CN116854103A - Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method - Google Patents

Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method Download PDF

Info

Publication number
CN116854103A
CN116854103A CN202310824145.2A CN202310824145A CN116854103A CN 116854103 A CN116854103 A CN 116854103A CN 202310824145 A CN202310824145 A CN 202310824145A CN 116854103 A CN116854103 A CN 116854103A
Authority
CN
China
Prior art keywords
fly ash
ssz
molecular sieve
stirring
clinker
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310824145.2A
Other languages
Chinese (zh)
Inventor
吴勤明
刘培
肖丰收
王亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Zhejiang University Institute Of New Materials And Chemical Industry
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN202310824145.2A priority Critical patent/CN116854103A/en
Publication of CN116854103A publication Critical patent/CN116854103A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a comprehensive utilization technology of fly ash, and aims to provide a method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by a one-step method. Comprising the following steps: weighing fly ash and solid sodium hydroxide, uniformly mixing and grinding, calcining, cooling and grinding to powder to obtain activated fly ash clinker; dissolving the fly ash clinker and NaOH in water, adding a silicon source after stirring, and continuing stirring until silica-alumina gel is formed; then adding copper sulfate pentahydrate and tetraethylenepentamine, and stirring uniformly; and filtering and drying the product after the crystallization reaction to obtain the raw powder of the nano FeCu-SSZ-13 zeolite molecular sieve. Compared with the prior art, the invention has wide sources of raw materials and reduces environmental pollution; the high-temperature alkali fusion is selected as the only pretreatment mode, so that the waste of the traditional process water resources is avoided; no impurity interference exists in the synthesis process, so that the purity of the product is improved; the process is simple, green and environment-friendly; the trace metal elements in the fly ash are effectively utilized.

Description

Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method
Technical Field
The invention relates to the technical field of comprehensive utilization of fly ash, in particular to a method for rapidly synthesizing nano FeCu-SSZ-13 zeolite by using fly ash in one step.
Background
The SSZ-13 molecular sieve is a molecular sieve with a CHA topological structure, has an eight-membered ring orifice and a three-dimensional cross pore canal structure, has the aperture of 0.38 multiplied by 0.38nm, forms an oval super cage with the cage size of 1.0 multiplied by 0.67nm at the intersection of the eight-membered ring orifice, and belongs to a small-hole molecular sieve. SSZ-13 molecular sieve is widely applied to preparing olefin (MTO) from methanol due to the characteristics of high catalytic activity, excellent thermal stability, strong poisoning resistance and the like, and ammonia selective catalytic reduction (NH) 3 SCR), ethylene To Propylene (ETP) and adsorption separation (N) 2 /CH 4 N 2 /CO), and the like.
The Cu-SSZ-13 molecular sieve is taken as a small pore molecular sieve, can effectively inhibit the phenomenon of high Wen Tuolv and has good N 2 Selectivity. In addition, the Cu-SSZ-13 molecular sieve can inhibit the generation of carbon deposit and has strong poisoning resistance to metals, so that the molecular sieve is widely paid attention to and is recognized as the next generation NH 3 -an SCR catalyst. Generally, two preparation methods of the Cu-SSZ-13 molecular sieve are mainly adopted, namely, an SSZ-13 molecular sieve carrier is synthesized firstly, then Cu species are loaded by an ion exchange method, and an expensive organic template agent N, N, N-trimethyl-N-alkylaminoammonium hydroxide is used in the preparation method, so that the industrial production cost is greatly increased, a large amount of distilled water is consumed in an ion exchange process carried out in the preparation process, the steps are complicated, and the copper species exchange degree of the SSZ-13 molecular sieve with different silicon-aluminum ratios is different, so that great inconvenience is brought to mass production; the other preparation method is to use the Cu-TEPA complex as a template agent to synthesize the Cu-SSZ-13 molecular sieve in situ by a one-pot method, and the template agent used by the method is cheap and easy to obtain, and the preparation process is simple, so that the method is very beneficial to the industrial production of the high-performance catalyst. However, the report of the presently disclosed technology results The Cu-SSZ-13 molecular sieve has larger (mostly micron-sized) particle size and is uneven, thereby being unfavorable for diffusion in the reaction process and easily causing the catalyst to be coked and deactivated.
Fly ash is a solid waste in modern industries such as power plants, and along with the development of the power industry, the fly ash emission of coal-fired power plants is increased year by year, so that the fly ash becomes one of industrial waste residues with larger emission in various countries. The large amount of fly ash is discharged to pollute the environment and occupy a large amount of cultivated land, and the power plant also pays the expensive construction and management cost of the ash field. This contradiction will be even more pronounced with the rapid development of the power industry. If the fly ash is piled up in a landfill, harmful elements in the fly ash can invade soil to cause large-area pollution along with the flushing of rainwater. The fly ash contains about 60 to 80 percent of SiO 2 And Al 2 O 3 Meanwhile, the fly ash contains a small amount of transition metal and rare earth metal, so that the waste of the fly ash also causes serious resource waste. The development of fine comprehensive utilization of the fly ash with high added value not only can bring great economic benefit, but also can objectively solve the problems of resource shortage and environment brought by the fly ash.
The preparation of zeolite molecular sieves using fly ash as a raw material has been carried out for many years, and researchers have adopted different methods to synthesize different types of zeolite molecular sieves. However, the existing preparation technology of the zeolite molecular sieve based on the fly ash generally has the defects of high manufacturing cost and complex preparation process, and can not solve the technical problems of unsuitable industrial production and the problems in the preparation of the Cu-SSZ-13 molecular sieve.
Therefore, a molecular sieve synthesis route with low production cost, simple preparation process and excellent performance is developed, and the comprehensive utilization of the fly ash and the NH of the Cu-SSZ-13 molecular sieve are realized 3 The large-scale industrial production and application in SCR reactions are of great importance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by a one-step method.
In order to solve the technical problems, the invention adopts the following solutions:
the method for rapidly synthesizing the fly ash-based nano FeCu-SSZ-13 zeolite by a one-step method comprises the following steps:
(1) High temperature alkali fusion
Weighing fly ash and solid sodium hydroxide according to the mass ratio of 1:1.0-1.5, uniformly mixing and grinding, and calcining at 650-900 ℃ for 2-6 h; grinding to powder after cooling to obtain activated fly ash clinker;
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve
Dissolving the fly ash clinker and NaOH in water, adding a silicon source after stirring, and continuing stirring until silica-alumina gel is formed; then adding copper sulfate pentahydrate and tetraethylenepentamine, and stirring uniformly; crystallizing at 100-180 deg.c for 12-84 hr, filtering and stoving to obtain nanometer FeCu-SSZ-13 zeolite molecular sieve powder;
Controlling the addition amount of each raw material to ensure that the molar ratio range of each material in the reaction system is Na 2 O:SiO 2 :Al 2 O 3 Organic template agent H 2 O=0.46 to 0.61:1:0.033 to 0.083:0.1 to 0.3:15 to 45; wherein the organic template agent is Cu-TEPA complex, and is generated by the meridian combination reaction of copper sulfate pentahydrate and tetraethylenepentamine; siO (SiO) 2 Refers to pure SiO 2 A scaled silicon source.
As a preferable scheme of the invention, the fly ash is from a coal-fired power plant and is solid waste fly ash collected from flue gas discharged by burning the fly ash; the total amount of the silicon dioxide and the aluminum oxide accounts for more than 80 percent of the mass of the fly ash.
As a preferable scheme of the invention, SSZ-13 zeolite molecular sieve seed crystals are added into the mixture in the process of uniformly stirring after adding the copper sulfate pentahydrate and the tetraethylenepentamine, so as to improve the crystallization speed and inhibit the growth of impurities; controlling the addition amount of the seed crystal relative to SiO 2 The molar ratio of (2) is 5-20%.
As a preferred embodiment of the present invention, the silicon source is SiO 2 Silica sol with a mass ratio of 40% or SiO 2 Quality ofFine silica gel with a ratio of 100%.
As a preferred embodiment of the present invention, the water is deionized water.
As a preferable scheme of the invention, the reaction kettle is a polytetrafluoroethylene stainless steel reaction kettle.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses the solid waste fly ash as the raw material, has wide sources, reduces the pollution of the fly ash to the environment, and provides a new idea for the high-value industrial application of the fly ash.
2. The invention adopts the high-temperature alkali fusion as the only pretreatment mode, thereby avoiding the waste of a large amount of water resources in the acid leaching process and other processes in the traditional process; and the product after high-temperature alkali fusion is used as the only source of silicon-aluminum and alkali, and the interference of other impurities is avoided in the synthesis process, so that the purity of the product is improved.
3. The invention directly takes the fly ash clinker after high-temperature alkali fusion as the raw material, and a series of silicon-aluminum ratios (SiO) can be prepared by adding the conventional silicon source method 2 /Al 2 O 3 Cu-SSZ-13 molecular sieves of =12-30) are used in Selective Catalytic Reduction (SCR) reactions of nitrogen oxides.
4. The Cu-SSZ-13 molecular sieve is synthesized by directly taking the Cu-TEPA complex as the organic template agent, so that the ion exchange process is avoided, the cost is greatly reduced, and the method is simple in process and environment-friendly.
5. The method effectively utilizes trace metal elements in the fly ash, does not need to introduce Fe elements into the molecular sieve by using complex steps, and improves the catalytic performance of the Cu-SSZ-13 molecular sieve in the Selective Catalytic Reduction (SCR) reaction of nitrogen oxides.
6. According to the invention, 5% -20% of SSZ-13 molecular sieve seed crystal is added in a proper amount, so that on one hand, the particle size of the micron-sized Cu-SSZ-13 molecular sieve can be controlled to be about 50nm, and the particle size is relatively uniform, thereby being beneficial to diffusion in SCR reaction; on the other hand, the crystallization time is shortened, so that the Cu-SSZ-13 molecular sieve can be crystallized at 160 ℃ for 12 hours.
Drawings
FIG. 1 is an XRD spectrum of a synthetic product of the invention.
FIG. 2 is a scanning electron microscope image of a composite product of the present invention.
FIG. 3 is a graph showing the performance of FeCu-SSZ-13 and Cu-SSZ-13 in nitrogen oxide Selective Catalytic Reduction (SCR) reactions in accordance with the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and detailed description:
fly ash samples used in the examples of the invention are derived from fly ash which is a main solid waste discharged after pulverized coal combustion in a coal-fired power plant in China, the chemical composition of the fly ash measured by XRF is shown in Table 1, wherein SiO 2 And Al 2 O 3 The total content of (2) is greater than 80%.
Table 1 oxide composition of the fly ash components
Composition of the components SiO 2 Al 2 O 3 Fe 2 O 3 CaO K 2 O TiO 2 Others
Content wt./wt.% 52 29.2 3.33 2 1.46 1.19 10.82
In each example, the addition amount was calculated from the molar ratio of each raw material in the crystallization reaction system. Wherein the fly ash clinker belongs to a mixture and is prepared by high-temperature alkali fusion according to the mass ratio of the fly ash to the solid sodium hydroxide of 1:1.0-1.5; therefore, when the invention calculates the fly ash clinker, the addition amount is calculated as follows:
When the mass ratio of the fly ash to the sodium hydroxide is 1, taking 1g of fly ash clinker as an example, 0.5g of fly ash and 0.5g of sodium hydroxide are contained in the fly ash clinker; and 0.5g of fly ash contains 0.26g of silicon dioxide and 0.146g of alumina, then the dosage of the silicon dioxide, the aluminum oxide and the sodium hydroxide to be added is calculated according to the mole ratio under different conditions, and then the addition amount of the fly ash clinker is calculated.
Example 1: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of fly ash/sodium hydroxide=1:1.0
(1) High temperature alkali fusion: weighing 20g of fly ash and 20g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: weighing 0.9726g of the fly ash clinker, dissolving 0.15g of sodium hydroxide in 7.8795g of deionized water, fully stirring for 10min, and adding 1.8675g of silica sol (SiO 2 40% by mass, the same applies below), after stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, after stirring for 5min, adding 0.631g of tetraethylenepentamine, after stirring for 2h, adding Adding 0.1g of SSZ-13 molecular sieve seed crystal, adding the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 12 hours to obtain a completely crystallized product, filtering the product, and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.1 seed crystal
The product obtained by crystallization reaction is subjected to X-ray diffraction analysis, and the structure of the product is SSZ-13 zeolite molecular sieve (figure 1). Fig. 2 is a Scanning Electron Microscope (SEM) picture of the product, wherein the left image is a SEM picture at low magnification, and the right image is a SEM picture at high magnification, and it can be seen from the figure that the product has a cubic shape with a particle size of 50 nm.
Example 2: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of fly ash/sodium hydroxide=1:1.2
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 O/0.1 seed crystal
Example 3: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of fly ash/sodium hydroxide=1:1.5
(1) High temperature alkali fusion: weighing 20g of fly ash and 30g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: weighing 1.2156g of the fly ash clinker, dissolving in 7.8795g of deionized water (without adding sodium hydroxide), fully stirring for 10min, adding 1.8675g of silica sol (40%), stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, stirring for 5min, adding 0.631g of tetraethylenepentamine, continuously stirring for 2h, adding 0.1g of SSZ-13 molecular sieve seed crystal, adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 12h to obtain a completely crystallized product, and carrying out suction filtration and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.1 seed crystal
Example 4: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of calcination time of 4h
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 4 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.1 seed crystal
Example 5: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of calcination time of 6h
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 6 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.1 seed crystal
Example 6: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at 650 ℃ of calcination temperature
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring to a porcelain boat, fully calcining for 2 hours at 650 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 O/0.1 seed crystal
Example 7: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at calcination temperature of 700 DEG C
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 700 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.1 seed crystal
Example 8: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at 900 ℃ of calcination temperature
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 900 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.1 seed crystal
Example 9: at H 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=15
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 3.3795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/15H 2 o/0.1 seed crystal
Example 10: at H 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=25
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 6.3795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/25H 2 O/0.1 seed crystal
Example 11: at H 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of 35
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 9.3795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/35H 2 o/0.1 seed crystal
Example 12: at H 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=40
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 10.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/40H 2 o/0.1 seed crystal
Example 13: at H 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=45
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 12.3795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.1g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/45H 2 O/0.1 seed crystal
Example 14: at seed crystal/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.05
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.05g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.05 seed crystal
Example 15: at seed crystal/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.15
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.15g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.15 seed crystal
Example 16: at seed crystal/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.20
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.20g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.2Cu-TEPA/30H 2 o/0.20 seed crystal
Example 17: in Cu-TEPA/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.10
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.4167g of copper sulfate pentahydrate is added, after stirring for 5min, 0.3155g of tetraethylenepentamine is added, after stirring for 2h, 0.10g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.10Cu-TEPA/30H 2 O/0.10 seed crystal
Example 18: in Cu-TEPA/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.15
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.625g of copper sulfate pentahydrate is added, after stirring for 5min, 0.4733g of tetraethylenepentamine is added, after stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.15Cu-TEPA/30H 2 o/0.10 seed crystal
Example 19: in Cu-TEPA/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.30
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 1.25g of copper sulfate pentahydrate is added, after stirring for 5min, 0.945g of tetraethylenepentamine is added, after stirring for 2h, 0.10g of seed crystal of SSZ-13 molecular sieve is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃ to obtain the finished product, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.30Cu-TEPA/30H 2 o/0.10 seed crystal
Example 20: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at crystallization temperature of 100 DEG C
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 84h at 100 ℃ to obtain the product, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 21: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at crystallization temperature of 120 DEG C
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out at 120 ℃ for 72h, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 O/0.10 seed crystal
Example 22: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at crystallization temperature of 140 DEG C
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 48h at 140 ℃, and the product is completely crystallized, and is filtered by suction and dried, thus obtaining the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 23: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve at crystallization temperature of 180 DEG C
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 180 ℃ to obtain the product, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 24: at Na (Na) 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.46
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: weighing 1.1131g of the fly ash clinker, dissolving in 7.8795g of deionized water, fully stirring for 10min, adding 1.8675g of silica sol (40%), stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, stirring for 5min, adding 0.631g of tetraethylenepentamine, continuously stirring for 2h, adding 0.10g of SSZ-13 molecular sieve seed crystal, adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 12h to obtain a completely crystallized product, carrying out suction filtration, and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.46Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Under the molar ratio, the dosage of NaOH contained in the fly ash clinker just meets the requirement after calculation, and no additional NaOH is needed.
Example 25: at Na (Na) 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.53
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.10g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.53Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 26: at Na (Na) 2 O/SiO 2 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of being=0.57
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.15g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is completely crystallized, filtered by suction and dried, thus obtaining the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.57Na 2 O/0.20Cu-TEPA/30H 2 O/0.10 seed crystal
Example 27: at Na (Na) 2 O/SiO 2 One-step method fast under condition of=0.61Synthesis of nano FeCu-SSZ-13 molecular sieve
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.20g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is carried out for 12h at 160 ℃, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.0833Al 2 O 3 /0.61Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 28: in SiO 2 /Al 2 O 3 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=15
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: weighing 0.8905g of the fly ash clinker, dissolving 0.15g of sodium hydroxide in 7.8036g of deionized water, fully stirring for 10min, adding 1.994g of silica sol (40%), stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, stirring for 5min, adding 0.631g of tetraethylenepentamine, continuously stirring for 2h, adding 0.10g of SSZ-13 molecular sieve seed crystal, adding the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 12h to obtain the product, and carrying out suction filtration and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.066Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
In examples 28-30, the silica to alumina ratio was different, so the added fly ash clinker was also different; siO in different fly ash clinker 2 The amount of silica sol to be added is different, but in all embodiments is 1g SiO 2 As a reference.
Example 29: in SiO 2 /Al 2 O 3 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=20
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: weighing 0.6679g of the fly ash clinker, dissolving 0.29g of sodium hydroxide in 7.7277g of deionized water, fully stirring for 10min, adding 2.1205g of silica sol (40%), stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, stirring for 5min, adding 0.631g of tetraethylenepentamine, continuously stirring for 2h, adding 0.10g of SSZ-13 molecular sieve seed crystal, adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 12h to obtain the product, and carrying out suction filtration and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.05Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 30: in SiO 2 /Al 2 O 3 One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of=30
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: weighing 0.4452g of the fly ash clinker, dissolving 0.42g of sodium hydroxide in 7.6518g of deionized water, fully stirring for 10min, adding 2.247g of silica sol (40%), stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, stirring for 5min, adding 0.631g of tetraethylenepentamine, continuously stirring for 2h, adding 0.10g of SSZ-13 molecular sieve seed crystal, adding the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 12h to obtain a completely crystallized product, and carrying out suction filtration and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.033Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 31: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under rotation condition
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 7.8795g of deionized water, after fully stirring for 10min, 1.8675g of silica sol (40%) is added, after stirring for 1h, 0.8333g of copper sulfate pentahydrate is added, after stirring for 5min, 0.631g of tetraethylenepentamine is added, after continuing stirring for 2h, 0.10g of SSZ-13 molecular sieve seed crystal is added, then the reaction raw material is added into a polytetrafluoroethylene stainless steel reaction kettle, crystallization is completed after crystallization for 12h at 160 ℃ and 50rpm, and the product is obtained after suction filtration and drying. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.083Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 32: one-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve under condition of taking fine silica gel as silicon source
(1) High temperature alkali fusion: weighing 20g of fly ash and 24g of sodium hydroxide, mixing in a mortar, grinding and uniformly mixing, transferring into a porcelain boat, fully calcining for 2 hours at 800 ℃, cooling to obtain calcined clinker, and grinding the calcined clinker into powder to obtain activated fly ash clinker.
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve: 1.1131g of the fly ash clinker is weighed, 0.05g of sodium hydroxide is dissolved in 9g of deionized water, and after fully stirring for 10min, 0.747g of fine silica gel (SiO) 2 The mass ratio is 100 percent), after stirring for 1h, adding 0.8333g of copper sulfate pentahydrate, after stirring for 5min, adding 0.631g of tetraethylenepentamine, after continuing stirring for 2h, adding 0.10g of SSZ-13 molecular sieve seed crystal, then adding the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ and 50rpm for 12h to obtain the product, and carrying out suction filtration and drying to obtain the product. The addition amount of each reaction raw material is controlled, so that the molar ratio range of each material in the reaction system is as follows:
1.0SiO 2 /0.083Al 2 O 3 /0.49Na 2 O/0.20Cu-TEPA/30H 2 o/0.10 seed crystal
Example 33: performance of nano FeCu-SSZ-13 molecular sieve rapidly synthesized by one-step method in nitrogen oxide Selective Catalytic Reduction (SCR) reaction
First, in order to obtain FeCu-SSZ-13 zeolite in the hydrogen form, nano-FeCu-SSZ-13 zeolite obtained in example 2 was put into HNO in an amount of 0.02mol/L 3 The solution was exchanged 2-3 times at 80℃for 2H each, and after suction filtration and drying, calcined at 550℃for 4H, an H-type zeolite containing both Fe and Cu was obtained, defined as H-FeCu-SSZ-13. The nano FeCu-SSZ-13 also maintains more than 75% of NO conversion rate at 550 ℃ in the Selective Catalytic Reduction (SCR) reaction of nitrogen oxides (figure 3) before hydrothermal treatment or after hydrothermal treatment at 750 ℃ for 16 hours, and is similar to the NO conversion rate of the Cu-SSZ-13 zeolite (defined as H-Cu-SSZ-13) synthesized by the traditional path.
The foregoing description of the invention is merely illustrative of several embodiments of the invention, and is not intended to limit the invention in any way, although the invention has been described in terms of preferred embodiments, and not intended to limit the invention. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the technical scope of the present invention.

Claims (6)

1. The method for rapidly synthesizing the fly ash-based nano FeCu-SSZ-13 zeolite by a one-step method is characterized by comprising the following steps of:
(1) High temperature alkali fusion
Weighing fly ash and solid sodium hydroxide according to the mass ratio of 1:1.0-1.5, uniformly mixing and grinding, and calcining at 650-900 ℃ for 2-6 h; grinding to powder after cooling to obtain activated fly ash clinker;
(2) One-step method for rapidly synthesizing nano FeCu-SSZ-13 molecular sieve
Dissolving the fly ash clinker and NaOH in water, adding a silicon source after stirring, and continuing stirring until silica-alumina gel is formed; then adding copper sulfate pentahydrate and tetraethylenepentamine, and stirring uniformly; crystallizing at 100-180 deg.c for 12-84 hr, filtering and stoving to obtain nanometer FeCu-SSZ-13 zeolite molecular sieve powder;
controlling the addition amount of each raw material to ensure that the molar ratio range of each material in the reaction system is Na 2 O:SiO 2 :Al 2 O 3 Organic template agent H 2 O=0.46 to 0.61:1:0.033 to 0.083:0.1 to 0.3:15 to 45; wherein the organic template agent is Cu-TEPA complex, and is generated by the meridian combination reaction of copper sulfate pentahydrate and tetraethylenepentamine; siO (SiO) 2 Refers to pure SiO 2 A scaled silicon source.
2. The method of claim 1, wherein the fly ash used is from a coal-fired power plant and is solid waste fly ash collected from flue gas discharged from the combustion of the pulverized coal; the total amount of the silicon dioxide and the aluminum oxide accounts for more than 80 percent of the mass of the fly ash.
3. The method according to claim 1, wherein SSZ-13 zeolite molecular sieve seeds are added to the mixture during the process of stirring uniformly after adding copper sulfate pentahydrate and tetraethylenepentamine to increase crystallization speed and inhibit impurity growth; controlling the addition amount of the seed crystal relative to SiO 2 The molar ratio of (2) is 5-20%.
4. The method of claim 1, wherein the silicon source is SiO 2 Silica sol with a mass ratio of 40% or SiO 2 Fine silica gel with a mass ratio of 100%.
5. The method of claim 1, wherein the water is deionized water.
6. The method of claim 1, wherein the reaction vessel is a polytetrafluoroethylene stainless steel reaction vessel.
CN202310824145.2A 2023-07-05 2023-07-05 Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method Pending CN116854103A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310824145.2A CN116854103A (en) 2023-07-05 2023-07-05 Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310824145.2A CN116854103A (en) 2023-07-05 2023-07-05 Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method

Publications (1)

Publication Number Publication Date
CN116854103A true CN116854103A (en) 2023-10-10

Family

ID=88222914

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310824145.2A Pending CN116854103A (en) 2023-07-05 2023-07-05 Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method

Country Status (1)

Country Link
CN (1) CN116854103A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106587097A (en) * 2016-12-26 2017-04-26 中国地质大学（武汉） Method for synthesizing SSZ-13 zeolite molecular sieve by utilizing micron-silicon powder
CN115385356A (en) * 2022-08-11 2022-11-25 浙江大学 Method for preparing 13X molecular sieve by using fly ash solid phase

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106587097A (en) * 2016-12-26 2017-04-26 中国地质大学（武汉） Method for synthesizing SSZ-13 zeolite molecular sieve by utilizing micron-silicon powder
CN115385356A (en) * 2022-08-11 2022-11-25 浙江大学 Method for preparing 13X molecular sieve by using fly ash solid phase

Similar Documents

Publication Publication Date Title
US11174171B2 (en) Hierarchical porous honeycombed nickel oxide microsphere and preparation method thereof
CN111389351B (en) CuFeO 2/biochar composite magnetic material and preparation method thereof
CN112619648B (en) Copper-cobalt-based catalyst for organic sulfur hydrolysis removal and preparation method thereof
CN109794245B (en) Honeycomb iron-based hydrogenation catalyst (Fe)3O4@ C)/C and preparation method and application thereof
CN107519905B (en) Vanadium carbide nano-sieve electrocatalytic material capable of being used in wide pH range and preparation method thereof
CN113582199A (en) Method for synthesizing chabazite by seed crystal guiding method and improving utilization rate of raw materials
CN111592011A (en) Method for directly synthesizing SSZ-13 zeolite molecular sieve by using TEAOH as organic template agent
CN105195188A (en) Nickel-tungsten carbide/porous carbon nano-fiber composite catalyst, intermediate and preparation
CN110217804B (en) ZSM-5 molecular sieve and preparation method thereof, hydrogen type ZSM-5 molecular sieve and application thereof, and methanol conversion method
CN106276963A (en) A kind of synthetic method of metal ZSM molecular sieve
CN113816432B (en) Nanosheet self-assembled spherical ferrous molybdate material and preparation method and application thereof
CN114210363A (en) Preparation method of SSZ-16 copper-containing catalyst
CN114308042A (en) Attapulgite-based ordered microporous zeolite catalyst and preparation method and application thereof
CN113845128A (en) MOR zeolite molecular sieve and preparation method thereof
CN116854103A (en) Method for rapidly synthesizing fly ash-based nano FeCu-SSZ-13 zeolite by one-step method
CN109647499B (en) Catalyst for growing Cu-SSZ-13 molecular sieve by taking HT-SiC as carrier and preparation method thereof
CN113877556B (en) Indium oxyhydroxide/modified attapulgite photocatalytic composite material and preparation method and application thereof
CN114405538B (en) Hierarchical pore Fe/ZSM-5 molecular sieve and preparation method and application thereof
CN114804136B (en) Preparation method and application of nano SSZ-13 molecular sieve
CN109264738A (en) The synthetic method of mesoporous ETS-10 zeolite of the Template-free method synthesis containing metal
CN113908839A (en) Preparation method of normal-temperature desulfurizing agent
CN112647132B (en) Single crystal (Bi) 19 S 27 I 3 ) 0.6667 Nano-rod and preparation method and application thereof
CN113200554A (en) Nano mordenite molecular sieve and preparation method and application thereof
CN113522293A (en) Preparation method and application of catalyst for hydrogen production by dry reforming of methane and carbon dioxide
CN114425384A (en) Catalyst for preparing synthetic gas and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20231016

Address after: 310058 Yuhang Tang Road, Xihu District, Hangzhou, Zhejiang 866

Applicant after: ZHEJIANG University

Applicant after: Shanxi Zhejiang University Institute of new materials and chemical industry

Address before: 310058 Yuhang Tang Road, Xihu District, Hangzhou, Zhejiang 866

Applicant before: ZHEJIANG University