CN110683556A - Novel structure silicon dioxide zeolite - Google Patents
Novel structure silicon dioxide zeolite Download PDFInfo
- Publication number
- CN110683556A CN110683556A CN201910825855.0A CN201910825855A CN110683556A CN 110683556 A CN110683556 A CN 110683556A CN 201910825855 A CN201910825855 A CN 201910825855A CN 110683556 A CN110683556 A CN 110683556A
- Authority
- CN
- China
- Prior art keywords
- silicalite
- zeolite
- new
- temperature
- silica
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a new structure of silicon dioxide zeolite, the mole ratio of silicon dioxide and aluminium oxide in its chemical composition is greater than 2000, and it has characteristic powder XRD diffraction spectrum, and the opening aperture of two channels in its structure is respectively 4.4x5.6A and 5.1x5.7A, and the BET surface area of the described zeolite is greater than 350m2The micropore volume of the zeolite is more than 0.20 ml/g. The silicalite-3 provided by the invention is prepared by roasting precursor silicalite-1 synthesized by hydrothermal reaction of high-purity fumed silica or tetraethoxysilane at a temperature of more than 500 ℃ in a certain atmosphere for a certain time and severely shrinking crystal lattices, has a specific pore channel shape and pore channel openings, and has the advantages of simple and easily realized generation process conditions and no discharge of waste water and waste gas.
Description
Technical Field
The invention relates to the technical field of silicon dioxide zeolite, in particular to silicon dioxide zeolite with a new structure.
Background
In the prior art, a zeolite molecular sieve which is composed of silica as a framework element can be called as silicalite, the structure of the silicalite has high thermal stability and hydrothermal stability, and the zeolite has the characteristics of inertia to catalytic properties and adsorption of hydrophobic and organophilic substances due to the fact that the framework structure does not contain aluminum atoms, solid acid properties and strong water adsorption centers, so that the zeolite is particularly suitable for being used in catalyst carriers, adsorption separation of small molecular isomers, removal of organic substances in waste water and waste gas and the like.
By no means perfect statistics, 28 silicalites that have been synthesized in the prior art and assigned the structural code by the international zeolite molecular sieve association (IZA) have their own characteristic XRD spectra with regular open channels or cages of different sizes in the framework structure. In addition, zeolites of several structures, such as mordenite, LTL, etc., are silicalites prepared by chemical dealumination, by extracting the aluminum from the silica-alumina framework structure, but leaving the crystal structure intact. At present, the structure types of the commonly used silicalite in international industrial production are totally 8, the silicalite is classified according to the pore diameter, the pore diameter of about 4A is called as a small pore, and only one type of the small pore is available; the pore diameter of the porous material is about 5A, namely mesopores, and the pore diameter is three; the pore size around 7A is called macropore, 4 kinds (see Table 1). The silicalite of different size ranges is suitable for adsorption separation of molecules with different sizes. The small-pore silicalite is suitable for adsorbing, separating and enriching small-molecular hydrocarbons such as methane, ethane, ethylene, propane, propylene and the like, and is also used for removing harmful and toxic gases such as ammonia, CO2, SO2, NOx, HCN, H2S, CSO and the like. The mesoporous silica zeolite is mainly used for adsorbing, separating or removing C4-C7 hydrocarbon, separating isomers of disubstituted aromatic hydrocarbon derivatives and the like. The large-pore silicon zeolite is mainly used for adsorbing, separating or removing hydrocarbons above C8, in particular heavy aromatic hydrocarbon derivatives or polycyclic aromatic hydrocarbons and the like. Of the silicalites listed in Table 1, the most widely used are the MFI type (Silicalite-1 or Silicalite-1) and (Silicalite-2 or Silicalite-2).
TABLE 1 Total silicalite name and structural pore size List
Disclosure of Invention
In view of this, the present invention proposes a new structure of silica zeolite.
The invention provides a new structure silicon dioxide zeolite, the mole ratio of silicon dioxide and aluminium oxide in its chemical composition is greater than 2000, and it has characteristic powder XRD diffraction spectrum, and the aperture of two channel openings in its structure are respectively 4.4x5.6A and 5.1 x5.7A.
Further, the BET surface area of the zeolite is greater than 350m2/g。
Further, the zeolite has a micropore volume greater than 0.20 ml/g.
Further, the characteristic diffraction line of the zeolite is d ═ 10.71 ± 0.1a (vs); 9.62 ± 0.1a (vs); 5.75 ± 0.05 a(s); 4.16 ± 0.02a (m); 3.70. + -. 0.01A (vs).
Further, the zeolite generation process is to carry out roasting treatment on the synthesized precursor silicon zeolite-1 in a certain atmosphere and a certain temperature interval for a certain time, and to generate the precursor silicon zeolite-1 through large-scale lattice contraction.
Further, the precursor silicon zeolite-1 is in R-SiO2-H2And synthesizing by hydrothermal reaction in an O reactant system.
Further, the R comprises C1-C4 quaternary ammonium hydroxide and C3-C6 alkylamine, and the silicon source of the reactant system is at least one of high-purity gas-phase white carbon black and tetraethoxysilane.
Further, the molar composition range of the reactant system is R/SiO2＝0.1-0.5，H2O/SiO210-40, the hydrothermal reaction temperature is 110-.
Further, the atmosphere is air, oxygen, nitrogen, carbon dioxide or mixed gas of air and oxygen with the relative humidity of 10-40%, and the precursor silicalite-1 is greatly shrunk by roasting at the temperature of 500-800 ℃ for 1-4 hours.
Further, the temperature of hydrothermal synthesis of the reaction mixture is 120-200 ℃, and the reaction time is 5-100 h.
Compared with the prior art, the invention has the beneficial effects that the silicalite-3 provided by the invention is generated by roasting precursor silicalite-1 synthesized by hydrothermal reaction of high-purity fumed silica or tetraethoxysilane at a temperature of more than 500 ℃ in a certain atmosphere for a certain time through severe shrinkage of crystal lattices, has a specific shape and an opening of a pore passage, is simple and easy to realize in the generation process condition, and does not discharge any waste water or waste gas.
The proposed silicalite-3 has a BET surface area of more than 350m2G, micropore volumeMore than 0.20ml/g, has good oleophylic and hydrophobic adsorption properties, and can be used for catalyst carriers, adsorption separation of small molecular isomers and removal of organic matters in waste water and waste gas. In the preparation process, a reaction mixture formed by mixing an amorphous silicon raw material and an organic guiding agent is subjected to hydrothermal reaction synthesis under a proper alkaline condition, and then is roasted for a certain time at a temperature of more than 500 ℃ in a certain atmosphere to prepare the hydrophobic Silicalite named as Silicalite-3 (Silicalite-3).
Drawings
FIG. 1 is a schematic structural view of a roasting apparatus with a humidifying pipe according to an embodiment of the present invention;
FIG. 2 is a powder diffraction XRD spectrum of self-made silicalite-1 and silicalite-3 generated therefrom according to an embodiment of the present invention;
FIG. 3 is a graph of the diffraction angle versus calcination temperature for silicalite-1 (051) according to example of the present invention;
FIG. 4 is a powder XRD spectrum of silicalite-1, silicalite-2 and silicalite-3 of examples of the present invention;
FIG. 5 is a schematic representation of the framework structure of silicalite-3 according to an embodiment of the invention;
FIG. 6 is a schematic diagram of the channel opening structure of silicalite-3 according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be further described with reference to specific examples, but the scope of the claims is not limited thereto.
The hydrophobic Silicalite of the new structure of the embodiment of the invention is named as Silicalite-3 (Silicalite-3), has a characteristic powder XRD spectrum, and a characteristic diffraction line d is 10.71 +/-0.1A (vs); 9.62 ± 0.1a (vs); 5.75 ± 0.05 a(s); 4.16 ± 0.02a (m); 3.70. + -. 0.01A (vs).
Specifically, the new structure zeolite has a chemical composition with a silica to alumina molar ratio (SAR) greater than 2000.
Specifically, the new structure zeolite has two kinds of pore channels in its skeleton structure, and the open pore diameters are 4.4X5.6A and 5.1X5.7A, respectively.
In particular, the BET surface area of the new structure zeolite is more than 350m2(iv)/g, micropore volume greater than 0.20 ml/g.
Specifically, the new structure zeolite is produced by sintering the synthesized precursor silicon zeolite-1 (Silicalite-1 with MFI type structure) in a certain atmosphere and a certain temperature interval for a certain time, and greatly shrinking the crystal lattice. In particular, the precursor silicalite-1 is prepared by roasting at 800 ℃ for 1-4 hours in the atmosphere of air, oxygen, nitrogen, carbon dioxide or the mixed gas of air and oxygen with the relative humidity of 10-40% to greatly shrink the crystal lattice of the precursor silicalite-1. The zeolite with the new structure has good oleophylic and hydrophobic adsorption properties, and can be used for catalyst carriers, adsorption separation of small molecular isomers and removal of organic matters in waste water and waste gas.
Wherein the precursor silicon zeolite-1 is in the form of R (organic template) -SiO2-H2Synthesized by hydrothermal reaction in an O reactant system; r comprises C1-C4 quaternary ammonium base and C3-C6 alkylamine, the silicon source of the reactant system is high-purity gas-phase white carbon black and tetraethoxysilane, and the molar composition range of the reactant system is R/SiO2＝0.1-0.5，H2O/SiO210-40, the hydrothermal reaction temperature is 110-180 ℃, and the hydrothermal reaction time is 24-40 hours.
Specifically, the synthesis process of the new-structure silicalite of this example is:
step a, synthesizing precursor silicon zeolite-1 by hydrothermal reaction;
in this process, a 500mL pressure resistant stainless steel autoclave with a capacity of 4F was used for the hydrothermal reaction. High-purity gas-phase white carbon black or ethyl orthosilicate is used as a silicon source, TPAOH (tetrapropylammonium hydroxide), tetrabutylammonium hydroxide (TBA), or n-butylamine and triethylamine are used as template agents R, and the molar ratio of R/SiO is calculated2＝0.1-0.5，H2O/SiO2Pouring 10-40 prepared sol reactant into a stainless steel reaction kettle, sealing, and then placing in an oven to heat to 110-180 ℃, wherein the hydrothermal reaction time is 10-40 hours. After the reaction is finished, cooling the reaction kettle, taking out the reaction product, filtering, washing, drying, roasting to 450-DEG and 500-DEG, removing the template agent R, and obtaining the precursor silicon zeolite-1.
B, roasting the precursor silicalite-1 at a high temperature to obtain silicalite-3 with a new structure, namely, silicalite with a new structure;
referring to fig. 1, a quartz tube or a corundum tube is placed in a hearth of a tubular high-temperature electric furnace, and a quartz boat or a ceramic boat containing precursor silicon zeolite-1 powder is placed in the quartz tube or the corundum tube. The heating temperature of the tubular high-temperature electric furnace is controlled by an electronic temperature controller, and the precision is +/-1 ℃.
The roasting apparatus of the present embodiment includes: the pipe orifice at one side of the quartz pipe or corundum pipe which is provided with the precursor silicon zeolite-1 sample is provided with a pipeline of an external air source which is arranged in a gas steel cylinder 1, the gas comprises air, nitrogen, oxygen or carbon dioxide, when in use, the gas released from a pressure reducing valve 2 of the steel cylinder firstly enters a humidifying device, and the humidifying device is composed of a constant temperature water tank 3 and a humidifying pipe 4 arranged in the constant temperature water tank. When the carrier gas is introduced into the water in the humidifying pipe 4 through the pipeline, the carrier gas is saturated by the water vapor in the humidifying pipe 4. The humidity of the gas flowing out from the humidifying pipe 4 can be controlled to be 10-50% of the relative humidity by a mode of adding ice into the constant-temperature water tank 3 or a mode of raising the temperature of the constant-temperature water tank to a certain degree and keeping the constant temperature. The relationship between the saturated vapor pressure of water and the temperature can be found in a physical and chemical handbook, which is not limited. The humidified gas enters a quartz tube or a corundum tube of a tube type electric furnace 6 to become an atmosphere required to be kept for roasting the precursor silicon zeolite-1, and the precursor silicon zeolite-1 loaded in a quartz boat or a ceramic boat 7 arranged in the quartz tube or the corundum tube is heated to over 500 ℃ in the atmosphere, so that the new structure silicon zeolite-3 is prepared due to the large shrinkage of crystal lattices.
The new-structure silicalite-3 powder prepared in the embodiment of the invention is subjected to XRD identification, and the prepared silicalite-3 powder XRD diffraction spectrum is measured by using an XD-2 powder X-ray diffractometer produced by Beijing Pujingyu general instrument company Limited. The X-ray source is a copper target, 40KV, 30mA and graphite monochromator. The scanning range is 5 degrees to 35 degrees/2 theta, and the speed is 8 degrees (2 theta)/minute. And (3) scanning an XRD powder diffraction spectrum generated by a sample to be detected, and using data processing software carried by the XRD powder diffractometer to print the surface spacing (d) and relative diffraction intensity (I/I0) data of main diffraction peaks of the sample, and comparing the data with the data of characteristic diffraction peaks of the silicalite-3 to identify whether the sample to be detected belongs to the silicalite-3 structure. The characteristic diffraction line for silicalite-3 is d ═ 10.71 ± 0.1a (vs); 9.62 ± 0.1a (vs); 5.75 ± 0.05 a(s); 4.16 ± 0.02a (m); 3.70. + -. 0.01A (vs).
TABLE 2 list of names and structural pore sizes of commonly used silicalites
The combined figure 2 shows the powder diffraction XRD spectrum of the self-made silicalite-1 and the silicalite-3 generated by the self-made silicalite-1 in the embodiment of the invention; the graph clearly shows that the two diffraction peaks have obvious difference in the peak shape and the peak position, the 2 theta angle of the diffraction peak of the silicalite-3 is obviously shifted to a large angle compared with the silicalite-1, and the shift is increasingly prominent for the diffraction peak at a high angle. The 2 theta angle of the diffraction peak of the silicalite-1 was shifted from about 23.1 degrees to about 24.05 degrees of the silicalite-3 at a shift of nearly 1.0 degree as seen from the spectrum of silicalite-1. This indicates that the crystal structures of silicalite-1 and silicalite-3 differ substantially and should not be of the same structural type.
TABLE 3 self-made silicalite-1
Diffraction angle of main diffraction peak in powder XRD diffraction pattern after different temperature roasting
The data in Table 3 show that the positions of the three main characteristic diffraction peaks of the silicalite-1 all have a sudden change towards a large angle when the roasting temperature is above 500 ℃. This phenomenon is indicative of a sudden contraction of the crystal lattice. Thus, the structure of silicalite-3 is clearly different from that of silicalite-1.
FIG. 3 is a graph showing the relationship between the diffraction angle and the calcination temperature of silicalite-1 (051) according to the embodiment of the present invention; the diffraction angle diagram is the diffraction angle diagram of the (051) diffraction peak in a powder XRD diffraction diagram which is shot by calcining self-made silicalite-1 (MFI type) with a silica-alumina molar ratio (SAR being 3000) in a nitrogen atmosphere with certain humidity at different temperatures for 2 hours and cooling. It can be seen that the diffraction angle of the diffraction peak suddenly increases at 500 ℃, indicating that the lattice shrinks significantly, and tends to be gentle above 700 ℃ and begins to stabilize at 780 ℃.
Specifically, the position of the diffraction peak in the XRD powder diffraction principle, i.e., the diffraction angle θ, and the value of the interplanar spacing (d) of the diffraction peak have the following formula relationship:
2d Sinθ＝nλ (1)
where λ is the wavelength of X-rays generated by the anode target material of the radiation source used in the XRD diffractometer, the XRD diffractometer used in this example was a copper target with a characteristic wavelength of 1.5410A (i.e. 0.1541 nm). n is the number of diffraction orders; so n λ is constant for a particular diffraction peak. This formula shows that the diffraction angle θ of a diffraction peak is inversely related to the d value of the diffraction peak.
The lattice symmetry of silicalite-1 is that of an orthorhombic system, the three symmetry axes of the crystal lattice are perpendicular to each other, and the axial lengths (i.e., lattice constants) are a, b, and c, respectively. The value of d for each diffraction peak is related to the lattice constant by the following equation:
1/d2＝h2/a2+k2/b2+l2/c2(2)
wherein h, k and l are diffraction indices of the diffraction peaks, respectively.
According to the formula 1 and the formula 2, the value of the surface distance d can be calculated from the diffraction angle 2 theta value of the series of diffraction peaks obtained by calculation of the actually measured powder XRD diffraction spectrum, and further the lattice constants a, b and c can be calculated from the formula 2.
TABLE 4 lattice constants of silicalite-1 and silicalite-3
| Lattice constant/A | Literature data | Boiling of siliconMeasured data of stone-1 | Actual measurement data of silicalite-3 |
| a | 20.02 | 19.78 | 19.20 |
| b | 19.90 | 19.42 | 17.28 |
| c | 13.38 | 13.26 | 13.39 |
| V (lattice volume/A3) | 5332 | 5095 | 4442 |
Collection of Simulated XRD Powder Patterns for Zeolites,FifthRevised Edition,2007,p.279。
Table 3 shows the literature values and the measured values of the lattice parameters of silicalite-1 and the measured values of silicalite-3. Comparing the literature data and the measured data for silicalite-3 and silicalite-1 leads to the following conclusions: in the lattice constant of the silicalite-3, the a value is shortened by 3-4%, the b value is shortened by 11-13%, the c value is basically unchanged, and the lattice volume is reduced by 12-17%.
Referring to FIG. 4, there are shown powder XRD spectra of silicalite-1, silicalite-2, and silicalite-3 of examples of the present invention; in the illustration, the Powder XRD spectra of silicalite-1 and silicalite-2 are "theoretical" Powder diffraction spectra calculated by simulations with specialized software using the coordinates of the Si and oxygen atoms constituting the Zeolites in the crystal lattice obtained by single crystal structure determination, see references:collectionof multiplexed XRD Powder Patterns for Zeolites, Fifth RevisedEdition,2007, p.269, p.279. In the embodiment of the invention, it is obvious from the XRD spectrum of FIG. 4 that the XRD diffraction spectra of silicalite-3, silicalite-1 and silicalite-2 do not belong to the same framework structure type in terms of the number, position and intensity order distribution of peaks.
TABLE 5 characteristic diffraction Peak data for several silicalites
USP 4061724 (1977); i-diffraction intensity; vs-very strong, s-strong, m-moderate
Table 5 shows the literature values of the characteristic diffraction spectrum data of silicalite-1, the measured values of the zeolite synthesized experimentally in this example, and the measured values of the characteristic diffraction spectrum of silicalite-3 produced by the lattice contraction thereof. Obviously, the characteristic XRD diffraction data of the self-made silicalite-1 adopted in the embodiment are consistent with literature values and are obviously different from the silicalite-3 generated by strong lattice contraction, and further prove that the silicalite-3 is different from the silicalite-1 in crystalline phase.
Fig. 5 is a schematic diagram of the framework structure of silicalite-3 according to an embodiment of the present invention, and fig. 6 is a schematic diagram of the pore opening structure of silicalite-3 according to an embodiment of the present invention. The change in lattice constant from Table 4 for this example can be plotted by simple simulations, where the data show that the [100] direction channel opening size for silicalite-3 is 4.4X5.6A and the [010] direction channel opening is 5.1 X5.7A. The [100] direction channel opening size is 5.5X 5.1A and the [010] direction channel opening is 5.6X 5.3A compared to the literature value for silicalite-1. In contrast, silicalite-3 has smaller pore openings than silicalite-1, and apparently becomes "flat" in the [100] direction.
TABLE 6 adsorption statistics of silicalite-1 and silicalite-3
The data in Table 6 show that silicalite-3 has a lower surface area and pore volume and average pore diameter, as measured by low temperature nitrogen adsorption, than silicalite-1, compared to the data for silicalite-1, which is due to lattice shrinkage. The water adsorption of the two is lower than that of normal hexane, which shows that the two have good hydrophobicity. Particular mention should be made of n-hexane adsorption, silicalite-3 being 67mg/g and 56% of 119mg/g of silicalite-1. This is due to the reduction of the opening size of the [100] direction channel to 4.4X5.6A, which prevents n-hexane from adsorbing from the pore.
The process for synthesizing the new-structure silicalite of this example is illustrated by the following examples.
Example one
Adding 25% tetrapropylammonium hydroxide (TPA) as template agent (R) into ethyl orthosilicate at room temperature, stirring for hydrolysis, heating to 70-80 deg.C for dealcoholization, adding water, and adjusting the molar ratio of TPAOH/SiO in the resultant reaction mixture2＝0.10，H2O/SiO225; transferring the reaction mixture into a stainless steel pressure-resistant reaction kettle, carrying out hydrothermal reaction for 36 hours at 125 ℃, cooling, taking out a reaction product, filtering, washing, drying, roasting to 450 ℃ for 6 hours, and removing a template agent R to obtain the precursor silicon zeolite-1.
The precursor silicon zeolite-1 is put into a quartz boat 7 in a roasting device shown in figure 1, the temperature of a tubular electric furnace 5 is raised to 650 ℃ and kept constant, a valve 2 of an air steel cylinder 1 is opened to lead air into a humidifying pipe 4 shown in figure 1, the water temperature of a constant temperature tank is adjusted, the relative humidity of the air flowing out of the humidifying pipe is adjusted to 20 percent and then is taken as a sample roasting gas to be led into a quartz pipe 6, and after roasting for 4 hours, the quartz boat is taken out and cooled to obtain a product-1. The calcined product, sample-1, was tested with an XD-2 powder XRD diffractometer. The scanning range is 5 degrees to 35 degrees/2 theta, and the speed is 8 degrees (2 theta)/minute. Scanning the generated XRD powder diffraction spectrum of the sample, and extracting the interplanar spacing (d) and the relative diffraction intensity (I/I) of the main diffraction peak of the product-1 by data processing software carried by the XRD diffractometer0) Are shown in Table 7.
Example two
Tetrabutylammonium hydroxide at 20% concentration at room temperature(TBA) as template agent (R) is added into ethyl orthosilicate for stirring and hydrolysis, heated to 70-80 ℃ for dealcoholization, added with water and adjusted to the molar ratio of TBAOH/SiO of each substance in the generated reaction mixture2＝0.20；H2O/SiO235; transferring the reaction mixture into a stainless steel pressure-resistant reaction kettle, carrying out hydrothermal reaction for 24 hours at 145 ℃, cooling, taking out the reaction product, filtering, washing, drying, roasting to 500 ℃, and removing the template agent R to obtain the precursor silicon zeolite-1.
The precursor silicon zeolite-1 is put into a quartz boat 7 in a roasting device shown in figure 1, the temperature of a tubular electric furnace 5 is raised to 750 ℃ and kept constant, a valve 2 of a nitrogen steel cylinder 1 is opened to introduce nitrogen into a humidifying pipe 4 shown in figure 1, the water temperature of a constant temperature tank is adjusted, and the relative humidity of the nitrogen flowing out of the humidifying pipe is adjusted to 30 percent and then is taken as a sample roasting gas to be introduced into a quartz pipe 6. After roasting for 2 hours, taking out the quartz boat and cooling to obtain a product-2. The calcined product, sample 2, was tested using an XD-2 powder XRD diffractometer. The scanning range is 5 degrees to 35 degrees/2 theta, and the speed is 8 degrees (2 theta)/minute. Scanning the generated XRD powder diffraction spectrum of the sample, and extracting the interplanar spacing (d) and the relative diffraction intensity (I) of the main diffraction peak of the product-2 by data processing software carried by the XRD diffractometer0) The data are shown in Table 7.
EXAMPLE III
At room temperature, n-butylamine is used as a template agent (R), water is added, the mixture is mixed with high-purity gas phase white carbon black powder, the mixture is stirred and mixed evenly, and the molar ratio of each substance in the generated reaction mixture is adjusted to be n-butylamine/SiO2＝0.50；H2O/SiO 220; transferring the reaction mixture into a stainless steel pressure-resistant reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 72 hours, cooling, taking out the reaction product, filtering, washing, drying, and roasting to 500 ℃ to remove the template agent R, thus obtaining the precursor silicon zeolite-1.
The precursor silicon zeolite-1 is placed in a quartz boat 7 in a roasting device shown in figure 1, the temperature of a tubular electric furnace 5 is raised to 780 ℃ and kept constant, a valve 2 of an oxygen steel cylinder 1 is opened to introduce oxygen into a humidifying pipe 4 shown in figure 1, the water temperature of a constant temperature tank is adjusted, and the relative humidity of the oxygen flowing out of the humidifying pipe is adjusted to 30 percentThen, the sample was passed through a quartz tube 6 as a sample baking gas. After roasting for 2 hours, taking out the quartz boat and cooling to obtain a product-3. The calcined product, sample 3, was tested using an XD-2 powder XRD diffractometer. The scanning range is 5 degrees to 35 degrees/2 theta, and the speed is 8 degrees (2 theta)/minute. Scanning the generated XRD powder diffraction spectrum of the sample, and extracting the interplanar spacing (d) and the relative diffraction intensity (I) of the main diffraction peak of the product-2 by data processing software carried by the XRD diffractometer0) The data are shown in Table 7.
Example four
Triethylamine is taken as a template agent (R) at room temperature, water is added, the mixture is mixed with high-purity gas phase white carbon black powder, the mixture is stirred and mixed evenly, and the molar ratio of each substance in the generated reaction mixture is adjusted to be triethylamine/SiO2＝0.50；H2O/SiO 230; transferring the reaction mixture into a stainless steel pressure-resistant reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 72 hours, cooling, taking out the reaction product, filtering, washing, drying, and roasting to 500 ℃ to remove the template agent R, thus obtaining the precursor silicon zeolite-1.
The precursor silicon zeolite-1 is put into a quartz boat 7 in a roasting device shown in figure 1, the temperature of a tubular electric furnace 5 is raised to 800 ℃ and kept constant, a valve 2 of a carbon dioxide steel cylinder 1 is opened to lead carbon dioxide into a humidifying pipe 4 shown in figure I, the water temperature of a constant temperature tank is adjusted, and the relative humidity of the carbon dioxide flowing out of the humidifying pipe is adjusted to 10 percent and then is taken as a sample roasting gas to be led into a quartz pipe 6. After roasting for 1 hour, taking out the quartz boat and cooling to obtain a product-4. The calcined product, sample 4, was tested using an XD-2 powder XRD diffractometer. The scanning range is 5 degrees to 35 degrees/2 theta, and the speed is 8 degrees (2 theta)/minute. Scanning the generated XRD powder diffraction spectrum of the sample, and extracting the interplanar spacing (d) and the relative diffraction intensity (I) of the main diffraction peak of the product-4 by data processing software carried by the XRD diffractometer0) The data are shown in Table 7.
TABLE 7 Zeolite-3 feature powder XDR diffraction data prepared by high temperature calcination
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A new-structure silica zeolite features that its mole ratio of silica to alumina is greater than 2000, and its structure has a characteristic powder XRD diffraction spectrum, and the open pore diameters of two channels in its structure are 4.4x5.6A and 5.1 x5.7A.
2. The new structure silica zeolite of claim 1, wherein said zeolite has a BET surface area greater than 350m2/g。
3. The new structure silica zeolite of claim 1, wherein said zeolite has a pore volume greater than 0.20 ml/g.
4. The new structure silica zeolite according to claim 1, wherein the zeolite has a characteristic diffraction line d ═ 10.71 ± 0.1a (vs); 9.62 ± 0.1a (vs); 5.75 ± 0.05 a(s); 4.16 ± 0.02a (m); 3.70. + -. 0.01A (vs).
5. The new-structure silica zeolite according to claim 1, wherein the zeolite is produced by subjecting the precursor-silicon zeolite-1 to calcination treatment in a predetermined atmosphere and at a predetermined temperature range for a predetermined period of time, and by causing the crystal lattice to shrink greatly.
6. The new structure silicalite as claimed in claim 5 wherein the precursor silica zeolite-1 is in R-SiO2-H2And synthesizing by hydrothermal reaction in an O reactant system.
7. The new structure silicalite as claimed in claim 6 wherein R comprises C1-C4 quaternary ammonium bases, C3-C6 alkyl amines and the silicon source of the reactant system is at least one of high purity fumed silica and ethyl orthosilicate.
8. The new structure silicalite according to claim 7 wherein the reactant system has a molar composition in the range of R/SiO2＝0.1-0.5，H2O/SiO210-40, the hydrothermal reaction temperature is 110-.
9. The new-structure silicalite as claimed in claim 5, wherein the atmosphere is a mixed gas of air and oxygen with a relative humidity of 10-40%, and the calcination is carried out at 500-800 ℃ for 1-4 hours to greatly shrink the crystal lattice of the precursor silicalite-1.
10. The new-structure silicalite as claimed in claim 9, wherein the hydrothermal synthesis temperature of the reaction mixture is 120-200 ℃ and the reaction time is 5-100 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910825855.0A CN110683556B (en) | 2019-09-03 | 2019-09-03 | Novel structure silicon dioxide zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910825855.0A CN110683556B (en) | 2019-09-03 | 2019-09-03 | Novel structure silicon dioxide zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110683556A true CN110683556A (en) | 2020-01-14 |
| CN110683556B CN110683556B (en) | 2021-07-16 |
Family
ID=69108777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910825855.0A Active CN110683556B (en) | 2019-09-03 | 2019-09-03 | Novel structure silicon dioxide zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110683556B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482158A (en) * | 2020-03-19 | 2020-08-04 | 复榆(张家港)新材料科技有限公司 | Preparation system of pure silicon zeolite-3 adsorbent without adhesive |
| WO2021042951A1 (en) * | 2019-09-03 | 2021-03-11 | 复榆(张家港)新材料科技有限公司 | Process for synthesizing silica zeolite having new structure |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262144A (en) * | 1991-12-26 | 1993-11-16 | Uop | Siliceous molecular sieves having low acid activity and process for preparing same |
| CN101590423A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of shape-selection and modification method of zeolite catalyst |
| CN103831128A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Modified nano molecular sieve hydrogenation aromatization catalyst and preparation method thereof |
| WO2015029055A1 (en) * | 2013-08-30 | 2015-03-05 | Süd-Chemie India Pvt Ltd. | An abbreviated process to custom-make titanium silicate based catalysts with variegated physico-chemical properties |
| CN109019626A (en) * | 2017-06-12 | 2018-12-18 | 中国石油化工股份有限公司 | A kind of total silicon mesoporous material and preparation method thereof and the application in rearrangement reaction |
| CN109745871A (en) * | 2019-03-01 | 2019-05-14 | 江苏赛清科技有限公司 | A kind of high separation selectivity pure silica zeolites composite membrane and preparation method thereof |
-
2019
- 2019-09-03 CN CN201910825855.0A patent/CN110683556B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262144A (en) * | 1991-12-26 | 1993-11-16 | Uop | Siliceous molecular sieves having low acid activity and process for preparing same |
| CN101590423A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of shape-selection and modification method of zeolite catalyst |
| CN103831128A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Modified nano molecular sieve hydrogenation aromatization catalyst and preparation method thereof |
| WO2015029055A1 (en) * | 2013-08-30 | 2015-03-05 | Süd-Chemie India Pvt Ltd. | An abbreviated process to custom-make titanium silicate based catalysts with variegated physico-chemical properties |
| CN109019626A (en) * | 2017-06-12 | 2018-12-18 | 中国石油化工股份有限公司 | A kind of total silicon mesoporous material and preparation method thereof and the application in rearrangement reaction |
| CN109745871A (en) * | 2019-03-01 | 2019-05-14 | 江苏赛清科技有限公司 | A kind of high separation selectivity pure silica zeolites composite membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MARTA NAVARRO ET AL.: "Activation of giant silicalite-1 monocrystals combining rapid thermal processing and ozone calcination", 《RSC ADVANCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021042951A1 (en) * | 2019-09-03 | 2021-03-11 | 复榆(张家港)新材料科技有限公司 | Process for synthesizing silica zeolite having new structure |
| CN111482158A (en) * | 2020-03-19 | 2020-08-04 | 复榆(张家港)新材料科技有限公司 | Preparation system of pure silicon zeolite-3 adsorbent without adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110683556B (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110683555B (en) | Synthesis process of new structure silicon dioxide zeolite | |
| TWI777925B (en) | Molecular sieve ssz-91, methods for preparing ssz-91, and uses for ssz-91 | |
| Corma et al. | Synthesis and characterization of the MCM-22 zeolite | |
| JP6371476B2 (en) | Method for producing molecular sieve SSZ-98 | |
| JP6381797B2 (en) | Molecular sieve SSZ-98 | |
| US8282908B2 (en) | Zeolite beta and process for producing the same | |
| US10384951B1 (en) | Molecular sieve SSZ-113, its synthesis and use | |
| CN110683556B (en) | Novel structure silicon dioxide zeolite | |
| US20200299142A1 (en) | Molecular sieve ssz-91, methods for preparing ssz-91, and uses for ssz-91 | |
| CN107930677B (en) | Modified ZSM-5 catalyst for alkylation reaction, preparation method and application thereof, and preparation method of p-xylene | |
| KR20200128044A (en) | *Synthesis of MRE framework type molecular sieve | |
| KR19990066988A (en) | Method for changing porosity of aluminosilicate and silica and mesoporous composition derived therefrom | |
| EP3445715A1 (en) | Synthesis of zeolite ssz-31 | |
| JP2023537372A (en) | EMM-58 zeolite composition, synthesis and use | |
| CN112694100B (en) | Fe-ZSM-5 molecular sieve, preparation method and application thereof | |
| CN114477209B (en) | Silicon-aluminum molecular sieve and preparation method and application thereof | |
| CN109422275B (en) | Rapid hydrothermal synthesis H-LTA type molecular sieve, and preparation method and application thereof | |
| EP3568376B1 (en) | Synthesis of zeolite ssz-31 | |
| US9663380B2 (en) | Molecular sieve SSZ-105 | |
| CN114477210B (en) | Beta molecular sieve and preparation method thereof | |
| CN114479909B (en) | Hydrocarbon conversion method, catalyst and catalyst preparation method | |
| RU2785394C2 (en) | Ssz-91 molecular sieve, ssz-91 production methods, and ssz-91 use | |
| CN114478181B (en) | Method for preparing ethylbenzene by gas phase method, catalyst and preparation method of catalyst | |
| US20230357030A1 (en) | Synthesis of aluminum-containing cit-13 and cit-15 molecular sieves | |
| CN111099637B (en) | Silicon-phosphorus-aluminum molecular sieve and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |