CN110127720B - Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds - Google Patents
Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds Download PDFInfo
- Publication number
- CN110127720B CN110127720B CN201910410350.8A CN201910410350A CN110127720B CN 110127720 B CN110127720 B CN 110127720B CN 201910410350 A CN201910410350 A CN 201910410350A CN 110127720 B CN110127720 B CN 110127720B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ssz
- crystallization
- temperature
- heterogeneous
- 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.)
- Active
Links
Images
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
- C01B39/46—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
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for synthesizing an SSZ-13 molecular sieve by heterogeneous crystal seed assistance, which comprises the following steps: uniformly stirring and mixing water, alkali, an organic template agent, a sodium silicate aqueous solution and heterogeneous seed crystals to obtain initial gel; transferring the initial gel into a closed high-temperature reaction kettle, heating to 140-180 ℃ in a homogeneous reactor, and stirring for crystallization; and after crystallization is finished, separating, drying and roasting the product to obtain the SSZ-13 molecular sieve. The invention utilizes the low-cost heterogeneous crystal seeds to prepare the SSZ-13 molecular sieve, and adopts the homogeneous reactor with the rotation function to carry out crystallization, thereby not only having good crystallinity and purity, but also having small size of the molecular sieve which is only 300-500 nm, being beneficial to rapid mass transfer and improving the performance.
Description
Technical Field
The invention relates to a method for synthesizing an SSZ-13 molecular sieve, in particular to a method for synthesizing a small-size SSZ-13 molecular sieve by adopting heterogeneous crystal seeds, belonging to the technical field of molecular sieve preparation.
Background
Molecular sieves have found wide application due to their special pore structure and large specific surface area. Wherein, SSZ-13 is a small-pore molecular sieve (structure is shown in figure 1) with a Chabazite (CHA) structure, and the molecular sieve has a special micropore structure and good hydrothermal stability, so that the molecular sieve can be used for selectively catalyzing and reducing nitrogen oxide (NH) in ammonia3SCR), Methanol To Olefin (MTO), gas separation and the like have great market application potential.
The preparation method of the SSZ-13 molecular sieve at present mainly comprises two types: one is to utilize sol-gel method, mainly mix water, aluminum source, silicon source, alkali source, template agent to get the initial gel, pass crystallization, separation, drying, roasting to get the molecular sieve raw powder. However, the size of the molecular sieve obtained by the method is relatively large, generally between 3 and 5 um, which causes the mass transfer process to be limited. The other is a seed crystal auxiliary method, which mainly adds SSZ-13 homogeneous seed crystals into the initial sol to improve the crystallization rate, but the synthesis period of SSZ-13 is long and the price is high, thereby improving the synthesis cost. Therefore, how to reduce the size of the molecular sieve to improve the mass transfer efficiency and reduce the synthesis cost of the molecular sieve is a major problem in the preparation of the SSZ-13 molecular sieve at present.
Disclosure of Invention
In order to solve the problems of large size and high cost of the SSZ-13 molecular sieve synthesized by the prior art, the invention provides a method for synthesizing the SSZ-13 molecular sieve by using heterogeneous crystal seeds, wherein the method uses the heterogeneous crystal seed ultrastable Y molecular sieve to replace homogeneous crystal seeds SSZ-13, so that the synthesis cost is reduced, and meanwhile, the small-size SSZ-13 molecular sieve is synthesized by improving and designing process conditions, so that the mass transfer process is increased.
The specific technical scheme of the invention is as follows:
a method for synthesizing SSZ-13 molecular sieve with the assistance of heterogeneous crystal seeds is characterized by comprising the following steps:
(1) uniformly stirring and mixing water, alkali, an organic template agent, a sodium silicate aqueous solution and heterogeneous crystal seeds to obtain initial gel, wherein the heterogeneous crystal seeds are ultrastable Y molecular sieves;
(2) transferring the initial gel into a closed high-temperature reaction kettle, heating to 140-180 ℃ in a homogeneous reactor, and stirring for crystallization;
(3) and after crystallization is finished, separating, drying and roasting the product to obtain the SSZ-13 molecular sieve.
The invention takes an ultrastable Y molecular sieve as a heterogeneous crystal seed, and the ultrastable Y molecular sieve is a superstable Y-type molecular sieve, which is called USY molecular sieve for short. The ultrastable Y molecular sieve not only serves as a crystal seed, but also provides a silicon element and an aluminum element. Wherein, the silicon element is provided by the sodium silicate aqueous solution and the ultrastable Y molecular sieve at the same time, and the aluminum element is provided by the ultrastable Y molecular sieve only without adding an extra aluminum source. By selection of these feedstocks, an advantageous basis is provided for the formation of small size SSZ-13 molecular sieves. The adding sequence of the raw materials can be selected at will, and the influence on the result is little.
Further, the specific surface area of the ultrastable Y molecular sieve is 600-700 m2·g-1The silicon-aluminum ratio of the ultrastable Y molecular sieve is 5.4-11.5. Ultrastable Y-score using this performance parameterAnd (3) a sub-sieve, which can form a small-sized SSZ-13 molecular sieve.
Further, the alkali is sodium hydroxide or potassium hydroxide. The organic template agent is N, N, N-trimethyl-1-adamantane ammonium hydroxide (N, N, N-trimethyl-1-adamantyl ammonium hydroxide) or N, N, N-trimethyl-1-adamantane ammonium iodide.
Furthermore, in the sodium silicate aqueous solution, the mass fraction of NaOH is 11.4-14.4%, and the mass fraction of Si is 12-13%.
Further, the silicon source is provided by sodium silicate aqueous solution and heterogeneous seed crystal, the aluminum source is provided by heterogeneous seed crystal, and the ratio of the silicon source: an aluminum source: alkali: h2O: the molar ratio of the organic template agent is 1: 0.03-0.05: 0.31-0.4: 23-33: 0.12 to 0.17, wherein the molar ratio of the silicon source is calculated as silica, the aluminum source is calculated as alumina, the alkali is calculated as metal oxide, and the water referred to herein is all water in the sample including aqueous sodium silicate and templating agent introduced water.
Furthermore, the invention improves and designs crystallization conditions, and the crystallization is carried out under stirring, so that the initial gel is uniformly heated, the crystallinity and the purity of the product are improved, and the formation of the small-size molecular sieve is facilitated. The stirring speed is preferably 40 to 80 revolutions per minute. The crystallization is preferably carried out in a rotary homogeneous reactor which is well able to ensure uniform heating.
Furthermore, the invention adopts a special program heating method to raise the crystallization temperature, namely raising the temperature to 80-100 ℃ at the speed of 1-4 ℃/min, preserving the temperature for 2-5min, and raising the temperature to 140-180 ℃ at the speed of 1-4 ℃/min.
Furthermore, the crystallization time is 4-6 days.
Further, in the step (3), the calcination is carried out at 550-600 ℃, and the calcination time is generally 6-10 h.
The invention obtains the small-size SSZ-13 molecular sieve by selecting the raw materials, the seed crystals and the process conditions, the size of the molecular sieve can be 300-500 nm, the crystal size is obviously reduced, the invention is favorable for rapid mass transfer, and the application performance of the molecular sieve is improved.
The invention has the following beneficial effects:
1. the invention selects the ultrastable Y molecular sieve as the crystal seed, the silicon source and the aluminum source, thereby greatly reducing the synthesis cost.
2. The invention improves the purity and the crystallinity of the molecular sieve product by the design and the improvement of the relation of the raw materials and the consumption of the raw materials and the crystallization mode, in addition, the size of the obtained SSZ-13 molecular sieve is 300-500 nm, the crystal size is obviously reduced, the fast mass transfer is facilitated, and the performance is improved.
Drawings
FIG. 1 is a schematic diagram of the structure of an SSZ-13 molecular sieve.
FIG. 2 is an SEM topography of the SSZ-13 molecular sieve prepared in example 1.
FIG. 3 is an XRD pattern of the SSZ-13 molecular sieve prepared in example 1.
Fig. 4 is an XRD pattern of the sample prepared in comparative example 1.
Fig. 5 is an XRD pattern of the sample prepared in comparative example 3.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be exemplary only and are not intended to be limiting.
In the following examples, the ultrastable Y molecular sieve is purchased from catalyst works of southern Kai university and has a specific surface area of 600-700 m2·g-1The N, N, N-trimethyl-1-adamantane ammonium hydroxide is purchased from Sn-free Sankai high-purity chemical Co., Ltd, and the N, N, N-trimethyl-1-adamantane ammonium iodide is prepared by the method described in J. Phys. chem. C2010, 114, 1633-. The mass fraction of NaOH in the sodium silicate aqueous solution is 11.4-14.4%, and the mass fraction of Si is 12-13%.
Example 1
First, 13.2 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide was dissolved in 30.68 g of water, stirred at room temperature for half an hour, and then 17 mL of an aqueous sodium silicate solution and 2 g of an ultrastable Y molecular sieve having a silicon-aluminum ratio of 6 (specific surface area of 600 m)2g-1) After stirring at room temperature for one hour, an initial gel was obtained, which was then transferred to 100 mL of stainless steelHeating to 100 ℃ at a heating rate of 4 ℃/min in a homogeneous phase rotary reactor in a kettle, preserving heat for 2 min, heating to 140 ℃ at a heating rate of 4 ℃/min, crystallizing at 140 ℃ at a speed of 60 rpm for 6 days, centrifuging, washing to neutrality, drying overnight at 100 ℃ for 12 h, heating to 575 ℃ at a heating rate of 1 ℃/min in a tubular furnace, and keeping for 8 h to obtain SSZ-13 raw powder.
FIG. 2 is an SEM image of the obtained SSZ-13 molecular sieve, from which it can be seen that the size of the molecular sieve is around 350-400 nm. FIG. 3 is an XRD pattern of the SSZ-13 molecular sieve, from which it can be seen that the molecular sieve has good crystallinity.
Example 2
First, 13.2 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide was dissolved in 31.98 g of water, stirred at room temperature for half an hour, and then 15.4 mL of an aqueous sodium silicate solution and 2 g of an ultrastable Y molecular sieve having a silicon-aluminum ratio of 6 (specific surface area of 600 m) were added2g-1) Stirring for one hour at room temperature to obtain initial gel, transferring the initial gel into a 100 mL stainless steel high-temperature reaction kettle, heating to 100 ℃ at the heating rate of 4 ℃/min in a homogeneous phase rotary reactor, keeping the temperature for 2 min, heating to 140 ℃ at the heating rate of 4 ℃/min, crystallizing at the speed of 60 rpm for 6 days at 140 ℃, centrifuging, washing to neutrality, drying overnight at 100 ℃ for 12 h, heating to 575 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and keeping for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 350-400 nm.
Example 3
First, 3.6 mL of sodium silicate aqueous solution was weighed and dissolved in 10.42 g of water, then 0.16 g of sodium hydroxide was added, stirring was carried out at room temperature for 15 min, and then 0.5 g of ultrastable Y molecular sieve (specific surface area: 700 m) having a silica-alumina ratio of 5.4 was added2g-1) Continuously stirring for 30 min, finally adding 2.1 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide, stirring for 30 min at room temperature to obtain initial gel, transferring to a 25 mL stainless steel high-temperature reaction kettle, heating to 100 ℃ at a heating rate of 4 ℃/min in a homogeneous phase rotary reactor, keeping the temperature for 2 min, heating to 140 ℃ at a heating rate of 4 ℃/min, crystallizing for 6 days at a speed of 60 r/min and 140 ℃, centrifuging, washing, and dryingWashing to be neutral, drying overnight at 100 ℃ for 12 h, finally heating to 575 ℃ in a tubular furnace at the heating rate of 1 ℃/min, and keeping for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 300-350 nm.
Example 4
First, 0.8333 g of sodium hydroxide was dissolved in 37.8 g of water, 10.56 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide was added, stirred at room temperature for half an hour, 11.1 mL of an aqueous solution of sodium silicate was added, and 2 g of an ultrastable Y molecular sieve (specific surface area 700 m) having a silica-alumina ratio of 5.4 was added2g-1) Stirring for one hour at room temperature to obtain initial gel, transferring to a 100 mL stainless steel high-temperature reaction kettle, heating to 100 ℃ at a heating rate of 4 ℃/min in a homogeneous phase rotary reactor, keeping the temperature for 2 min, heating to 140 ℃ at a heating rate of 4 ℃/min, crystallizing for 6 days at a speed of 60 rpm and 140 ℃, centrifuging, washing to neutrality, drying overnight at 100 ℃ for 12 h, heating to 575 ℃ at a heating rate of 1 ℃/min in a tubular furnace, and keeping for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 450-500 nm.
Example 5
First, 0.2 g of sodium hydroxide was dissolved in 32.9 g of water, 13.2 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide was added, stirred at room temperature for half an hour, 14.4 mL of an aqueous sodium silicate solution was added, and 2 g of an ultrastable Y molecular sieve (specific surface area 700 m) having a silica-alumina ratio of 5.4 was added2g-1) Stirring for one hour at room temperature to obtain initial gel, transferring the initial gel into a 100 mL stainless steel high-temperature reaction kettle, heating to 100 ℃ at the heating rate of 4 ℃/min in a homogeneous phase rotary reactor, keeping the temperature for 2 min, heating to 140 ℃ at the heating rate of 4 ℃/min, crystallizing at the speed of 60 rpm for 6 days at 140 ℃, centrifuging, washing to neutrality, drying overnight at 100 ℃ for 12 h, heating to 575 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and keeping for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 300-350 nm.
Example 6
First, 13.2 mL of N, N-trimethyl-1-adamantane ammonium hydroxide dissolved in 30.92 g of water, stirred at room temperature for half an hour, then 16.7 mL of an aqueous sodium silicate solution and 2 g of an ultrastable Y molecular sieve having a silica/alumina ratio of 11.5 (specific surface area of 640 m) were added2g-1) After stirring at room temperature for one hour, an initial gel was obtained, which was then transferred to a 100 mL stainless steel autoclave in a homogeneous rotary reactor at 4oRaising the temperature rise rate of C/min to 100 ℃, preserving the heat for 2 min, raising the temperature rise rate of 4 ℃/min to 140 ℃, crystallizing at the speed of 60 r/min to 140 ℃ for 6 days, centrifuging, washing to be neutral, drying at 100 ℃ overnight for 12 h, raising the temperature rise rate of 1 ℃/min to 575 ℃ in a tubular furnace, and preserving the temperature for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 350-400 nm.
Example 7
First, 5.0936 g N, N, N-trimethyl-1-adamantane ammonium iodide was dissolved in 40.97 g of water, stirred at room temperature for half an hour, and then 16.7 mL of an aqueous sodium silicate solution and 2 g of an ultrastable Y molecular sieve (specific surface area: 640 m) having a silica-alumina ratio of 11.5 were added2g-1) Stirring for one hour at room temperature to obtain initial gel, transferring the initial gel into a 100 mL stainless steel high-temperature reaction kettle, heating to 800 ℃ at the heating rate of 1 ℃/min in a homogeneous phase rotary reactor, preserving the temperature for 5min, heating to 140 ℃ at the heating rate of 1 ℃/min, crystallizing at the speed of 60 rpm for 6 days at 140 ℃, centrifuging, washing to neutrality, drying overnight at 100 ℃ for 12 h, heating to 550 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and keeping for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 350-400 nm.
Example 8
First, 1.1666 g of potassium hydroxide was dissolved in 37.8 g of water, 13.2 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide was added, stirred at room temperature for half an hour, 11.1 mL of an aqueous solution of sodium silicate was added, and 2 g of an ultrastable Y molecular sieve (specific surface area: 700 m) having a silica-alumina ratio of 5.4 was added2g-1) Stirred at room temperature for one hour to give an initial gel, which was then transferred to a 100 mL stainless steel autoclave in a homogeneous rotary reactor at 4Raising the temperature rise rate to 100 ℃ per minute, keeping the temperature for 2 min, raising the temperature to 140 ℃ at the temperature rise rate of 4 ℃/min, crystallizing at the speed of 80 r/min for 6 days at 140 ℃, centrifuging, washing to be neutral, drying overnight at 100 ℃ for 12 h, raising the temperature to 550 ℃ at the temperature rise rate of 1 ℃/min in a tubular furnace, and keeping the temperature for 10 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 450-500 nm.
Example 9
First, 0.28 g of potassium hydroxide was dissolved in 42.95 g of water, then 5.0936 g N, N, N-trimethyl-1-adamantane ammonium iodide was added, stirred at room temperature for half an hour, then 14.4 mL of an aqueous sodium silicate solution was added, and then 2 g of an ultrastable Y molecular sieve (specific surface area 700 m) having a silica-alumina ratio of 5.4 was added2g-1) Stirring for one hour at room temperature to obtain initial gel, transferring to a 100 mL stainless steel high-temperature reaction kettle, heating to 80 ℃ at the heating rate of 1 ℃/min in a homogeneous phase rotary reactor, keeping the temperature for 5min, heating to 140 ℃ at the heating rate of 1 ℃/min, crystallizing for 6 days at the speed of 40 rpm at 140 ℃, centrifuging, washing to neutrality, drying overnight for 12 h at 100 ℃, heating to 600 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and keeping for 6 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 400-450 nm.
Example 10
First, 3.6 mL of sodium silicate aqueous solution was weighed and dissolved in 10.42 g of water, then 0.16 g of sodium hydroxide was added, stirring was carried out at room temperature for 15 min, and then 0.5 g of ultrastable Y molecular sieve (specific surface area: 700 m) having a silica-alumina ratio of 5.4 was added2g-1) Continuously stirring for 30 min, finally adding 2.1 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide, stirring for 30 min at room temperature to obtain initial gel, then transferring to a 25 mL stainless steel high-temperature reaction kettle, raising the temperature to 100 ℃ at the heating rate of 4 ℃/min in a homogeneous phase rotary reactor, preserving the temperature for 2 min, raising the temperature to 180 ℃ at the heating rate of 4 ℃/min, crystallizing for 4 days at the speed of 60 r/min and 180 ℃, then centrifuging, washing to be neutral, drying overnight at 100 ℃ for 12 h, finally raising the temperature to 550 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and preserving for 10 h to obtain SSZ-13 raw powder. The resulting SSZ-13 moleculeThe sieve has high purity and good crystallinity, and the size is 300-350 nm.
Example 11
First, 3.6 mL of sodium silicate aqueous solution was weighed and dissolved in 11.97 g of water, then 0.224 g of potassium hydroxide was added, stirring was carried out at room temperature for 15 min, and then 0.5 g of ultrastable Y molecular sieve (specific surface area: 700 m) having a Si/Al ratio of 5.4 was added2g-1) Continuously stirring for 30 min, finally adding 0.7894 g N, N, N-trimethyl-1-adamantane ammonium iodide, stirring for 30 min at room temperature to obtain initial gel, then transferring to a 25 mL stainless steel high-temperature reaction kettle, heating to 100 ℃ at the heating rate of 4 ℃/min in a homogeneous phase rotary reactor, preserving heat for 2 min, heating to 180 ℃ at the heating rate of 4 ℃/min, crystallizing for 4 days at the speed of 80 r/min at 180 ℃, then centrifuging, washing to be neutral, drying overnight for 12 h at 100 ℃, finally heating to 575 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and preserving for 8 h to obtain SSZ-13 raw powder. The obtained SSZ-13 molecular sieve has high purity and good crystallinity, and the size is 350-400 nm.
Comparative example 1
First, 13.2 mL of N, N, N-trimethyl-1-adamantane ammonium hydroxide was dissolved in 45.48 g of water, stirred at room temperature for half an hour, and then 2 g of an ultrastable Y molecular sieve (specific surface area 600 m) having a silica-alumina ratio of 6 was added2g-1) Stirring for one hour at room temperature to obtain initial gel, transferring the initial gel into a 100 mL stainless steel high-temperature reaction kettle, heating to 100 ℃ at the heating rate of 4 ℃/min in a homogeneous phase rotary reactor, preserving the temperature for 2 min, heating to 140 ℃ at the heating rate of 4 ℃/min, crystallizing for 6 days at the speed of 60 r/min at 140 ℃, centrifuging, washing to be neutral, overnight drying for 12 h at 100 ℃, and finally heating to 575 ℃ at the heating rate of 1 ℃/min in a tubular furnace, and keeping for 8 h to obtain the molecular sieve raw powder. FIG. 4 is an XRD pattern of the resulting sample from which we can see that SSZ-13 molecular sieve was not successfully synthesized.
Comparative example 2
An SSZ-13 molecular sieve was prepared according to the method of example 1, except that: 17 mL of sodium silicate aqueous solution was replaced with 31.33g of sodium silicate Solid (SiO)2 Content 20%). As a result, SSZ-13 molecular sieves were not successfully synthesized.
Comparative example 3
An SSZ-13 molecular sieve was prepared according to the method of example 1, except that: crystallizing under standing environment without stirring. The XRD pattern of the final synthesized SSZ-13 molecular sieve is shown in FIG. 5, and the crystallinity is poor.
Although the present invention has been described with reference to particular embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A method for synthesizing SSZ-13 molecular sieve with the assistance of heterogeneous crystal seeds is characterized by comprising the following steps:
(1) uniformly stirring and mixing water, alkali, an organic template agent, a sodium silicate aqueous solution and heterogeneous crystal seeds to obtain initial gel, wherein the heterogeneous crystal seeds are ultrastable Y molecular sieves;
(2) transferring the initial gel into a closed high-temperature reaction kettle, heating to 140-180 ℃ in a homogeneous reactor, and stirring for crystallization;
(3) after crystallization is finished, separating, drying and roasting the product to obtain the SSZ-13 molecular sieve;
the specific surface area of the ultrastable Y molecular sieve is 600-700 m2·g-1The silicon-aluminum ratio of the ultrastable Y molecular sieve is 5.4-11.5;
the silicon source is provided by sodium silicate aqueous solution and heterogeneous seed crystal, the aluminium source is provided by heterogeneous seed crystal, the silicon source: an aluminum source: alkali: h2O: the molar ratio of the organic template agent is 1: 0.03-0.05: 0.31-0.4: 23-33: 0.12 to 0.17, the silicon source is calculated as silica, the aluminum source is calculated as alumina, and the alkali is calculated as metal oxide;
during crystallization, the temperature is raised to 80-100 ℃ at the speed of 1-4 ℃/min, the temperature is kept for 2-5min, and then the temperature is raised to 140-180 ℃ at the speed of 1-4 ℃/min;
the size of the obtained SSZ-13 molecular sieve is 300-500 nm.
2. The method of claim 1, further comprising: the alkali is sodium hydroxide or potassium hydroxide; the organic template agent is N, N, N-trimethyl-1-adamantane ammonium hydroxide or N, N, N-trimethyl-1-adamantane ammonium iodide.
3. The method of claim 1, further comprising: in the sodium silicate aqueous solution, the mass fraction of NaOH is 11.4-14.4%, and the mass fraction of Si is 12-13%.
4. The method of claim 1, further comprising: the crystallization is carried out at a stirring speed of 40-80 rpm.
5. The method of claim 1 or 4, wherein: the crystallization time is 4-6 days.
6. The method of claim 1, further comprising: in the step (3), the roasting is carried out at the temperature of 550-600 ℃, and the roasting time is 6-10 h.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410350.8A CN110127720B (en) | 2019-05-16 | 2019-05-16 | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds |
| PCT/CN2020/071033 WO2020228369A1 (en) | 2019-05-16 | 2020-01-09 | Method for synthesizing ssz-13 molecular sieve under assistance of heterogeneous seed crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410350.8A CN110127720B (en) | 2019-05-16 | 2019-05-16 | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110127720A CN110127720A (en) | 2019-08-16 |
| CN110127720B true CN110127720B (en) | 2020-03-31 |
Family
ID=67574772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910410350.8A Active CN110127720B (en) | 2019-05-16 | 2019-05-16 | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110127720B (en) |
| WO (1) | WO2020228369A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127720B (en) * | 2019-05-16 | 2020-03-31 | 济南大学 | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds |
| CN111348660B (en) * | 2020-03-16 | 2022-08-09 | 江西师范大学 | Medium-silicon CHA type molecular sieve and preparation method and application thereof |
| CN111408401B (en) * | 2020-04-02 | 2021-05-18 | 济南大学 | Preparation method of Cu-SSZ-13 with wide temperature window, obtained product and application |
| CN114162832B (en) * | 2021-12-13 | 2023-03-24 | 大连理工大学 | Synthesis method and application of SSZ-13 molecular sieve in ultra-low template system |
| CN114835133B (en) * | 2022-05-12 | 2023-08-11 | 济南大学 | Preparation method of SSZ-13 molecular sieve with multistage pore structure, obtained product and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276953A (en) * | 2016-08-26 | 2017-01-04 | 天津南化催化剂有限公司 | A kind of preparation method of SSZ 13 molecular sieve |
| CN106629761A (en) * | 2016-12-20 | 2017-05-10 | 上海卓悦化工科技有限公司 | Synthesis method of SSZ-13 molecular sieve |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107010640B (en) * | 2016-01-27 | 2019-02-01 | 中国科学院上海高等研究院 | A kind of method for the synthesis in solid state molecular sieve that crystallite dimension is controllable |
| CN107758691B (en) * | 2017-12-12 | 2018-08-31 | 太原理工大学 | The preparation method of high silicon CHA types SSZ-13 molecular sieves |
| CN110127720B (en) * | 2019-05-16 | 2020-03-31 | 济南大学 | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds |
-
2019
- 2019-05-16 CN CN201910410350.8A patent/CN110127720B/en active Active
-
2020
- 2020-01-09 WO PCT/CN2020/071033 patent/WO2020228369A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276953A (en) * | 2016-08-26 | 2017-01-04 | 天津南化催化剂有限公司 | A kind of preparation method of SSZ 13 molecular sieve |
| CN106629761A (en) * | 2016-12-20 | 2017-05-10 | 上海卓悦化工科技有限公司 | Synthesis method of SSZ-13 molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| Conversion of Faujasites to High-silica Chabazite SSZ-13 in the Presence of N,N,N-Trimethyl-l -adamantammonium Iodide;S.I.Zones et al.;《J. CHEM. SOC. FARADAY TRANS》;19911231;第87卷(第22期);第3709-3716页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110127720A (en) | 2019-08-16 |
| WO2020228369A1 (en) | 2020-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110127720B (en) | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds | |
| CN106185977B (en) | A kind of method of green syt ZSM-5 molecular sieve | |
| CN101759198B (en) | Small crystal particle Y-shaped molecular sieve and preparation method thereof | |
| CN101723400B (en) | Small crystal grain Y-shaped molecular sieve and preparation method thereof | |
| CN102311124B (en) | Method for preparing Silicalite-1/ZSM-5 composite molecular sieve | |
| CN112678842B (en) | Synthesis method of nano Sn-Beta molecular sieve | |
| CN105645429B (en) | A kind of method of the synthesis silica zeolites of Silicalite 2 | |
| CN103121695B (en) | Synthetic method of molecular sieve ZSM-5 (zeolite socony mobil-5) with heteroatom-containing frame | |
| CN109279621B (en) | Method for synthesizing silicon-based zeolite molecular sieve by adopting general ionothermal method | |
| CN110342535A (en) | A kind of preparation method for the porous HZSM-5 zeolite molecular sieve that soda acid is modified | |
| CN110860307A (en) | Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method | |
| CN102674389A (en) | Preparation method of titanium-containing nano-mordenite molecular sieve | |
| WO2016078016A1 (en) | Preparation method for beta zeolite | |
| CN104386707A (en) | Synthesis method of ultralow-sodium high-silicon nano ZSM-5 molecular sieve | |
| CN108097293B (en) | Synthesis method and application of tin-doped MFI structure zeolite molecular sieve | |
| CN101279746A (en) | Method for quickly synthesizing ZSM-5 molecular sieve by variable-temperature crystallization method | |
| CN108439427A (en) | A kind of method that fabricated in situ is rich in mesoporous NaY molecular sieve | |
| CN108862313B (en) | Method for synthesizing MCM-56 molecular sieve by HMI/PI composite template agent | |
| CN102910642B (en) | Preparation method for ZSM-48 molecular sieve | |
| CN112875719B (en) | Method for preparing SSZ-13 molecular sieve by crystal transformation method | |
| CN104649290B (en) | Method for synthesizing beta molecular sieve without organic template | |
| CN113998708B (en) | Method for synthesizing high-crystallinity ZSM-35 molecular sieve without amine and ZSM-35 molecular sieve | |
| CN105523567B (en) | A kind of preparation method of the NaY molecular sieve of controlled dimensions | |
| CN112174162B (en) | Method for preparing Silicalite-1 molecular sieve | |
| CN108584982B (en) | Method for synthesizing flat SSZ-13 molecular sieve by using mixed template agent |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190816 Assignee: SHANDONG ATK ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Assignor: University of Jinan Contract record no.: X2021980002402 Denomination of invention: A method of heteroseed assisted synthesis of SSZ-13 molecular sieve Granted publication date: 20200331 License type: Common License Record date: 20210402 |
|
| EE01 | Entry into force of recordation of patent licensing contract |