CN113998707B - Super-macroporous IRR structure silicate molecular sieve material and preparation method thereof - Google Patents
Super-macroporous IRR structure silicate molecular sieve material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super-macroporous silicate molecular sieve with an IRR (iron-reducing) framework crystal structure, which has a chemical composition form of p (M) 1/n XO 2 )·qYO 2 ·SiO 2 Wherein M represents a proton or an inorganic cation of + n valency; x represents one or more trivalent elements; y represents one or more tetravalent elements other than Si and Ge; p =0-0.03, q =0-0.03. The molecular sieve has oversized 18-membered pore channels in the c-axis direction of a unit cell, 12-membered pore channels in the a-axis and b-axis directions, and 18 multiplied by 12 crossed three-dimensional pore channels. The invention further discloses a preparation method of the molecular sieve, which is obtained by using an organic template and a certain amount of seed crystals to promote crystallization through a hydrothermal synthesis method, and the molecular sieve has a stable skeleton structure after the organic template is removed, and has potential application value in the field of catalysis.
Description
Technical Field
The invention belongs to the technical field of zeolite molecular sieve preparation, and particularly relates to a preparation method of a super-macroporous IRR structure silicate molecular sieve material.
Background
Molecular sieves are of the type consisting of TO 4 The (T = Si, al, ge and the like) tetrahedron is made of a porous material with shared vertexes, and has excellent chemical and hydrothermal stability, variable chemical composition, specific pore diameter and pore shape, so that the performances of solid acidity, gas selective adsorption and separation, ion exchange, object molecule transportation and the like are displayed. Has an empirical chemical formula: x (M) 1/ n XO 2 )·yYO 2 ·zR·qH 2 O, wherein M represents one or more organic or inorganic cations having a valence of + n; x represents one or more trivalent elements; y represents one or more tetravalent elements, usually Si; r represents one or more organic molecules.
According TO TO of the enclosed tunnel 4 The tetrahedral number, the molecular sieve material can be divided into small, medium, large and ultra-large pore molecular sieves, with corresponding 8-membered rings (i.e. 8 TO) 4 Tetrahedral formation), 10-membered rings, 12-membered rings, and more than 12-membered rings. Molecular sieve materials successfully used in industry have pore sizes below 1nm, which limits the molecular size and shape of the reaction substrate during adsorption, separation and catalysis, and is an artificial brake for the practical application of molecular sieve materials. Due to the large pore channels, the ultra-large pore molecular sieve has huge application prospects in the aspects of cracking processes, fine chemical production, selective catalysis and macromolecular separation, and attracts the attention of chemists and industries for a long time. In the past decades, the synthesis of ultra-large pore molecular sieves has been pursuedGreat developments have been made but the preparation of stable very large pore molecular sieves remains a challenge.
Crystallization of ultra-large pore silicate molecular sieves is very difficult, and the number of synthesized silicate molecular sieve materials having an ultra-large pore structure is very limited. In recent years, the successful synthesis of ultra-large pore molecular sieves has been attributed primarily to the use of specific organic structure directing agents and heteroatoms in the synthesis. Among them, the existence of germanium has lower geometrical constraint on the formation of primary structural units, so that the primary structural units tend to form double four-membered rings or double three-membered rings, and the ultra-large pore molecular sieve is easier to form, thereby leading to the synthesis of a series of silicon germanate molecular sieves. Germanium is a relatively rare and expensive element, and the poor hydrothermal stability of the silicon germanosilicate molecular sieve limits its industrial application.
The ultra large pore silicon germanate molecular sieve ITQ-44 of IRR structure (IRR is the structure code identified by the international molecular sieve association) has 18 × 12 × 12 intersecting three-dimensional channels and a secondary structural unit consisting of a double ternary ring cage (j.jiang, j.l. jorda, m.j).
J.yu, a.corma, angelw.chem.int.ed.2010, 49. The three-dimensional channel has an eighteen-membered ring channel in the direction of a unit cell c, and each of the a and b directions has a twelve-membered ring channel to form a channel structure crossed with the eighteen-membered ring channel. Unfortunately, the presence of large amounts of germanium in the ITQ-44 framework, not only is costly, but also limits the hydrothermal stability of this material, largely limiting its industrial application, while the structure still does not synthesize pure silicate (silica) and aluminosilicate forms. The pure silicate and aluminosilicate molecular sieves have good hydrothermal stability, and aluminum atoms are introduced into acid sites, so that the pure silicate and aluminosilicate molecular sieves can be directly used for acid catalysis. Therefore, the synthesis and development of the pure silicate and aluminosilicate zeolite molecular sieve with the ultra-large pore IRR structure have very important application value.
Disclosure of Invention
The invention aims to provide an ultra-large pore silicate molecular sieve with an IRR structure, which can be obtained by a hydrothermal synthesis method and promoted crystallization by using an organic template and a certain amount of IRR seed crystals (containing germanium or not containing germanium). The super-macroporous IRR structure silicate molecular sieve has an IRR framework crystal structure, does not contain germanium element in a framework, has good hydrothermal stability, and provides a new choice for application of a molecular sieve material in industrial catalysis.
The technical scheme of the invention is as follows:
a super-macroporous silicate molecular sieve with IRR skeleton crystal structure and p (M) as chemical composition 1/ n XO 2 )·qYO 2 ·SiO 2 Wherein M represents a proton or an inorganic cation of + n valency; x represents one or more trivalent elements; y represents one or more tetravalent elements other than silicon and germanium; p =0-0.03, q =0-0.03.
Preferably M represents a proton or sodium; x is Al or B, X is Ti, and p =0-0.02; q =0-0.02.
The super-macroporous IRR structure silicate molecular sieve can be prepared by the following method, and comprises the following steps: (1) Uniformly mixing a silicon source substance, a boron family element compound, a tetravalent element compound except silicon and germanium, an organic template agent, a fluorine source substance, an IRR Seed crystal Seed and water in proportion under stirring, and reacting under the conditions of static stirring and dynamic stirring to obtain reaction gel, wherein the chemical composition of the reaction gel is as follows: rROH, aHF, xX 2 O 3 :yYO 2 :SiO 2 :bSeed:wH 2 O, wherein R represents a positively charged group of the organic templating agent; x represents one or more trivalent elements, preferably X is Al or B; y represents one or more tetravalent elements other than silicon and germanium, preferably Y is Ti; r =0.1-1.0, a =0-1.0, b =0.001-0.05, x =0-0.03, y =0-0.03, w =1-50, preferably r =0.5-0.75, a =0.5-0.75, b =0.01-0.05, x =0-0.02, y =0-0.02, w =1-10; r is Ar- (im) + An organic cation, wherein Ar represents para-and meta-substituted tert-butylbenzyl, and im represents N-substituted imidazole;
(2) Removing excessive solvent (such as infrared lamp or 80 deg.C oven) from the reaction gel to theoretical weight, transferring the reaction gel into stainless steel reaction kettle, and reacting at 140-170 deg.C under sealed condition for 7-30 days, preferably 14-20 days;
(3) And (3) washing and drying the product crystallized in the step (2), and roasting at 400-650 ℃ for 2-5 hours in the air atmosphere to obtain the super-macroporous silicate molecular sieve without the template agent.
Preferably, the silicon source material is one or more of water glass, silica sol, ethyl orthosilicate or butyl orthosilicate. The boron compound is preferably one or more of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate, aluminum hydroxide or boric acid. Preferably, the fluorine source material is hydrofluoric acid and/or ammonium fluoride. The tetravalent element compound other than silicon and germanium is preferably tetra-n-butyl titanate, tin dioxide.
In the preparation method of the ultra-large pore molecular sieve, the organic template is tert-butyl benzyl imidazolium salt, and the positive charge group R is preferably listed in Table 1.
TABLE 1
The IRR Seed crystal Seed is an IRR structure molecular sieve of silicate germanate, pure silicate, aluminosilicate or silicate titanate. The IRR silicon germanosilicate ITQ-44 can be prepared by adding a compound containing germanium element, such as germanium dioxide, in the step (1) on the basis of the preparation method disclosed by the invention. Or by literature methods (e.g., j.jiang, j.l.jorda, m.j).
J.yu, a.corma, angelw.chem.int.ed.2010, 49; r.bai, q.sun, n.wang, y.zou, g.guo, s.iborra, a.corma, j.yu, chem.mater.2016,28, 6455) to form ITQ-44 germanosilicate. The pure silicate, aluminosilicate or titanosilicate molecular sieves of the present invention may be further seeded for large scale production.
In the above method, before the reaction gel is prepared, the organic template is exchanged to the form of hydroxide base (ROH) through an ion exchange resin, and the concentration of the organic template is calibrated by 0.1M hydrochloric acid solution for later use.
If the silicon titanate or silicon silicate molecular sieve is prepared, firstly, a compound containing titanium or germanium elements is added into the obtained basic template solution, the mixture is stirred and dissolved, then a silicon source is added and the mixture is continuously stirred, finally, a corresponding boron group element compound is added, a fluorine source substance is added after the mixture is uniformly stirred, and the mixture is heated under an infrared lamp or in an oven to remove redundant solvent in the system, so that the target gel is obtained.
The invention has the advantages that:
the invention utilizes a specific template agent, adds a certain IRR structure seed crystal (containing germanium or not containing germanium), and prepares the silicate molecular sieve with a micro-germanium or germanium-free super-macroporous IRR structure by hydrothermal synthesis, thereby avoiding the defect that the prior molecular sieve with the structure is synthesized into the silicon silicate ITQ-44 with the IRR structure by using germanium, and then pure silicate and aluminosilicate molecular sieve with the IRR structure can be obtained by removing germanium and supplementing silicon or supplementing aluminum. The silicate molecular sieve with the IRR structure prepared by the invention has 18-membered pore channels in the c direction of the crystal axis and 12-membered pore channels in the a and b directions, has good thermal stability, can be doped with heteroatoms and has potential application value in the field of catalysis.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (Cu target) of the synthesized product.
FIG. 2 is a scanning electron micrograph of the synthesized all-silicon molecular sieve product.
Detailed Description
The following examples illustrate specific steps of the present invention, but are not intended to limit the invention.
Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
Example 1: the synthesis process of the template is described by taking template 1 in Table 1 as an example.
15mL of 4-tertButyl benzyl chloride was dissolved in 150mL of tetrahydrofuran, and 6.2mL of 1-methylimidazole was added thereto, followed by reflux reaction for 2 days. Then cooled to room temperature, filtered to give a white solid product, washed with ether (3X 10 mL), dried overnight under vacuum, yield 95%. Subjecting the product to liquid nuclear magnetic resonance (D) 2 O) and electrospray mass spectrometry, and identifying the target compound.
The obtained product is dissolved in 100mL of deionized water, and ion exchange is carried out through 717 strongly basic anion exchange resin, so that the template agent aqueous alkali in the form of hydroxide radical can be obtained through exchange. The appropriate amount of this solution was weighed and calibrated with 0.1mol/L hydrochloric acid solution, phenolphthalein was used as the indicator. The calibration results confirmed that the exchange efficiency of the template 1 chloride salt to hydroxide base reached 94%.
The templating agents 2-4 in Table 1 were prepared according to the methods described above.
Example 2: according to the molar ratio of 1SiO 2 ：0.2GeO 2 :0.5ROH：0.5HF：3H 2 O ratio preparing the gel synthesized by the molecular sieve, and the steps are as follows: weighing metered aqueous alkali of the template agent 1, respectively adding 0.2mmol (0.0209 g) of germanium dioxide and 1mmol (0.2084 g) of ethyl orthosilicate, stirring for about two hours at normal temperature to completely dissolve the germanium dioxide and the ethyl orthosilicate, then adding a designed amount of hydrofluoric acid solution, uniformly stirring, placing the mixed gel under an infrared lamp or in an oven at 80 ℃, and removing the redundant solvent to the theoretical weight. And transferring the finally obtained reaction gel into a 15mL stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 15 days at 160 ℃ under a sealed condition, washing the product twice by water and twice by ethanol, and drying for later use. The single crystal X-ray diffraction test is carried out at the temperature of minus 180 ℃, and the result shows that the crystal is crystallized in space group P6/mmm,
the molecular sieve is structurally isomorphic with ITQ-44, has 18-membered ring channels in the c direction of the crystal axis and 12-membered channels in the a and b directions, and is the silicon germanate molecular sieve ITQ-44 with IRR structure. Theoretical analysis of powder diffraction of molecular sieve based on single crystal X-ray resultsAnd fitting, wherein the result is consistent with the result of the actual powder X-ray diffraction analysis. The above-described silicon germanate molecular sieves can be used as seeds for the synthesis of silicate molecular sieves.
Example 3: according to the molar ratio of 1SiO 2 ：0.75ROH：0.03Seed：0.75HF：3H 2 O ratio preparing the gel synthesized by the molecular sieve, and the steps are as follows: weighing a metered alkali solution of the template agent 1, adding 1mmol (0.2084 g) of tetraethoxysilane, stirring for about two hours at normal temperature to completely dissolve the tetraethoxysilane, then adding a designed amount of hydrofluoric acid solution, uniformly stirring, finally adding 0.03mmol (0.0120 g) of the product of example 2 serving as a seed crystal, placing the mixed gel under an infrared lamp or in an oven at 80 ℃, and removing the redundant solvent to the theoretical weight. And transferring the finally obtained reaction gel into a 15mL stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 15 days at 160 ℃ under a sealed condition, washing the product twice with water and ethanol, and drying for later use. The X-ray powder diffractogram phase identified it as a silicate molecular sieve (named NUD-16) with IRR structure, which was calcined at 550 ℃ for 4 hours in air atmosphere to remove the template molecules, and the structure remained stable, as shown in FIG. 1. Scanning electron microscopy showed that the product was spherical (see FIG. 2).
Example 4: according to the molar ratio of 1SiO 2 ：0.5ROH：0.01Al 2 O 3 ：0.03Seed：0.5NH 4 F：3H 2 O ratio molecular sieve synthesized gel was prepared as follows: weighing a metered alkali solution of the template agent 1, firstly adding 0.01mmol (0.0021 g) of aluminum isopropoxide into the alkali solution, stirring for about half a hour, later adding 1mmol (0.2084 g) of tetraethoxysilane, stirring for about two hours at normal temperature to completely dissolve the tetraethoxysilane, then adding a designed amount of ammonium fluoride solution, uniformly stirring, finally adding 0.03mmol (0.0120 g) of the product of example 3 serving as a seed crystal, placing the mixed gel under an infrared lamp or in an oven at 80 ℃, and removing the redundant solvent to the theoretical weight. And transferring the finally obtained reaction gel into a 15mL stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 20 days at 160 ℃ under a sealed condition, washing the product twice with water and twice with ethanol, and identifying the product as an aluminosilicate molecular sieve Al-NUD-16 with an IRR structure by an X-ray powder diffraction phase. As described aboveThe molecular sieve is calcined for 2 hours at 550 ℃ in the air atmosphere to remove the template agent molecules, and the structure of the molecular sieve is kept stable. The X-ray powder diffraction results of the molecular sieve are shown in fig. 1.
Example 5: according to the molar ratio of 1SiO 2 ：0.75ROH：0.01TiO 2 ：0.05Seed：0.75HF：3H 2 O ratio preparing the gel synthesized by the molecular sieve, and the steps are as follows: weighing a metered aqueous alkali solution of the template agent 2, firstly adding 0.01mmol (0.0035 g) of tetrabutyl titanate into the aqueous alkali solution, stirring for about half a hour, later adding 1mmol (0.2084 g) of tetraethoxysilane, stirring for about two hours at normal temperature to completely dissolve the tetraethoxysilane, then adding a designed amount of hydrofluoric acid solution, uniformly stirring, finally adding 0.05mmol (0.0200 g) of the product of example 3 serving as a seed crystal, placing the mixed gel under an infrared lamp or in an oven at 80 ℃, and removing the redundant solvent to the theoretical weight. And transferring the finally obtained reaction gel into a 15mL stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 15 days at 170 ℃ under a sealed condition, washing the product twice with water and ethanol, and identifying the product as a titanosilicate molecular sieve Ti-NUD-16 with an IRR structure by an X-ray powder diffraction phase. The molecular sieve is calcined for 2 hours at 550 ℃ in the air atmosphere to remove the template agent molecules, and the structure of the molecular sieve is kept stable. The X-ray powder diffraction results for the molecular sieve are substantially in accordance with figure 1.
Example 6: molecular sieve synthesis gel was prepared and synthesized according to the material ratios and procedure of example 3, except that the template used was an alkali solution of para-substituted methylbenzylimidazole cation. The resulting product was identified as amorphous by X-ray powder diffraction (as shown in figure 1).
Claims (9)
1. The super-macroporous silicate molecular sieve with IRR structure is characterized by having IRR framework crystal structure and having chemical composition form ofp(M 1/n XO 2 )·qYO 2 ·SiO 2 Wherein M represents a proton or an inorganic cation of + n valency; x represents one or more trivalent elements; y represents one or more tetravalent elements other than silicon and germanium;p = 0–0.03，q=0-0.03, the ultra-large pore IRR structure silicate molecular sieve adopts the following componentsThe preparation method comprises the following steps:
(1) Uniformly mixing a silicon source substance, a boron family element compound, a tetravalent element compound except silicon and germanium, an organic template agent, a fluorine source substance, an IRR Seed crystal Seed and water in proportion under stirring to obtain a reaction gel, wherein the reaction gel comprises the following chemical components:rROH:aHF:xX 2 O 3 : yYO 2 :SiO 2 :b Seed: wH 2 o, wherein R represents a positively charged group of the organic templating agent; x represents one or more trivalent boron group elements; y represents one or more tetravalent elements other than silicon and germanium,r=0.1-1，a=0-1，b=0.001-0.05，x=0-0.03，y=0-0.03，w1-50; r is Ar- (im) + An organic cation wherein Ar represents para-or meta-substituted tert-butylbenzyl, im represents N-substituted imidazole;
(2) Removing excessive solvent from the reaction gel, transferring the reaction gel into a stainless steel reaction kettle, and reacting for 7-30 days at 140-170 ℃ under a sealed condition;
(3) And (3) washing and drying the product crystallized in the step (2), and roasting for 2-5 hours at 400-650 ℃ in the air atmosphere to obtain the super-macroporous silicate molecular sieve without the template agent.
2. Molecular sieve according to claim 1, characterized in that M represents a proton or sodium, X is Al or B, Y is Ti,p =0-0.02；q =0-0.02。
3. the method for preparing the ultra-large pore IRR structure silicate molecular sieve according to claim 1 or 2, characterized by comprising the following steps:
(1) Uniformly mixing a silicon source substance, a boron family element compound, a tetravalent element compound except silicon and germanium, an organic template agent, a fluorine source substance, an IRR Seed crystal Seed and water in proportion under stirring to obtain a reaction gel, wherein the reaction gel comprises the following chemical components:rROH:aHF:xX 2 O 3 : yYO 2 :SiO 2 :b Seed: wH 2 o, wherein R represents the positive charge of the organic templating agentA group; x represents one or more trivalent boron group elements; y represents one or more tetravalent elements other than silicon and germanium,r=0.1-1，a=0-1，b=0.001-0.05，x=0-0.03，y=0-0.03，w1-50; r is Ar- (im) + An organic cation wherein Ar represents para-or meta-substituted tert-butylbenzyl, im represents N-substituted imidazole;
(2) Removing excessive solvent from the reaction gel, transferring the reaction gel into a stainless steel reaction kettle, and reacting for 7-30 days at 140-170 ℃ under a sealed condition;
(3) And (3) washing and drying the product crystallized in the step (2), and roasting for 2-5 hours at 400-650 ℃ in the air atmosphere to obtain the super-macroporous silicate molecular sieve without the template agent.
4. The method according to claim 3, wherein step (1) X is Al and/or B.
5. The preparation method according to claim 3, wherein the silicon source substance is selected from one or more of white carbon black, water glass, silica sol, ethyl orthosilicate and butyl orthosilicate; the boron group element compound is selected from one or more of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate, aluminum hydroxide or boric acid; the fluorine source substance is hydrofluoric acid and/or ammonium fluoride; the tetravalent element compound except silicon and germanium is tetrabutyl titanate and/or tin dioxide.
6. The production method according to claim 3 or 4, characterized in that step (1)r、a、x、yAndwrespectively as follows:r=0.5-0.75，a=0.5-0.75，b=0.01-0.05，x=0-0.02，y=0-0.02，w=1-10。
7. the method according to claim 3, wherein R is selected from one or more of the following structures:
8. the method of claim 3, wherein the IRR Seed is an IRR structure molecular sieve selected from the group consisting of a silicon germanosilicate, a pure silicate, an aluminosilicate, and a titanosilicate.
9. The use of the extra-large pore IRR structure silicate molecular sieve of claim 1 or 2 as an adsorption material, a separation material, a catalyst in the chemical and chemical field.
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