CN110562999A - Method for synthesizing ZSM-48 with low silica-alumina ratio by crystal seed assistance - Google Patents
Method for synthesizing ZSM-48 with low silica-alumina ratio by crystal seed assistance Download PDFInfo
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- CN110562999A CN110562999A CN201910847856.5A CN201910847856A CN110562999A CN 110562999 A CN110562999 A CN 110562999A CN 201910847856 A CN201910847856 A CN 201910847856A CN 110562999 A CN110562999 A CN 110562999A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a method for synthesizing ZSM-48 with low silica-alumina ratio by seed crystal auxiliary, which comprises the steps of respectively uniformly mixing homogeneous seed crystals or heterogeneous seed crystals with a silicon source, an aluminum source, an alkali source, an organic template and water to form gel, and carrying out hydrothermal crystallization to obtain the ZSM-48 molecular sieve with the low silica-alumina ratio of 40-100, wherein the shape of crystal grains is a rod shape with the length of 2-5 mu m and the diameter of 0.5-2.0 mu m, and a large number of short rods are interpenetrated and aggregated in the rod-shaped center. The dosage of the seed crystal can be reduced to one ten thousandth by controlling the addition mode and the sequence of the seed crystal, and the aim of synthesizing the ZSM-48 with the low silica-alumina ratio by using the ultra-low seed crystal is fulfilled.
Description
Technical Field
The invention belongs to a synthesis method of a molecular sieve, and relates to a method for synthesizing ZSM-48 with a low silica-alumina ratio by using a seed crystal as an auxiliary material.
Background
The high-silica zeolite ZSM-48, developed by Mobil corporation in the early 80 s of the 20 th century, had ten-membered ring pore openingsThe structure and the one-dimensional linear straight channel are ideal straight-chain alkane hydroisomerization carrier materials. As one of important catalytic conversion processes in the petrochemical industry, hydrocarbon isomerization is widely applied to the field of oil quality improvement, such as gasoline fraction octane number improvement, diesel fraction pour point depression, lubricating oil base oil viscosity-temperature performance improvement and the like. Excellent catalytic hydrogenation activity and isomerization selectivity require the mutual synergistic matching and combined action of carrier acid centers and metal centers. ZSM-48 has limited its wide application in the field of petrochemical industry due to its long synthesis period, expensive template agent cost, high silica-alumina ratio, low acid content and other problems of molecular sieve products. Therefore, how to find a strategy for quickly synthesizing the ZSM-48 molecular sieve with low silica-alumina ratio at low cost becomes a problem which needs to be solved urgently at present.
US6923949 discloses a method for synthesizing a ZSM-48 molecular sieve with a silica/alumina ratio lower than 150 using heterogeneous molecular sieve as seed crystal, which can be used as heterogeneous seed crystal for ZSM-11, ZSM-12, X, Y, ZSM-5, etc. US8003074 discloses a method for synthesizing a ZSM-48 molecular sieve with a silica-alumina ratio less than 100 by using ZSM-48 as a seed crystal and pentamethyldiammonium bromide as a template or simultaneously using the synergy of pentamethyldiammonium bromide and other biquaternary ammonium salts, and the template system must contain pentamethyldiammonium bromide, thus resulting in higher cost of the template. US7482300 discloses a method for synthesizing a ZSM-48 molecular sieve with a silica-alumina ratio lower than 110 with hexamethonium chloride as a template agent under seed crystal assisted conditions, although the effect is significant, hexamethonium chloride is very expensive and toxic. Meanwhile, the dosage of the seed crystal in the ZSM-48 synthesis systems with low silica alumina ratios is about 4 percent, which is not negligible in the practical production process of the molecular sieve.
CN103332703B in Chinese patent discloses a method for synthesizing silicon-rich ZSM-48 by using tetramethylammonium hydroxide as a single template agent and potassium hydroxide as an alkali source, wherein the silicon-aluminum ratio is 266-1000, the aging is carried out for 3-10h at room temperature, and the crystallization period is as high as 6-15 d. CN103803576B discloses a method for synthesizing ZSM-48 molecular sieve with low silica-alumina ratio by using crown ether (12-crown ether-4) as template agent and ZSM-48 as crystal seed, wherein the silica-alumina ratio is in the range of 30-50, but crown ether existsThe template agent is expensive and the dosage of the seed crystal is too high (seed crystal/SiO)2Mass ratio of 0.05-0.5), long crystallization period (4-8d), etc. CN106608635B discloses a method for synthesizing a ZSM-48 molecular sieve with a silicon-aluminum ratio ranging from 10 to 50 by taking dinitrogen oxacycloalkane dibromide salt as a structure directing agent in the presence of organic alkali, wherein the problem of high cost of the structure directing agent is also existed, and the crystallization process is divided into two sections: crystallizing for 1-5 days at 80-140 ℃; ② crystallizing for 5-14 days at 150-250 ℃, and the crystallizing process is complicated and time-consuming.
In order to promote the industrial wide application of the ZSM-48 molecular sieve, the key factor is how to reduce the synthesis cost of the ZSM-48 molecular sieve as much as possible while reducing the silica-alumina ratio of the ZSM-48 and increasing the acid content of the unit molecular sieve. In summary, it was found that, in any case with an improved synthesis method, there are unavoidable disadvantages: firstly, when a cheap template agent is adopted and seed crystals are not used, the synthesized ZSM-48 molecular sieve has higher silicon-aluminum ratio which is generally more than 150; secondly, when an expensive template agent is adopted, although the silica-alumina ratio of the molecular sieve can be lower than 100, the template agent has high cost, about 4 percent of seed crystal is needed for auxiliary synthesis, and the crystallization period is longer.
Disclosure of Invention
The invention aims to provide a method for synthesizing ZSM-48 with low silica-alumina ratio by using a seed crystal to assist in synthesizing a ZSM-48 molecular sieve with the silica-alumina ratio of 40-100 by using a homogeneous seed crystal or a heterogeneous seed crystal, and the dosage of the seed crystal can be reduced to one ten thousandth (0.01%) by adjusting the seed crystal adding mode and sequence.
The technical scheme of the invention is as follows:
A method for synthesizing ZSM-48 with low silica-alumina ratio by using a seed crystal seed in an auxiliary way, which synthesizes a ZSM-48 molecular sieve with the silica-alumina ratio of 40-100 by using a homogeneous seed crystal or a heterogeneous seed crystal in an auxiliary way, and comprises the following specific steps: adding homogeneous seed crystal or heterogeneous seed crystal into a gel system composed of a silicon source, an aluminum source, an alkali source, water and a template agent, stirring uniformly, aging at room temperature for 0-24h, and crystallizing at 140-220 ℃ under hydrothermal autogenous pressure for 9-80h, wherein the molar ratio of the materials is as follows: (1.40-4.50) Na2O：60SiO2：(0.60-1.50)Al2O3: (0.80-2.40) template: (1000-2800) H2O, seed crystal addition amount and SiO2The mass ratio of (A) to (B) is 0.01-7.00%; condensing the aboveAfter hydrothermal crystallization of the colloid system, the obtained product is filtered, washed and dried, and is roasted for 3-5h at 500-650 ℃, and finally the ZSM-48 molecular sieve is obtained.
Seed crystal adding mode and sequence: pre-treating the seed crystal in the solution formed by the alkali source for 0-24h in advance, or adding the seed crystal after the gel system is formed for 0-2 h.
The heterogeneous crystal seed is one or a mixture of more than two of Beta, ZSM-22, ZSM-23, ZSM-5 and MOR.
The homogeneous seed crystal is ZSM-48.
The aluminum source is one or a mixture of more than two of aluminum nitrate, aluminum sulfate, sodium metaaluminate and aluminum isopropoxide.
The silicon source is one or a mixture of more than two of gas-phase silicon dioxide, silica sol and tetraethoxysilane.
The template agent is ammonium hexamethobromide.
The invention has the beneficial effects that: the ZSM-48 molecular sieve with the silicon-aluminum ratio as low as 40-100 can be successfully synthesized by adopting the homogeneous seed crystal and the heterogeneous seed crystal, the dosage of the ZSM-48 molecular sieve can be reduced to 0.01 percent by adjusting the addition mode and the sequence of the seed crystal, and the addition amount of the seed crystal in the prior publication is about 4 percent, so the method greatly reduces the dosage of the seed crystal. In addition, the synthesis period is also greatly shortened, and the crystallization period can be less than 12 h. The crystal seed auxiliary synthesis system can obviously increase the number of crystal nuclei in a nucleation period, further promote crystallization in a growth period, effectively shorten the synthesis period of the ZSM-48 molecular sieve with the low silica-alumina ratio and inhibit mixed crystals.
Drawings
FIG. 1 is an XRD diffraction pattern of ZSM-48 having a silica to alumina ratio of 80.
FIG. 2 is a graph of nitrogen physisorption-desorption of ZSM-48 having a silica to alumina ratio of 80.
FIG. 3 is an SEM scanning electron micrograph of ZSM-48 with a silica to alumina ratio of 80.
FIG. 4 is an XRD diffraction pattern of the ZSM-48 molecular sieve prepared in example 9.
FIG. 5 is an XRD diffraction pattern of the ZSM-48 molecular sieve prepared in example 10.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
example 1
According to the molar ratio of the components: 3.95Na2O：60SiO2：0.75Al2O3: 1.2 template agent: 1200H2And O, sequentially adding 0.78g of sodium hydroxide, 0.38g of sodium metaaluminate, 1.33g of hexamethonium bromide and 11g of fumed silica into 66g of deionized water, uniformly stirring and mixing for 0.5h to obtain white gel, adding 0.022g of beta molecular sieve as heterogeneous crystal seed, continuously stirring and uniformly mixing, transferring to a 100mL hydrothermal kettle, crystallizing at 180 ℃ for 24h, filtering and washing the obtained product, drying the filter cake in a 100 ℃ oven for 12h, and roasting at 550 ℃ for 6h to obtain the ZSM-48 molecular sieve with the low silica-alumina ratio. The obtained ZSM-48 molecular sieve has a silica-alumina ratio of 82 by ICP test analysis.
Example 2
The procedure of example 1 was repeated except that: pretreating a Beta molecular sieve heterogeneous crystal seed in a sodium hydroxide solution for 1h, sequentially adding sodium metaaluminate, hexamethonium bromide and fumed silica, transferring the obtained gel into a 100ml hydrothermal kettle, crystallizing at 180 ℃ for 24h, filtering and washing the obtained product, drying a filter cake in a 100 ℃ drying oven for 12h, and roasting at 550 ℃ for 6h to obtain the ZSM-48 molecular sieve with the low silica-alumina ratio. ICP analysis indicated that the ZSM-48 molecular sieve obtained had a silica to alumina ratio of 78.
Example 3
The procedure of example 1 was repeated except that: beta seed crystal is replaced by ZSM-48 molecular sieve as homogeneous seed crystal. ICP analysis indicated an obtained ZSM-48 molecular sieve silica to alumina ratio of 88.
Example 4
The procedure of example 1 was repeated except that: and replacing Beta crystal seeds with ZSM-23 molecular sieve as heterogeneous crystal seeds. ICP analysis indicated an 84 silica to alumina ratio for the ZSM-48 molecular sieve obtained.
Example 5
The procedure of example 1 was repeated except that: the Beta seed crystal is replaced by ZSM-22 molecular sieve as a heterogeneous seed crystal. ICP analysis showed that the ZSM-48 molecular sieve obtained had a silica to alumina ratio of 79.
Example 6
The procedure of example 2 was repeated except that: 0.022g of beta seed crystal is replaced by 0.011g of ZSM-5 molecular sieve as heterogeneous seed crystal, and pretreated in sodium hydroxide solution for 6 h. ICP analysis indicated that the ZSM-48 molecular sieve obtained had a silica to alumina ratio of 74.
Example 7
The procedure of example 2 was repeated except that: 0.022g of Beta seed was replaced with 0.011g MOR molecular sieve as heterogeneous seed and pretreated in sodium hydroxide solution for 10 h. ICP analysis indicated that the ZSM-48 molecular sieve obtained had a silica to alumina ratio of 76.
Example 8
The procedure of example 2 was repeated except that: weighing 0.0011g of beta molecular sieve as a heterogeneous seed crystal, pretreating in a sodium hydroxide solution for 2h, and crystallizing at 180 ℃ for 42 h. ICP analysis showed the ZSM-48 molecular sieve obtained to have a silica to alumina ratio of 85.
Example 9
According to the molar ratio of the components: 3.95Na2O：60SiO2：1.00Al2O3: 1.2 template agent: 1200H2And O, sequentially adding 0.72g of sodium hydroxide, 0.50g of sodium metaaluminate, 1.33g of hexamethonium bromide and 11g of fumed silica into 66g of deionized water, stirring for 0.25h to obtain white gel, adding 0.077g of molecular sieve ZSM-48 serving as homogeneous seed crystal, continuously stirring and uniformly mixing, transferring to a 100mL hydrothermal kettle, crystallizing at 180 ℃ for 38h, filtering and washing the obtained product, drying the filter cake in a 100 ℃ oven for 12h, and roasting at 550 ℃ for 6h to obtain the ZSM-48 molecular sieve with the low silica-alumina ratio. ICP test analysis indicated that the ZSM-48 molecular sieve obtained had a silica to alumina ratio of 58.
Example 10
According to the molar ratio of the components: 3.55Na2O：60SiO2：1.00Al2O3: 1.2 template agent: 1200H2O, 0.50g of sodium hydroxide, 0.75g of sodium metaaluminate and 1.33g of hexamethonium bromide are sequentially addedAdding 11g of fumed silica into 66g of deionized water, stirring for 0.25h to obtain white gel, adding 0.077g of molecular sieve ZSM-48 as homogeneous seed crystal, continuously stirring and uniformly mixing, transferring to a 100mL hydrothermal kettle, crystallizing at 180 ℃ for 74h, filtering and washing the obtained product, placing a filter cake in a 100 ℃ oven for drying for 12h, and roasting at 550 ℃ for 6h to obtain the ZSM-48 molecular sieve with the low silica-alumina ratio. ICP test analysis indicated an obtained ZSM-48 molecular sieve silica to alumina ratio of 42.
Claims (10)
1. A method for synthesizing ZSM-48 with low silica-alumina ratio by using a seed crystal auxiliary is characterized in that a ZSM-48 molecular sieve with the silica-alumina ratio of 40-100 is synthesized by using a homogeneous seed crystal or a heterogeneous seed crystal auxiliary, and the method comprises the following specific steps: adding homogeneous seed crystal or heterogeneous seed crystal into a gel system composed of a silicon source, an aluminum source, an alkali source, water and a template agent, stirring uniformly, aging at room temperature for 0-24h, and crystallizing at 140-220 ℃ under hydrothermal autogenous pressure for 9-80h, wherein the molar ratio of the materials is as follows: (1.40-4.50) Na2O：60SiO2：(0.60-1.50)Al2O3: (0.80-2.40) template: (1000-2800) H2O, seed crystal addition amount and SiO2The mass ratio of (A) to (B) is 0.01-7.00%; and (3) carrying out hydrothermal crystallization on the gel system, filtering, washing and drying the obtained product, and roasting at 500-650 ℃ for 3-5h to finally obtain the ZSM-48 molecular sieve.
2. The method of claim 1, wherein the seed crystal is added in a manner and in a sequence that: pre-treating the seed crystal in the solution formed by the alkali source for 0-24h in advance, or adding the seed crystal after the gel system is formed for 0-2 h.
3. The method according to claim 1 or 2, wherein the heterogeneous seed crystal is one or a mixture of more than two of Beta, ZSM-22, ZSM-23, ZSM-5 and MOR; the homogeneous seed crystal is ZSM-48.
4. The method as claimed in claim 1 or 2, wherein the aluminum source is one or more of aluminum nitrate, aluminum sulfate, sodium metaaluminate and aluminum isopropoxide.
5. The method as claimed in claim 3, wherein the aluminum source is one or more of aluminum nitrate, aluminum sulfate, sodium metaaluminate and aluminum isopropoxide.
6. The method according to claim 1, 2 or 5, wherein the silicon source is one or a mixture of two or more of fumed silica, silica sol and tetraethoxysilane.
7. The method according to claim 3, wherein the silicon source is one or more of fumed silica, silica sol, and tetraethoxysilane.
8. The method according to claim 4, wherein the silicon source is one or more of fumed silica, silica sol, and tetraethoxysilane.
9. The method of claim 1, 2, 5, 7 or 8, wherein the templating agent is hexamethonium bromide.
10. The method of claim 6, wherein the templating agent is hexamethonium bromide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547738A (en) * | 2020-05-11 | 2020-08-18 | 沈阳师范大学 | Three-dimensional ordered macroporous ZMS-5 molecular sieve material and preparation method thereof |
| CN113620309A (en) * | 2020-05-09 | 2021-11-09 | 中国石油化工股份有限公司 | ZSM-48 molecular sieve and synthesis method and application thereof |
| CN114849765A (en) * | 2022-05-13 | 2022-08-05 | 苏州大学 | Ultrafast preparation method of molecular sieve catalyst |
| CN116425171A (en) * | 2023-03-17 | 2023-07-14 | 大连理工大学 | Preparation method of high-performance hydroisomerization catalyst mesoporous and microporous step structure ZSM 48 molecular sieve |
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|---|---|---|---|---|
| US6923949B1 (en) * | 2004-03-05 | 2005-08-02 | Exxonmobil Research And Engineering Company | Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding |
| US20090076317A1 (en) * | 2007-09-18 | 2009-03-19 | Wenyih Frank Lai | Synthesis of high activity ZSM-48 |
| CN105967202A (en) * | 2016-05-03 | 2016-09-28 | 太原理工大学 | Synthetic method of ZSM-48 molecular sieve with low silica-alumina ratio |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6923949B1 (en) * | 2004-03-05 | 2005-08-02 | Exxonmobil Research And Engineering Company | Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding |
| US20090076317A1 (en) * | 2007-09-18 | 2009-03-19 | Wenyih Frank Lai | Synthesis of high activity ZSM-48 |
| CN105967202A (en) * | 2016-05-03 | 2016-09-28 | 太原理工大学 | Synthetic method of ZSM-48 molecular sieve with low silica-alumina ratio |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620309A (en) * | 2020-05-09 | 2021-11-09 | 中国石油化工股份有限公司 | ZSM-48 molecular sieve and synthesis method and application thereof |
| CN113620309B (en) * | 2020-05-09 | 2023-05-05 | 中国石油化工股份有限公司 | ZSM-48 molecular sieve and synthesis method and application thereof |
| CN111547738A (en) * | 2020-05-11 | 2020-08-18 | 沈阳师范大学 | Three-dimensional ordered macroporous ZMS-5 molecular sieve material and preparation method thereof |
| CN111547738B (en) * | 2020-05-11 | 2023-03-24 | 沈阳师范大学 | Three-dimensional ordered macroporous ZMS-5 molecular sieve material and preparation method thereof |
| CN114849765A (en) * | 2022-05-13 | 2022-08-05 | 苏州大学 | Ultrafast preparation method of molecular sieve catalyst |
| CN116425171A (en) * | 2023-03-17 | 2023-07-14 | 大连理工大学 | Preparation method of high-performance hydroisomerization catalyst mesoporous and microporous step structure ZSM 48 molecular sieve |
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Application publication date: 20191213 |