CN108059171A - A kind of method of flyash synthesis HZSM-5 type zeolites - Google Patents
A kind of method of flyash synthesis HZSM-5 type zeolites Download PDFInfo
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- CN108059171A CN108059171A CN201810037084.4A CN201810037084A CN108059171A CN 108059171 A CN108059171 A CN 108059171A CN 201810037084 A CN201810037084 A CN 201810037084A CN 108059171 A CN108059171 A CN 108059171A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention relates to a kind of methods of flyash synthesis 5 type zeolites of HZSM；Flyash obtains the pretreatment product that silica alumina ratio significantly improves by the molten processing of acid under the conditions of grinding screening, alkali fusion, boiling.Then a certain amount of water and template are added in the product, and with sodium hydrate regulator solution pH after stirring evenly, after being aged a period of time at ambient temperature, the 5 type zeolites of HZSM of high-quality have been synthesized by hydro-thermal reaction；The present invention is easy to operate, realizes the recycling of solid waste coal ash.The zeolite product of synthesis is the 5 type zeolites of HZSM of single crystalline phase, and crystallinity is more than 95%, and purity is more than 98%, in preferable hexagonal prisms characters and appearances.
Description
Technical field
The sial component in solid waste coal ash is the present invention relates to the use of, HZSM-5 type zeolites are synthesized by hydro-thermal method
Method.The method can realize the recycling of solid waste, while realize synthetic product in chemical industry, material, environment
The application in the fields such as protection, belongs to Solid Waste Treatment and recycling field.
Background technology
As one of most important energy, coal has become the energy core of China's industrial development, and raw coal consumption figure is for many years
To account for primary energy total quantity consumed more than 70% always.Chinese coal consumption in 2016 reaches 18.88 hundred million tons of oil equivalents, accounts for generation
The 50.58% of boundary's coal aggregate consumption.Coal burn after about 20% solid formed incineration residue, other about 80% solids with
The form of flying dust forms flyash.With a large amount of uses of coal, the annual output of China's flyash occupies the world more than 600,000,000 tons
First place, but utilization rate is relatively low.According to statistics, China's flyash adds up volume of cargo in storage more than 2,500,000,000 t, 50,000 hm of floor space2With
On.The random accumulation of flyash had both occupied a large amount of arable lands, while soil, water resource and air are caused seriously to pollute.Flyash
Comprehensive utilization is the important topic that China researchs and solves for many years.
At present, the utilization of flyash, which essentially consists in, makees construction material, prepares ceramics, road pavement and local soil improvement etc.
Aspect pertains generally to low value-added, low technical content extensive style and utilizes.Due to containing a large amount of unformed aluminium oxide in flyash
And silica, it is similar to the chemical composition of zeolite, it is considered as most having for resource reutilization using synthetic zeolite from flyash therefore
One of effect approach.Synthetic zeolite from flyash generally has larger specific surface area and pore volume, there is good cation exchange property
And absorption property, the field of environment protection such as soil remediation, gas phase isolation of purified, stain disease processing can be applied, can also be used as
The special materials such as catalyst, detergent, heat preservation play a significant role in fields such as chemical industry, petrochemical industry, materials.
HZSM-5 zeolites are a kind of crystalline alumino metal salt, are the bodies formed by silicon (aluminium) oxygen tetrahedron for structural unit
Space net structure has the pore passage structure (0.56nm × 0.53nm and 0.55nm × 0.51nm) of two-dimentional 10 × 10 yuan of rings.Its
Crystal belongs to preferable orthorhombic system, and structure cell composition can be expressed as：Nan(AlnSi96-nO192)·16H2O (n is 0-20 or so),
Space group Pmna and lattice constant are a=20.1, b=19.9, c=13.4.HZSM-5 zeolites possess unique intersection duct knot
Structure, while have hydro-thermal stabilization, acidity is adjustable, and thermal stability is excellent, and catalytic activity is strong, stronger anti-carbon deposition ability and excellent
The features such as different selectivity, therefore obtained in the multiple fields such as petroleum refining, chemical industry catalysis, one chemical industry of carbon, fine chemistry industry, environmental protection
Extensive use.
At present, the synthesis of HZSM-5 zeolite molecular sieves is mainly chemical synthesis, by the use of cheap mineral as whole silicon
Silicon source hydrothermal synthesis is seldom.And since synthesis condition is more complicated, the reasons such as synthesis technology is not perfect, the big polycrystalline of synthetic product
Degree and purity are relatively low, it is impossible to meet application requirement.It is complete the present invention provides a kind of synthetic method of the HZSM-5 type zeolites of simplicity
Complete utilization flyash, using grinding screening-alkali fusion-pickling-hydro-thermal synthesis process, successfully synthesizes crystallinity as silicon and aluminum source
More than 95%, purity is more than 98% HZSM-5 type zeolites, has a good application prospect.
The content of the invention
The object of the present invention is to provide the method for flyash synthesis HZSM-5 type zeolites, improvement that can be for flyash and resource
Change to utilize and the choice of technology is provided.
The synthetic method of the flyash synthesis HZSM-5 type zeolites of the present invention, characterization step are as follows：
1) screening process is ground：Flyash crude product is ground with comminuted grinder, is then carried out by 100 mesh sieves
Screening；
2) alkali fusion is handled：After flyash and sodium hydrate solid mixing that step 1) is obtained, at 650 DEG C -850 DEG C
2h is calcined, after being cooled to room temperature, calcined product is ground to product；
3) the molten processing of acid：Add in sulfuric acid solution into step 2) calcined product, be heated to seething with excitement, under the conditions of condensing reflux into
Row reaction 1-3h, filters product after cooling, then washing obtains flyash in oven drying；
4) hydrothermal synthesis：It is obtained to step 3) and distilled water is added in the product of flyash, after stirring, added into solution
Enter template 4-propyl bromide, after it is completely dissolved, it is 10-11.5 to adjust mixed solution pH with sodium hydroxide solution；It is mixed
It closes material and is aged 12h-24h at room temperature, be then transferred in hydrothermal reaction kettle, seal, then hydrothermal reaction kettle is put into baking oven
Middle reaction；After hydrothermal reaction kettle is cooled to room temperature, supernatant is outwelled, solid product is filtered, and is washed with distilled water filter cake extremely
Filtrate pH, then by product in being put into oven drying, obtains HZSM-5 type zeolites to neutrality.
Flyash and sodium hydroxide mass ratio are 1 in the step 2):0.5-0.8.
Sulfuric acid mass fraction 65% in the step 3), solid-to-liquid ratio use 1:5-15 (mass/volume, g/ml).
Flyash and distilled water solid-to-liquid ratio scope 1 in the step 4):12-18 (mass/volume, g/ml), mixing time
15-30min。
Template and flyash quality are than scope 0.4-1.8 in the step 4):1(g/g).
Step 4) the hydrothermal reaction kettle is put into 140-180 DEG C of reaction temperature in baking oven, reaction time 36-48h.
The step 3) and 4) in drying temperature be 100-105 DEG C.
It is described as follows:
Milled processed：Raw material flyash using comminuted grinder is ground, and passes through the screening of 100 mesh sieves, takes sieve
Raw material of the lower flyash as subsequent processing；The purpose of this step is to reduce grain graininess, and is more uniformly distributed solid particle,
It is more advantageous to subsequent reactions.The powder x-ray diffraction (XRD) and scanning electron microscope (SEM) of raw materials used flyash respectively as Fig. 1,
Shown in Fig. 2.
Alkali fusion processing：Above-mentioned flyash and sodium hydrate solid are taken according to quality 1:After 0.5-0.8 ratio mixings,
2h is calcined at 650 DEG C -850 DEG C, after being cooled to room temperature, product is ground；The purpose of the step is in flyash is removed
While carbon component, silicon and aluminum source in activating fly ash improves its reactivity.
The molten processing of acid：According to solid-to-liquid ratio (mass/volume, g/ml) 1:5-1:15 add in mass fraction into calcined product
65% sulfuric acid solution is heated to seething with excitement, and reaction 1-3h is carried out under the conditions of condensing reflux, and product is filtered after cooling, washing, then
It is dry under the conditions of 100-105 DEG C of baking oven.The purpose of the processing is in the impurity such as iron, calcium, sulphur in flyash is removed, raising fine coal
The silica alumina ratio of ash.
Hydrothermal synthesis：Distilled water is added in into acid-treated product, after stirring, template tetrapropyl bromination is added in into solution
Ammonium, after it is completely dissolved, it is 10-11.5 to adjust pH value of solution with sodium hydrate aqueous solution, and mixed material is aged at room temperature
12h-24h is then transferred in hydrothermal reaction kettle, sealing, then hydrothermal reaction kettle is put into baking oven, anti-at 140-180 DEG C
Answer 36-48h；After hydrothermal reaction kettle is cooled to room temperature, supernatant is outwelled, solid product is filtered, and is washed with distilled water filter cake
To filtrate pH to neutrality, product is then put into 100-105 DEG C of drying of baking oven, obtains HZSM-5 type zeolites.The powder of zeolite product
Last X-ray diffraction (XRD) and scanning electron microscope difference are as shown in Figure 3, Figure 4.
The present invention provides a kind of methods of easy-to-use alkali fusion-pickling-hydrothermal synthesis HZSM-5 zeolites.Synthesis
The powder x-ray diffraction figure (XRD) of zeolite product is without miscellaneous peak, and for the HZSM-5 type zeolites of single crystalline phase, crystallinity is more than
95%, purity is more than 98%, in preferable hexagonal prisms characters and appearances.The present invention is easy to operate, realizes solid waste fine coal
The recycling of ash.The zeolite product of synthesis is its X-ray powder diffraction statistics indicate that its characteristic peak angle of diffraction (2 θ) point
Wei not be 7.859 °, 8.770 °, 13.825 °, 14.727 °, 15.821 °, 20.751 °, 22.986 °, 23.205 °, 23.842 °,
24.299 °, 25.799 ° and 29.756 °, as shown in Figure 3.The infrared spectrum of synthetic zeolite has the characteristic absorption of HZSM-5 zeolites
Peak (Fig. 5).
Description of the drawings
Fig. 1 powdered coal ash x-ray diffraction patterns；
Fig. 2 powdered coal ash scanning electron microscope (SEM) photographs；
Fig. 3 synthesizes the powder x-ray diffraction figure of HZSM-5 type zeolites；
Fig. 4 synthesizes the scanning electron microscope (SEM) photograph of HZSM-5 type zeolites；
Fig. 5 synthesizes the infared spectrum of HZSM-5 type zeolites.
Specific embodiment
Embodiment 1.
1)：Certain fly ash in electric power plant is taken, fine ash is ground into grinder, then aperture is used to be sieved for the sieve of 100 mesh
Point；
2)：The the 1) undersized product 6g in step is taken, 3.0g sodium hydrate solids is added in, is put into after mixing fully in crucible,
2.0h is calcined at 650 DEG C, be then cooled to room temperature and grinds calcined product；
3)：Step 2) product is placed in conical flask, 65% sulfuric acid 45mL of mass fraction is added in thereto, is heated to seething with excitement,
3h is reacted under the conditions of condensing reflux, is then filtered, solid product is washed, is then placed in 105 DEG C of dryings of baking oven；
4)：72mL distilled water is added in into step 3) obtained solid, after magnetic agitation 30min, adds in 8.5g tetrapropyl bromines
Change ammonium, after it is completely dissolved, it is 10.0 to adjust mixed solution pH with 2mol/LNaOH, and ageing is then stirred at room temperature for 24 hours,
Then mixture is transferred in hydrothermal reaction kettle, after good seal at 180 DEG C crystallization 36h；After the completion of reaction, take out simultaneously
It is cooled to room temperature, outwells supernatant, filter solid product, and filter cake is washed with clear water, until washing lotion pH is neutrality, with
After being dried at 105 DEG C to get to HZSM-5 type zeolites.
Embodiment 2.
1)：Certain fly ash in electric power plant is taken, fine ash is ground into grinder, then aperture is used to be sieved for the sieve of 100 mesh
Point；
2)：The the 1) undersized product 6g in step is taken, 4.8g sodium hydrate solids is added in, is put into after mixing fully in crucible,
2.0h is calcined at 850 DEG C, be then cooled to room temperature and grinds calcined product；
3)：Step 2) product is placed in conical flask, 65% sulfuric acid 162mL of mass fraction is added in thereto, is heated to seething with excitement,
1h is reacted under the conditions of condensing reflux, is then filtered, solid product is washed, is then placed in 105 DEG C of dryings of baking oven；
4)：108mL distilled water is added in into step 3) obtained solid, after magnetic agitation 15min, adds in 3.8g tetrapropyl bromines
Change ammonium, after it is completely dissolved, it is 11.5 to adjust mixed solution pH with 2mol/LNaOH, and ageing 12h is then stirred at room temperature,
Then mixture is transferred in hydrothermal reaction kettle, after good seal at 160 DEG C crystallization 40h；After the completion of reaction, take out simultaneously
It is cooled to room temperature, outwells supernatant, filter solid product, and filter cake is washed with clear water, until washing lotion pH is neutrality, with
After being dried at 105 DEG C to get to HZSM-5 type zeolites.
Embodiment 3.
1)：Certain fly ash in electric power plant is taken, fine ash is ground into grinder, then aperture is used to be sieved for the sieve of 100 mesh
Point；
2)：The the 1) undersized product 6g in step is taken, 3.5g sodium hydrate solids is added in, is put into after mixing fully in crucible,
2.0h is calcined at 750 DEG C, be then cooled to room temperature and grinds calcined product；
3)：Step 2) product is placed in conical flask, 65% sulfuric acid 95mL of mass fraction is added in thereto, is heated to seething with excitement,
2h is reacted under the conditions of condensing reflux, is then filtered, solid product is washed, is then placed in 105 DEG C of dryings of baking oven；
4)：90mL distilled water is added in into step 3) obtained solid, after magnetic agitation 20min, adds in 1.4g tetrapropyl bromines
Change ammonium, after it is completely dissolved, it is 11.0 to adjust mixed solution pH with 2mol/LNaOH, and ageing 20h is then stirred at room temperature,
Then mixture is transferred in hydrothermal reaction kettle, after good seal at 140 DEG C crystallization 48h；After the completion of reaction, take out simultaneously
It is cooled to room temperature, outwells supernatant, filter solid product, and filter cake is washed with clear water, until washing lotion pH is neutrality, with
After being dried at 105 DEG C to get to HZSM-5 type zeolites.
The powder x-ray diffraction figure (XRD) of the zeolite product of above-described embodiment synthesis is without miscellaneous peak, for single crystalline phase, X
Ray powder diffraction data shows that its characteristic peak angle of diffraction (2 θ) is respectively 7.859 °, 8.770 °, 13.825 °, 14.727 °,
15.821 °, 20.751 °, 22.986 °, 23.205 °, 23.842 °, 24.299 °, 25.799 ° and 29.756 °, as shown in Figure 3.It closes
Infrared spectrum into zeolite has the characteristic absorption peak (Fig. 5) of HZSM-5 zeolites.
The method that the present invention disclosed and proposed simple, efficient water of coal ash thermal synthesis HZSM-5 type zeolites.This field skill
Art personnel can be by using for reference present disclosure, and the appropriate preparation method for changing coal ash alkali heat treatment of raw materials or treatment conditions can be real
It is existing.In particular, it should be pointed out that all similar replacements and change are apparent to those skilled in the art, he
Be considered as being included in spirit of the invention, scope and content.
Claims (9)
- A kind of 1. method of flyash synthesis HZSM-5 type zeolites；Its characterization step is as follows：1) screening process is ground：Flyash crude product is ground with comminuted grinder, is then sieved by 100 mesh sieves Point；2) alkali fusion is handled：After flyash and sodium hydrate solid mixing that step 1) is obtained, calcined at 650 DEG C -850 DEG C 2h after being cooled to room temperature, is ground product to obtain calcined product；3) the molten processing of acid：Sulfuric acid solution is added in into step 2) calcined product, is heated to seething with excitement, is carried out under the conditions of condensing reflux anti- 1-3h is answered, product is filtered after cooling, washing then in oven drying, obtains flyash；4) hydrothermal synthesis：It obtains adding in distilled water in product flyash to step 3), after stirring, template four is added in into solution Propyl ammonium bromide, after it is completely dissolved, it is 10-11.5 to adjust mixed solution pH with sodium hydroxide solution；Mixed material is in room The lower ageing 12h-24h of temperature, is then transferred in hydrothermal reaction kettle, seals, then hydrothermal reaction kettle is put into baking oven and is reacted；Treat water After thermal response kettle is cooled to room temperature, supernatant is outwelled, filter solid product, and be washed with distilled water filter cake to filtrate pH into Property, then by product in being put into oven drying, obtain HZSM-5 type zeolites.
- 2. the method as described in claim 1, it is characterized in that flyash and sodium hydroxide mass ratio are 1 in the step 2): 0.5-0.8。
- 3. the method as described in claim 1, it is characterized in that sulfuric acid mass fraction 65% in the step 3), solid-to-liquid ratio 1:5-15 (g/ml)。
- 4. the method as described in claim 1, it is characterized in that flyash and distilled water solid-to-liquid ratio scope 1 in the step 4):12- 18(g/ml)。
- 5. the method as described in claim 1, it is characterized in that adding in the mixing time of distilled water in the step 4) in flyash 15-30min。
- 6. the method as described in claim 1, it is characterized in that template and flyash quality are than scope 0.4- in the step 4) 1.8:1。
- 7. the method as described in claim 1, it is characterized in that the step 4) hydrothermal reaction kettle is put into reaction temperature in baking oven 140-180℃。
- 8. the method as described in claim 1, it is characterized in that the step 4) hydrothermal reaction kettle is put into reaction time 36- in baking oven 48h。
- 9. the method as described in claim 1, it is characterized in that the step 3) or 4) in drying temperature be 100-105 DEG C.
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Cited By (5)
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| CN109879295A (en) * | 2019-04-25 | 2019-06-14 | 太原理工大学 | A kind of ZSM-5 molecular sieve |
| CN110980913A (en) * | 2019-12-27 | 2020-04-10 | 张家港三得利染整科技有限公司 | Composite flocculant for treating printing and dyeing wastewater and preparation method and application thereof |
| CN111333081A (en) * | 2020-02-29 | 2020-06-26 | 山西大学 | Method for preparing ZSM-5 molecular sieve with low silica-alumina ratio by using high-alumina pulverized coal furnace fly ash |
| WO2021014513A1 (en) * | 2019-07-19 | 2021-01-28 | 株式会社環境浄化センター | Production method relating to industrial mass-production of high-purity artificial zeolite |
| CN115784254A (en) * | 2022-11-02 | 2023-03-14 | 吉林化工学院 | Preparation method of fly ash-based MFI structure nano zeolite rich in mesopores |
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| CN106495181A (en) * | 2016-10-26 | 2017-03-15 | 天津大学 | A kind of method that flyash synthesizes y-type zeolite |
| WO2017221192A1 (en) * | 2016-06-23 | 2017-12-28 | University Of The Western Cape | Process for production of high silica content zeolite from fly ash |
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| WO2017221192A1 (en) * | 2016-06-23 | 2017-12-28 | University Of The Western Cape | Process for production of high silica content zeolite from fly ash |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109879295A (en) * | 2019-04-25 | 2019-06-14 | 太原理工大学 | A kind of ZSM-5 molecular sieve |
| WO2021014513A1 (en) * | 2019-07-19 | 2021-01-28 | 株式会社環境浄化センター | Production method relating to industrial mass-production of high-purity artificial zeolite |
| CN112533869A (en) * | 2019-07-19 | 2021-03-19 | 久保田满 | Method for producing high-purity artificial zeolite in industrial batch |
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| CN112533869B (en) * | 2019-07-19 | 2023-10-20 | 久保田满 | Industrial mass production method of high-purity artificial zeolite |
| CN110980913A (en) * | 2019-12-27 | 2020-04-10 | 张家港三得利染整科技有限公司 | Composite flocculant for treating printing and dyeing wastewater and preparation method and application thereof |
| CN111333081A (en) * | 2020-02-29 | 2020-06-26 | 山西大学 | Method for preparing ZSM-5 molecular sieve with low silica-alumina ratio by using high-alumina pulverized coal furnace fly ash |
| CN115784254A (en) * | 2022-11-02 | 2023-03-14 | 吉林化工学院 | Preparation method of fly ash-based MFI structure nano zeolite rich in mesopores |
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