according to claim 2, is characterized in that: the contained SiO of flyash in melting process described in step b
2with the mass ratio of NaOH be 1:2.2, melt temperature is 400-500 ℃, fusion time 3-5h.
4. the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve according to claim 3, it is characterized in that: in step b before melting operation, by flyash porphyrize after treatment step a, to 300-400 order, after porphyrize, the mass ratio of melts and deionized water is 1:2～4; Bath temperature is 80 ℃, and churning time is 24 hours; Centrifugal speed is 4000-6000rpm, and centrifugation time is 8-10min.
5. the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve according to claim 4, is characterized in that: SiO in template TPAOH, supernatant liquor in step c
2and H
2o and mineralizer NH
4the mol ratio of F is 0.2:1:25:0.2, and the hybrid reaction time is 6～12h; Crystallization temperature is 170 ℃; In roasting process, be warming up to 550 ℃ of roasting 6h with the speed of 2 ℃/min.
6. according to the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve described in claim 1～4 any one, it is characterized in that: step c changes into: get the supernatant liquor obtaining in step b, take TPAOH as template, dehydrated alcohol is directed agents, by supernatant liquor, TPAOH with after dehydrated alcohol hybrid reaction for some time, carry out crystallization, take out quenching to room temperature after crystallization, washing, oven dry, roasting obtain ZSM-5 type zeolite molecular sieve.
7. the preparation method of a kind of low cost ZSM-5 type zeolite molecular sieve according to claim 6, is characterized in that: SiO in template TPAOH, supernatant liquor in step c
2and H
2the mol ratio of O and directed agents dehydrated alcohol is 1:5:500:20, and the hybrid reaction time is 6～12h; Crystallization temperature is 170 ℃; In roasting process, be warming up to 550 ℃ of roasting 6h with the speed of 2 ℃/min.
8. utilize an application for ZSM-5 type zeolite molecular sieve prepared by the method for claim 1, it is characterized in that: described zeolite molecular sieve is for the absorption of Cr (VI) ion.
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