CN112520756A - Method for preparing SAPO-17 molecular sieve - Google Patents
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Abstract
The invention discloses a method for preparing an SAPO-17 molecular sieve. The method comprises the following steps: 1) mixing a molecular sieve seed crystal with an ERI structure, an organic template agent R and a long-chain quaternary ammonium salt cationic compound, and then carrying out heat treatment to obtain a precursor A; 2) mixing an aluminum source, a phosphorus source and a solvent S, and carrying out heat treatment to obtain a mixed material B; 3) mixing the precursor A, a silicon source and a mixed material B to form a crystallized mixture; 4) pretreating the crystallized mixture obtained in the step 3), and then carrying out crystallization reaction to obtain the SAPO-17 molecular sieve. The method can quickly synthesize the SAPO-17 molecular sieve and can be carried out at a lower temperature. The SAPO-17 molecular sieve synthesized by the method can be used for industrial production of downstream products of methanol, industrial production of downstream products of synthesis gas and hydrocarbon cracking, and shows excellent performance.
Description
Technical Field
The invention relates to a preparation method of a molecular sieve, in particular to a preparation method of an SAPO-17 molecular sieve.
Background
Due to the wide distribution range of the sizes of the inner cavities and the rich diversity of topological structures, the zeolite molecular sieve material is widely applied to the fields of adsorption, heterogeneous catalysis, carriers of various guest molecules, ion exchange and the like. They are mainly characterized by selective adsorption and their unique system of channels gives them the ability to screen molecules of different sizes, which is why these materials are called "molecular sieves". Early zeolites were aluminosilicates which were made of SiO4Tetrahedron and AlO4Tetrahedron is a basic structural unit and is connected by bridge oxygen to form a microporous compound with a cage-shaped or pore canal structure. In the last 40 th century, Barrer and others synthesized artificial zeolite which did not exist in nature for the first time in the laboratory, and in nearly ten years thereafter, Milton, Breck and Sand and others synthesized A-type, X-type, L-type and Y-type zeolites, mordenite and the like by adding alkali metal or alkaline earth metal hydroxide to aluminosilicate gel by hydrothermal technology; in the sixties of the twentieth century, along with the introduction of organic base cations, a series of zeolite molecular sieves with brand new structures, such as ZSM-n series (ZSM-1, ZSM-5, ZSM-11, ZSM-22 and ZSM-48), were preparedEtc.) zeolite molecular sieves, which have the advantages of better catalytic activity, hydrothermal stability, higher corrosion resistance and the like, are widely applied to the fields of petroleum processing, fine chemical engineering and the like, and have been the hot points of research of people for many years.
In 1982, Wilson S.T. and Flarigen E.M. of scientists of United states of America Union carbide (UCC) and others successfully synthesized and developed a brand-new molecular sieve family, aluminum phosphate molecular sieve AlPO, using aluminum source, phosphorus source and organic template4N, n represents the model number (US 4310440). Two years later, UCC in AlPO4Based on-n, Si atoms are used for partially replacing Al atoms and P atoms in an AlPO framework, and another series of silicoaluminophosphate molecular sieves SAPO-n are successfully prepared, wherein n represents the type (US4440871, US 4499327). In the structure of SAPO-n, Si atom replaces P or Al atom in original AlPO to form SiO4、AlO4And PO4A non-neutral molecular sieve framework of tetrahedral composition, in which silicon is present in two ways: (1) one Si atom replacing one P atom; (2)2 silicon atoms respectively replace a pair of aluminum atoms and phosphorus atoms, and show certain acidity, oxidability and the like, thereby greatly improving the catalytic activity of the catalyst and having wide application prospect in the field of petrochemical industry. The SAPO-17 molecular sieve is a molecular sieve with a topological structure of an ERI type erionite-like structure, and is also an SAPO-n small-pore molecular sieve synthesized by UCC company in 1984, and the molecular sieve has eight-membered ring three-dimensional pore passages the same as those of SAPO-34.
Molecular sieves with known topological results are prepared by hydrothermal or solvothermal synthesis. A typical hydrothermal or solvothermal synthesis method comprises the main steps of uniformly mixing reactants such as a metal source, a nonmetal source, an organic template agent and a solvent to obtain an initial sol, namely a crystallized mixture, then placing the crystallized mixture into a reaction kettle with a polytetrafluoroethylene lining and a stainless steel outer wall, sealing the reaction kettle, and then carrying out crystallization reaction at a certain temperature under a certain autogenous pressure, like the process of earth rock-making, namely the process of precipitating molecular sieve crystals from the crystallized mixture. Specifically, for example, in the synthesis of the silicoaluminophosphate ERI (SAPO-17) molecular sieve, the reaction mixture comprises a framework reactant (such as silica sol, phosphoric acid and alumina), a Structure Directing Agent (SDA) and water, the mixture is uniformly mixed, the mixture is statically placed or dynamically placed in an oven (190 ℃ C. -.
In the synthesis of SAPO-17 molecular sieves, small cyclic amine species are generally used as a template, and then, for example, quinuclidine (Intrazeolite Chemistry,1983, Vol218, P79, piperidine (Acta crystalline graphica Section C Crystal Structure Communications,1986, Vol42, P283) and cyclohexylamine (Solid State Magnetic Resonance,1992, Vol1, P137) are successively applied to the synthesis system of SAPO-17. furthermore, Liu et al (ChemSum, 2011, Vol4, P91) synthesize acicular AlPO-17 crystals with neopentyl amine as a Structure directing agent. TuPO-17 et al (computers RendChimi, 2005, Vol8, P531) synthesize single Crystal crystals with N, N, N ', N' -tetramethyl-1, 6-hexanediamine as a template, and AlPO-17. FIG. 5. the synthesis system of Mono-17. AlPO-17 crystals with a template of N, N, N ', N' -tetramethyl-1, 6-hexanediamine as a template, and the AlPO-17. Alpo-17. III, a synthesis system without a disc shaped Crystal template, PO-17. Alpo-2. with a template, Alpo-2. a disc-shaped Crystal synthesis system, a disc-shaped Crystal synthesis, a method for synthesizing SAPO-17 by using 6-hexamethylenediamine and derivatives thereof as organic templates; CN103922361A discloses a preparation method of SAPO-17 molecular sieve, which adopts T-type zeolite or SSZ-13 zeolite or Y-type zeolite or A-type zeolite or MOR-type zeolite crystalline silicon as a silicon source to prepare the SAPO-17 molecular sieve in a high-temperature hydrothermal system, wherein the crystallization temperature is 160-210 ℃, and the crystallization time basically needs more than 12 h.
In addition, ERI (SAPO-17) molecular sieves have been used by researchers as MTO (methanol to olefin) catalysts due to their micro-topology and the moderate Bronsted acid center (Catalysis,1992, Vol9, p 1). US4499327 discloses the use of water as a diluent, with a weight hourly space velocity of not more than 1h-1Under the conditions of (1), the SAPO-17 molecular sieve has a higher ratio of ethylene to propylene than SAPO-34 and SAPO-56 under the same conversion conditions. The literature [ novel materials for chemical industry, 2015,43,166 ] and the literature [ Studies in Surface Science and Catalysis,1994,81,393 ] also use SAPO-17 as an olefin for methanolCatalyst for reaction in the presence of a large amount of diluent and at a low space velocity (less than 1 h)-1) Higher ethylene to propylene ratios are also obtained under the conditions of (1).
The existing method for preparing the SAPO-17 molecular sieve generally needs to crystallize for more than tens of hours or even more than several days at the temperature of about 150-240 ℃ to prepare the SAPO-17 molecular sieve, and the preparation time is long.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel method for preparing the SAPO-17 molecular sieve, the method can quickly synthesize the SAPO-17 molecular sieve and can be carried out at a lower temperature, and the SAPO-17 molecular sieve synthesized by the method can be used for industrial production of downstream products of methanol, industrial production of downstream products of synthesis gas and hydrocarbon cracking, and shows excellent performance.
The invention provides a method for preparing an SAPO-17 molecular sieve, which comprises the following steps:
1) mixing a molecular sieve seed crystal with an ERI structure, an organic template agent R and a long-chain quaternary ammonium salt cationic compound, and then carrying out heat treatment to obtain a precursor A;
2) mixing an aluminum source, a phosphorus source and a solvent S, and carrying out heat treatment to obtain a mixed material B;
3) mixing the precursor A, a silicon source and a mixed material B to form a crystallized mixture;
4) pretreating the crystallized mixture obtained in the step 3), and then carrying out crystallization reaction to obtain the SAPO-17 molecular sieve.
In the step 1), the molecular sieve seed crystal with the ERI structure is at least one of T-type molecular sieve seed crystal or AlPO-17 molecular sieve seed crystal.
In the step 1), the organic template R is at least one of 1, 10-phenanthroline, 2-bipyridine, 4-bipyridine, piperazine, cyclohexylamine, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine and ethylamine; preferably at least one of piperazine, cyclohexylamine, triethylamine, n-butylamine, ethylenediamine and ethylamine.
In the step 1), the long-chain quaternary ammonium salt cationic compound comprises a long-chain quaternary ammonium salt cationic compound I and a long-chain quaternary ammonium salt cationic compound II; wherein the long-chain quaternary ammonium salt cationic compound I is at least one selected from tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide and tetrabutylammonium hydroxide; the long-chain quaternary ammonium salt cationic compound II is at least one selected from 4- (benzoyl) benzyl-N-dodecyl-N, N-dimethyl ammonium bromide (BDDB for short), 2- (methacrylic acid) ester propyl (4-benzoyl benzyl) dimethyl ammonium bromide (MDAB for short), benzoyl benzyl dimethyl octadecyl ammonium bromide (BDOB for short) and N, N-dimethyl-N-vinyl benzyl octadecyl quaternary ammonium salt (OVBAC for short).
The long-chain quaternary ammonium salt cationic compound I is preferably at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium hydroxide; the long-chain quaternary ammonium salt cationic compound II is preferably at least one of 4- (benzoyl) benzyl-N-dodecyl-N, N-dimethyl ammonium bromide (BDDB for short) and N, N-dimethyl-N-vinylbenzyl octadecyl quaternary ammonium salt (OVBAC for short).
In the step 1), the mass ratio of the added molecular sieve seed crystal with the ERI structure, the organic template agent R and the long-chain quaternary ammonium salt cationic compound is as follows: 0.001-0.1: 1-100: 1 to 100. The mass ratio of the long-chain quaternary ammonium salt cationic compound I to the long-chain quaternary ammonium salt cationic compound II in the long-chain quaternary ammonium salt cationic compound is 1-100: 1.
in the step 1), the temperature of the heat treatment is 40-80 ℃, and the time is 0.5-2 h.
In the step 2), the aluminum source is at least one of aluminum salt, aluminate, meta-aluminate, aluminum hydroxide, aluminum oxide and aluminum-containing minerals; preferably at least one of an aluminum salt (e.g., aluminum sulfate, aluminum nitrate, aluminum isopropoxide), an aluminate and a meta-aluminate.
In the step 2), the phosphorus source is at least one of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate; phosphoric acid is preferred.
In the step 2), the solvent S is at least one of N, N-dimethylformamide, N-dimethylacetamide, ethanol, glycol and water; preferably at least one of N, N-dimethylformamide, ethanol and water (such as deionized water).
In the step 2), the temperature of the heat treatment is 40-80 ℃, and the time is 0.5-2 h.
In the step 3), the silicon source is at least one of organic silicon, amorphous silica, silica sol, solid silica, silica gel, diatomite and water glass; preferably at least one of amorphous silica, silica sol and white carbon.
The molar ratio of the aluminum source, the silicon source, the phosphorus source, the template agent R and the solvent S added in the steps 1) to 3) is as follows: Si/Al is 0.01-0.3, P/Al is 0.75-1.5, R/Al is 1-500, S/Al is 10-1000, wherein the aluminum source, the silicon source and the phosphorus source are calculated by atom.
In the step 4), the pretreatment conditions are as follows: stirring for 0.5-2 h at 80-120 ℃.
In the step 4), the crystallization reaction conditions are as follows: crystallizing at 130-220 deg.C for 10-110 min.
In the step 4), after the crystallization reaction is finished, conventional post-treatment can be carried out, such as filtration, washing, drying and roasting, so as to obtain the SAPO-17 molecular sieve. The drying conditions are as follows: the temperature is 80-120 ℃, the time is 4-12 h, and the roasting conditions are as follows: the temperature is 400-600 ℃, and the time is 4-8 h.
The invention also provides an application of the SAPO-17 molecular sieve prepared by the method as a catalyst.
The SAPO-17 molecular sieve prepared by the invention can be applied to the reaction of preparing hydrocarbon from methanol, the reaction of preparing olefin from synthesis gas and the reaction of cracking hydrocarbon.
Wherein, the reaction conditions for preparing the hydrocarbon from the methanol are as follows: methanol is used as a raw material, the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-10 MPa, and the weight space velocity of the methanol is 0.1-15 h-1。
The reaction conditions for preparing olefin from synthesis gas are as follows: using synthetic gas as raw material H20.5-1/CO: 1, the reaction temperature is 200-400 ℃, the reaction pressure is 0.1-10 MPa, and the weight space velocity of the synthesis gas is 20-2000 h-1。
The hydrocarbon cracking reaction conditions are as follows: the reaction temperature is 500-650 ℃, and the weight ratio of the diluent to the raw materials is 0-1: 1, the liquid phase space velocity is 1-30 h-1The reaction pressure is-0.05 to 0.2MPa, and the hydrocarbon preferably contains at least one olefin, and more preferably contains at least one C4And the above olefins.
When the SAPO-17 molecular sieve prepared by the invention is applied to the reaction of preparing hydrocarbons from methanol, the conversion rate of the methanol is 100 percent, the one-way selectivity of ethylene and propylene can reach 81.8 percent at most, the selectivity ratio (ethylene/propylene) is adjustable within the range of 2.0-2.5, and the catalyst has good stability; the SAPO-17 molecular sieve prepared by the invention is applied to the reaction process of preparing olefin from synthesis gas, and the highest CO conversion rate can reach 39.9 percent and C can reach C within the set evaluation condition range2-C4The selectivity of olefin can reach 85.3 percent at most, and the selectivity ratio (ethylene/propylene) is adjustable within the range of 2.0-2.5; the SAPO-17 molecular sieve prepared by the invention is applied to hydrocarbon cracking reaction, and within the set evaluation condition range, the one-way selectivity of ethylene and propylene in a cracking product can reach 64.99 percent at most.
Compared with the prior art, the invention has the following advantages:
the method for preparing the SAPO-17 molecular sieve comprises the steps of mixing a molecular sieve seed crystal with an ERI structure, an organic template agent R and a long-chain quaternary ammonium salt cationic compound to prepare a precursor A, simultaneously mixing an aluminum source, a phosphorus source and a solvent S to prepare a mixed material B, then mixing the precursor A and the silicon source with the mixed material B to prepare a crystallized mixture, and carrying out reaction after pretreatment to obtain the SAPO-17 molecular sieve. Particularly, the invention adopts a specific long-chain quaternary ammonium salt cationic compound, thereby obviously improving the synthesis speed of the SAPO-17 molecular sieve.
Drawings
FIG. 1 is an XRD pattern of the SAPO-17 molecular sieve of example 1;
FIG. 2 is an SEM photograph of the SAPO-17 molecular sieve of example 1;
FIG. 3 is an XRD pattern of a SAPO-17 molecular sieve of comparative example 1;
FIG. 4 is an SEM photograph of the SAPO-17 molecular sieve of comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, but it should be understood that the scope of the present invention is not limited by the examples. In the present invention, percentages and percentages are by mass unless otherwise specifically indicated.
In the invention, the crystal phase of the product is measured by an X' Pert PRO type X-ray powder diffraction (XRD) instrument of Pynaud Pynaudiaceae, the working voltage is 40kV, the current is 40mA, and the scanning range is 5-50 degrees. The morphology of the product was photographed by a field emission scanning electron microscope (Fe-SEM) of model S-4800 of HITACHI, Japan.
[ example 1 ]
Synthesis of SAPO-17 molecular sieve
14765.35g of tetraethylammonium hydroxide (TEAOH, 25 wt.% in water, 25.06 mol.) were added at room temperature]1134.45g of benzyl-N-dodecyl-N, N-dimethylammonium bromide (BDDB for short), 32.89g of AlPO-17 molecular sieve seeds and 16172.64g of cyclohexylamine [ HCHA, 163.08 mol%]Fully stirring, and then placing at 80 ℃ for heat treatment for 0.5h to obtain a precursor A1. 60421.77g of aluminum nitrate [ Al (NO) were weighed3)3·9H2O，161.07mol]Dissolved in 201155.42mL of deionized water, after which 18357.13g of phosphoric acid [ H ] was added3PO485 wt.% aqueous solution, 159.22mol]Fully stirring to form a solution S1And heat-treated at 80 ℃ for 0.5h to obtain a mixed material B1. The precursor A is added1And 734.57g of acidic silica sol SiO 240 wt.% aqueous solution, 4.90mol]Adding the mixture B at 80 deg.C under sealed stirring1Continuously stirring for 0.5h, and then continuously stirring for 0.5h at 120 ℃; and then placing at 140 ℃ for crystallization for 90min, filtering and washing the product, drying at 120 ℃ for 4h, then heating to 500 ℃, and roasting at constant temperature for 6.5h to obtain the SAPO-17 molecular sieve which is marked as LSSP-1, wherein XRD (X-ray diffraction) patterns and SEM (scanning Electron microscope) photographs of the product are shown in figures 1 and 2.
[ example 2 ]
Synthesis of SAPO-17 molecular sieve
821.57g of tetrapropylammonium hydroxide TPAOH, 25 wt.% aqueous solution, 1.01mol were added at room temperature]10.03g of N, N-dimethyl-N-vinylbenzyloctadecyl quaternary ammonium salt (abbreviated as OVBAC), 1.33g of T-type molecular sieve seed crystal and 86.16g of piperazine [ PIP, 1.01 mol%]Fully stirring, and then placing at 40 ℃ for heat treatment for 2h to obtain a precursor A2. 39.98g of aluminum sulfate [ Al ] was weighed2(SO4)3·18H2O，0.06mol]Dissolved in 46.45mL of deionized water, 6.63g of phosphoric acid [ H ] was added3PO485 wt.% aqueous solution, 0.05mol]Fully stirring to form a solution S2And heat-treating at 40 deg.C for 2 hr to obtain mixed material B2. The precursor A is added2And 0.36g of white carbon black SiO2，0.006mol]Adding the mixed material B at 40 ℃ under the stirring state2Continuously stirring for 1.1h, and then placing at 80 ℃ for closed stirring for 2 h; and then crystallizing at 130 ℃ for 100min, filtering and washing the product, drying at 80 ℃ for 12h, then heating to 600 ℃, and roasting at constant temperature for 4h to obtain a product, which is marked as LSSP-2. The XRD pattern and SEM photograph of the product were similar to those of example 1.
[ example 3 ]
Synthesis of SAPO-17 molecular sieve
1211.56g of tetrapropylammonium bromide [ TPABr, 3.76mol ] were added at room temperature]110.22g of BDDB, 2.13g of AlPO-17 molecular sieve seeds and 816.35g of cyclohexylamine [ HCHA, 99 wt.%, 123.08mol ]]689.76g of piperazine [ PIP, 1.01mol]Fully stirring, and then placing at 60 ℃ for heat treatment for 1h to obtain a precursor A3. 613.69g of aluminum nitrate [ Al (NO) were weighed3)3·9H2O，1.63mol]Dissolved in 5324.67mL of deionized water, after which 226.62g of phosphoric acid [ H ] was added3PO485 wt.% aqueous solution, 1.96mol]Fully stirring to form a solution S3And heat-treating at 60 deg.C for 1 hr to obtain mixed material B3. The precursor A is added3And 12.25g of acidic silica sol [ SiO ]240 wt.% aqueous solution, 0.08mol]Adding the mixed material B at 60 ℃ under the stirring state3Continuously stirring for 1h, and then placing at 100 ℃ for closed stirring for 1 h; then placing at 220 ℃ for crystallizationAnd (3) filtering and washing the product for 10min, drying the product at 80 ℃ for 9h, then heating to 400 ℃, and roasting at constant temperature for 8h to obtain a product, which is marked as LSSP-3. The XRD pattern and SEM photograph of the product were similar to those of example 1.
[ example 4 ]
Synthesis of SAPO-17 molecular sieve
71698.78g of tetraethylammonium hydroxide (TEAOH, 50 wt.% in water, 247.38 mol) were added at room temperature]18945.22g of OVBAC, 120.15g of T-type molecular sieve crystals and 18575.59g of piperazine [ PIP, 215.62mol]Fully stirring, and then placing at 50 ℃ for heat treatment for 1.5h to obtain a precursor A4. 10847.09g of sodium metaaluminate [ NaAlO ] were weighed2，132.33mol]Dissolved in 205656.18mL of deionized water, after which 12965.4g of phosphoric acid [ H ] was added3PO485 wt.% aqueous solution, 112.46mol]Fully stirring to form a solution S4And heat-treating at 70 deg.C for 0.8 hr to obtain mixed material B4. The precursor A is added4And 119.7g of white carbon black SiO2，1.99mol]Mixing the material B at 40 ℃ under stirring4Stirring for 2h, and then placing at 90 ℃ to stir for 1.5h in a sealed manner; and crystallizing at 195 deg.C for 30min, filtering, washing, drying at 80 deg.C for 8 hr, heating to 550 deg.C, and calcining at constant temperature for 6 hr to obtain LSSP-4. The XRD pattern and SEM photograph of the product were similar to those of example 1.
[ example 5 ]
Synthesis of SAPO-17 molecular sieve
138.22g of tetrapropylammonium bromide [ TPABr, 0.43mol ] were added at room temperature]61.35g BDDB, 1.45g AlPO-17 molecular sieve seed and 38.94g cyclohexylamine [ HCHA, 0.39mol]Fully stirring the mixture, and then performing heat treatment at 70 ℃ for 0.8h to obtain a precursor A5. 202.57g of aluminum nitrate [ Al (NO) were weighed3)3·9H2O，0.54mol]Dissolved in 321.77mL of deionized water, after which 99.83g of phosphoric acid [ (H) was added3PO485 wt.% aqueous solution, 0.76mol]Fully stirring to form a solution S5And heat-treating at 70 deg.C for 0.8 hr to obtain mixed material B5. The precursor A is added5And 2.93g of white carbon black SiO2，0.05mol]Adding the mixed material B at 70 ℃ under the stirring state5Stirring the mixtureAfter 0.8h, the mixture is placed at 80 ℃ and stirred for 2h in a sealed way; and then crystallizing at 205 ℃ for 20min, filtering and washing the product, drying at 110 ℃ for 5h, then heating to 450 ℃, and roasting at constant temperature for 7h to obtain the product, which is marked as LSSP-5. The XRD pattern and SEM photograph of the product were similar to those of example 1.
[ examples 6 to 10 ] to provide a toner
SAPO-17 molecular sieves were synthesized according to the method of example 5, using the raw materials shown in Table 1, while controlling the different ratios and conditions of the reaction materials (Table 2).
TABLE 1
TABLE 2
Comparative example 1
According to the synthesis method of the SAPO-17 molecular sieve described in the literature (Chinese patent CN 103922361A), aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, silica sol is used as a silicon source, cyclohexylamine is used as a template agent, 81g of aluminum isopropoxide is added into 48.9g of ultrapure water, after uniform stirring, 45.7g of phosphoric acid (85 wt.%) is added, after stirring for 1h, 11.5mL of cyclohexylamine is added into a mixed solution, after stirring and aging for 2h, 30 wt.% of SiO is added into the system2After aging for several hours, the sol is put into a stainless steel reaction kettle containing polytetrafluoroethylene lining and crystallized for 120 hours at 200 ℃ to obtain a short and thick rod-shaped SAPO-17 molecular sieve, and the XRD (X-ray diffraction) spectrum and SEM (scanning Electron microscope) photos of the product are shown in figures 3 and 4.
Comparative example 2
According to the synthesis method of SAPO-17 molecular sieve described in the literature (Tianjin chemical industry, 2016, 30(3):17-19.), aluminum isopropoxide is used as aluminum source, phosphoric acid is used as phosphorus source, silica sol is used as silicon source, cyclohexylamine is used as template agent, and the reaction ratio is 1Al2O3∶1P2O5∶0.3SiO2∶1CHA∶1HF∶40H2O, fixed aluminumAccording to the scheme, 3.06g of aluminum isopropoxide is added into 5.4g of deionized water, 1.7g of phosphoric acid (85 wt.%) is added after uniform stirring, 0.7g of cyclohexylamine is added into the mixed solution after continuous stirring for 1.5h, 2.25g of silica sol (40 wt.%) is added into the reaction system after stirring and aging for 1.5h, the sol is placed into a stainless steel reaction kettle containing a polytetrafluoroethylene lining and crystallized for 72h at 200 ℃ to obtain the SAPO-17 molecular sieve after continuous stirring for several hours.
[ example 11 ]
Application of SAPO-17 molecular sieve in methanol-to-hydrocarbon reaction
And (3) roasting the LSSP-9 molecular sieve synthesized in the example 9 at 550 ℃ for 4 hours, cooling to room temperature, tabletting, breaking, and screening, and taking 12-20-mesh particles for later use. Methanol is used as raw material, a fixed bed reactor with the diameter of 15 mm is used, the mass space velocity is 0.1h at the temperature of 400 DEG C-1When the pressure is evaluated under the condition of 0.01MPa, the yield of ethylene and propylene reaches 68.9 percent, and the selectivity ratio (ethylene/propylene) is 2.07, thereby obtaining better technical effects.
[ example 12 ]
Application of SAPO-17 molecular sieve in methanol-to-hydrocarbon reaction.
The LSSP-2 molecular sieve synthesized in the example 2 is taken, the catalyst is prepared by the catalyst preparation method of the example 11, methanol is used as a raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 2.2h at 449 DEG C-1When evaluated under the condition of the pressure of 1.44MPa, the yield of ethylene and propylene reaches 74.5 percent, and the selectivity ratio (ethylene/propylene) is 2.16, thereby obtaining better technical effects.
[ example 13 ]
Application of SAPO-17 molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The LSSP-3 molecular sieve synthesized in the example 3 is taken, the catalyst is prepared by the catalyst preparation method of the example 11, methanol is used as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 7.2h at 476 ℃-1When the pressure was evaluated under 2.7MPa, the yields of ethylene and propylene reached 81.8%, and the selectivity ratio (ethylene/propylene) was 2.49, a good technique was obtainedAnd (5) effect.
[ example 14 ]
Application of SAPO-17 molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The LSSP-6 molecular sieve synthesized in the example 6 is taken, the catalyst is prepared by the catalyst preparation method of the example 11, methanol is used as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 15h at 550 DEG C-1When evaluated under the condition of 10MPa, the yield of ethylene and propylene reaches 72.8 percent, and the selectivity ratio (ethylene/propylene) is 2.13, thereby obtaining better technical effect.
[ example 15 ]
Application of SAPO-17 molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The LSSP-5 molecular sieve synthesized in the example 5 is taken, the catalyst is prepared by the catalyst preparation method of the example 11, methanol is used as raw material, a fixed bed reactor with the diameter of 15 mm is used, and the mass space velocity is 4.6h at the temperature of 600 DEG C-1When evaluated under a pressure of 1.1MPa, the yields of ethylene and propylene reached 77.6%, and the selectivity ratio (ethylene/propylene) was 2.35, which resulted in a good technical effect.
Comparative example 3
The SAPO-17 molecular sieve synthesized in comparative example 2 was selected, and the catalyst prepared by the catalyst preparation method of example 11 was evaluated in the manner of example 15, and the yields of ethylene and propylene reached 52.1%, the selectivity ratio (ethylene/propylene) was 1.19,
[ example 16 ]
Application of SAPO-17 molecular sieve in the reaction of preparing hydrocarbon from synthesis gas.
The LSSP-10 molecular sieve synthesized in the embodiment 10 is taken, roasted for 6 hours at the temperature of 550 ℃, then tabletted, broken and sieved, particles of 20-40 meshes are taken, and the catalyst filler mass ratio is ZnCrOx/LSSP＝1.0(ZnCrOxRepresenting a mixture of zinc oxide and chromium oxide to make an oxide-molecular sieve catalyst ready for use). The synthesis gas is used as a raw material, a fixed bed reactor with the diameter of 15 mm is used, and the process conditions are as follows: the reaction temperature is 353 ℃, the pressure is 1.15MPa, and the space velocity is 499h-1Composition of syngas H2/CO＝0.75：1，COHas a conversion of 39.9%, wherein C2＝-C4＝The selectivity was 62.6% and the selectivity ratio (ethylene/propylene) was 2.02.
[ example 17 ]
Application of SAPO-17 molecular sieve in the reaction of preparing hydrocarbon from synthesis gas.
A catalyst was prepared by the catalyst preparation method of example 16 using the LSSP-7 molecular sieve synthesized in example 7. The process conditions are as follows: the reaction temperature is 200 ℃, the pressure is 0.10MPa, the space velocity is 399h-1Composition of syngas H21/CO: 1, conversion of CO 33.5%, where C2＝-C4＝The selectivity was 67.8%, and the selectivity ratio (ethylene/propylene) was 2.14.
[ example 18 ]
Application of SAPO-17 molecular sieve in the reaction of preparing hydrocarbon from synthesis gas.
A catalyst was prepared by the catalyst preparation method of example 16 using the LSSP-8 molecular sieve synthesized in example 8. The process conditions are as follows: the reaction temperature is 370 ℃, the pressure is 7.47MPa, and the space velocity is 998h-1Composition of syngas H20.66/CO: 1, conversion of CO 35.8%, where C2 ＝-C4 ＝The selectivity was 79.2% and the selectivity ratio (ethylene/propylene) was 2.32.
[ example 19 ]
Application of SAPO-17 molecular sieve in the reaction of preparing hydrocarbon from synthesis gas.
A catalyst was prepared by the catalyst preparation method of example 16 using the LSSP-1 molecular sieve synthesized in example 1. The process conditions are as follows: the reaction temperature is 400 ℃, the pressure is 9.8MPa, and the space velocity is 1998h-1Composition of syngas H20.5/CO: 1, conversion of CO 31.6%, where C2＝-C4＝The selectivity was 85.3% and the selectivity ratio (ethylene/propylene) was 2.49.
Comparative example 4
The SAPO-17 molecular sieve synthesized in comparative example 2 was selected, and the catalyst prepared by the catalyst preparation method of example 17 was evaluated in the manner of example 17 to obtain a CO conversion of 22.3%, wherein C2＝-C4＝SelectingThe selectivity was 36.8%, and the selectivity ratio (ethylene/propylene) was 1.21.
[ example 20 ]
Application of SAPO-17 molecular sieve in olefin cracking reaction
Selecting the LSSP-3 molecular sieve synthesized in the example 3, preparing the catalyst by adopting the catalyst preparation method of the example 11, selecting C4 olefin as a raw material, and controlling the reaction temperature to 649 ℃, the reaction pressure to 0.04MPa and the weight space velocity to 1.49h-1The results are shown in Table 3.
Comparative example 5
A catalyst prepared by the method for preparing the catalyst of example 11 using the SAPO-17 molecular sieve synthesized in comparative example 1 was evaluated in the manner of example 20, and the results are shown in Table 3.
Comparative example 6
A catalyst prepared by the method for preparing the catalyst of example 11 using the SAPO-17 molecular sieve synthesized in comparative example 2 was evaluated in the manner of example 20, and the results are shown in Table 3.
TABLE 3
| Ethylene yield (% by weight) | Propylene yield (% by weight) | Diene yield (% by weight) | |
| Example 20 | 45.77 | 19.22 | 64.99 |
| Comparative example 5 | 26.12 | 13.77 | 39.89 |
| Comparative example 6 | 26.68 | 13.10 | 39.78 |
Claims (10)
1. A method for preparing a SAPO-17 molecular sieve, comprising the steps of:
1) mixing a molecular sieve seed crystal with an ERI structure, an organic template agent R and a long-chain quaternary ammonium salt cationic compound, and then carrying out heat treatment to obtain a precursor A;
2) mixing an aluminum source, a phosphorus source and a solvent S, and carrying out heat treatment to obtain a mixed material B;
3) mixing the precursor A, a silicon source and a mixed material B to form a crystallized mixture;
4) pretreating the crystallized mixture obtained in the step 3), and then carrying out crystallization reaction to obtain the SAPO-17 molecular sieve.
2. The method of claim 1, wherein: in the step 1), the molecular sieve seed crystal with the ERI structure is at least one of T-type molecular sieve seed crystal or AlPO-17 molecular sieve seed crystal; the organic template agent R is at least one of 1, 10-phenanthroline, 2-bipyridine, 4-bipyridine, piperazine, cyclohexylamine, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine and ethylamine, and preferably at least one of piperazine, cyclohexylamine, triethylamine, n-butylamine, ethylenediamine and ethylamine.
3. The method of claim 1, wherein: in the step 1), the long-chain quaternary ammonium salt cationic compound comprises a long-chain quaternary ammonium salt cationic compound I and a long-chain quaternary ammonium salt cationic compound II; wherein the long-chain quaternary ammonium salt cationic compound I is at least one selected from tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide and tetrabutylammonium hydroxide; the long-chain quaternary ammonium salt cationic compound II is selected from at least one of 4- (benzoyl) benzyl-N-dodecyl-N, N-dimethyl ammonium bromide, [2- (methacrylic acid) ester propyl ] (4-benzoyl benzyl) dimethyl ammonium bromide, benzoyl benzyl dimethyl octadecyl ammonium bromide and N, N-dimethyl-N-vinyl benzyl octadecyl quaternary ammonium salt; the long-chain quaternary ammonium salt cationic compound I is preferably at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium hydroxide; the long-chain quaternary ammonium salt cationic compound II is preferably at least one of 4- (benzoyl) benzyl-N-dodecyl-N, N-dimethyl ammonium bromide and N, N-dimethyl-N-vinyl benzyl octadecyl quaternary ammonium salt.
4. The method of claim 1, wherein: in the step 1), the mass ratio of the added molecular sieve seed crystal with the ERI structure, the organic template agent R and the long-chain quaternary ammonium salt cationic compound is as follows: 0.001-0.1: 1-100: 1 to 100.
5. A method according to claim 3, characterized by: the mass ratio of the long-chain quaternary ammonium salt cationic compound I to the long-chain quaternary ammonium salt cationic compound II in the long-chain quaternary ammonium salt cationic compound is 1-100: 1.
6. the method of claim 1, wherein: in the step 1), the temperature of the heat treatment is 40-80 ℃, and the time is 0.5-2 h; in the step 2), the temperature of the heat treatment is 40-80 ℃, and the time is 0.5-2 h.
7. The method of claim 1, wherein: in the step 2), the aluminum source is at least one of aluminum salt, aluminate, meta-aluminate, aluminum hydroxide, aluminum oxide and aluminum-containing mineral, and preferably at least one of aluminum salt, aluminate and meta-aluminate; the phosphorus source is at least one of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate, and phosphoric acid is preferred; the solvent S is at least one of N, N-dimethylformamide, N-dimethylacetamide, ethanol, glycol and water, and preferably at least one of N, N-dimethylformamide, ethanol and water.
8. The method of claim 1, wherein: in the step 3), the silicon source is at least one of organic silicon, amorphous silica, silica sol, white carbon black, silica gel, diatomite and water glass, and preferably at least one of amorphous silica, silica sol and white carbon black.
9. The method of claim 1, wherein: the molar ratio of the aluminum source, the silicon source, the phosphorus source, the template agent R and the solvent S added in the steps 1) to 3) is as follows: Si/Al is 0.01-0.3, P/Al is 0.75-1.5, R/Al is 1-500, S/Al is 10-1000, wherein the aluminum source, the silicon source and the phosphorus source are calculated by atom.
10. The method of claim 1, wherein: in the step 4), the pretreatment conditions are as follows: stirring for 0.5-2 h at 80-120 ℃; the crystallization reaction conditions are as follows: crystallizing at 130-220 deg.C for 10-110 min.
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| CN115231583A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | ERI framework single crystal molecular sieve and preparation method and application thereof |
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