CN111099638B - AEI/ERI composite structure molecular sieve and synthetic method thereof - Google Patents

AEI/ERI composite structure molecular sieve and synthetic method thereof Download PDF

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CN111099638B
CN111099638B CN201811250941.5A CN201811250941A CN111099638B CN 111099638 B CN111099638 B CN 111099638B CN 201811250941 A CN201811250941 A CN 201811250941A CN 111099638 B CN111099638 B CN 111099638B
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乔健
袁志庆
刘松霖
张铁柱
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to an AEI/ERI composite structure molecular sieve and a synthesis method thereof, and the AEI/ERI composite structure molecular sieve is adopted, has two phases of an AEI (SAPO-18) molecular sieve and an ERI (SAPO-17) molecular sieve, and can be used for industrial production of downstream methanol products.

Description

AEI/ERI composite structure molecular sieve and synthetic method thereof
Technical Field
The invention relates to an AEI/ERI composite structure molecular sieve and a synthesis method thereof.
Background
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. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous materials can be classified into the following three classes according to their pore diameters: the material with the pore diameter less than 2nm is microporous material; the material with the pore diameter between 2 and 50nm is mesoporous material (mesoporous materials); materials with pore sizes greater than 50nm are macroporous materials (macroporous materials) and zeolite molecular sieve channels are typically below 2nm in diameter and are therefore classified as microporous materials. And 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 object molecules, ion exchange and the like. They are mainly characterized by selective adsorption, and their unique channel system makes them possess the capability of sieving different size molecules, so that this kind of material is called "moleculeSieve "reason for.
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 the next more than ten years, 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 using a 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, ZSM-48 and the like) zeolite molecular sieves, are prepared, and have the advantages of good catalytic activity, good hydrothermal stability, high corrosion resistance and the like, so that the zeolite molecular sieves are widely applied to the fields of petroleum processing, fine chemical engineering and the like and are the hot spots 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
SAPO-18 as an important member for developing silicoaluminophosphate SAPO-n molecular sieves (n represents the type), has unique one-dimensional ten-membered ring straight channel (0.39nm multiplied by 0.63nm), and has a topological structure of AEI. According to the name of AEI topological structure of the international molecular sieve society, the material is a molecular sieve with three-dimensional eight-membered ring channels,the structures are respectively [100 ]]Direction, [110 ]]And [001 ]]With 3.8x in three directions
Figure BDA0001841676770000021
The eight-membered ring channel has the characteristic similar to that of CHA structure (SAPO-34 molecular sieve) and the material has high heat stability because the basic structural unit of the structure is D6Rs (double six-membered ring). AEI framework type molecular sieves do not exist in nature, but many aluminosilicates, aluminophosphates, and metalloaluminophosphates having the AEI topology have been successfully prepared, including AlPO-18 (aluminophosphates), RUW-18 (silicoaluminophosphates), SAPO-18 (silicoaluminophosphates), and SSZ-39 (silicoaluminophosphates). And due to the specific small pore structure of AEI-type molecular sieve materials are well suited as catalysts for a variety of important chemical processes including oxygenate conversion to olefins (US 5095163).
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 synthesizing the silicoaluminophosphate AEI (SAPO-18) molecular sieve, for example, the reaction mixture comprises framework reactants (such as silica sol, phosphoric acid and alumina) and a Structure Directing Agent (SDA) which are uniformly mixed with water, and the mixture is statically or dynamically placed in an oven (140-200 ℃) with a fixed temperature for a plurality of days for crystallization reaction. And when the crystallization reaction is finished, filtering out a solid product containing the AEI molecular sieve, and drying for later use.
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 channels which are the same as those of SAPO-34, and the pore diameter is 0.36 multiplied by 0.51nm (U.S. Pat. No. 4,4440871). In general, the synthesis of aluminophosphate molecular sieves is mainly carried out by hydrothermal method, and in the synthesis of SAPO-17, small cyclic amines are generally used as templates, and then, in the synthesis of SAPO-17, such as quinuclidine (Intra zeolite Chemistry,1983, Vol218, P79, piperidine (Acta crystalline semiconductor 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 (ChemSus chem, Vol4, P91) have synthesized needle-like AlPO-17 Crystal using neopentylamine as Structure-directing agent (Mono Crystal synthesis), Tupo-17 Crystal et al (U. Rendus, 2005, Vol8, P531, N', N-4776, N-tetramethyl diamine, P477-17. mu. mono-Crystal synthesis, and Alpo-17. mu. mono-Crystal synthesis using mono-diamine as template (Alpo-17. mu. g Crystal synthesis system, PO-17. mu. O-17. mu. A. synthesis system of mono-tetramethyl diamine (Alpo-17) is also reported in the synthesis system of Alpo-17. A. is prepared by using Alpo-2. A template synthesis method of Alpo-2. A. synthesis method of synthesizing Alpo-2, and a single Crystal synthesis method of synthesizing a single Crystal synthesis method of Alpo-P-2, and a method of the same as a single Crystal synthesis method of SAPO-17, and a method of the same as well as a method of the same as a method of the synthesis of SAPO-type of the synthesis of the type Method for synthesizing SAPO-17 by using 1, 6-hexanediamine and derivatives thereof as organic template agent Chinese patent CN 103922361A adopts T-type zeolite or SSZ-13 zeolite or Y-type zeolite or A-type zeolite or MOR-type zeolite crystalline silicon as silicon source, namely SAPO-17 molecular sieve is prepared by crystal seed crystal transformation method under high-temperature hydrothermal system.
In addition, because of the structural property of ERI (SAPO-17) molecular sieve and the moderate Bronsted acid center (Catalysis,1992, Vol9, p1), it is used as MTO (methanol to olefin) catalyst by researchers, and the U.S. Pat. No. 3, 4499327 shows that the weight hourly space velocity does not exceed 1h by using water as diluent-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 of chemical industry, 2015,43,166 ] and the literature [ Studies in Surface Science and Catalysis,1994,81,393 ] also use SAPO-17 as catalyst for the methanol to olefins reaction, in the presence of large amounts of diluent and at low space velocity (less than 1 h)-1) Higher ethylene to propylene ratios are also obtained under the conditions of (1).
So far, no reports about AEI/ERI composite structure molecular sieves and synthetic methods thereof are found in documents.
Disclosure of Invention
The invention provides an AEI/ERI composite structure molecular sieve which has the advantages of complex pore structure distribution, more total amount of strong and weak acid centers and higher catalytic activity.
The technical scheme adopted by the invention is as follows: the AEI/ERI composite structure molecular sieve is characterized in that the AEI/ERI composite structure molecular sieve has two phases of an AEI (SAPO-18) molecular sieve and an ERI (SAPO-17) molecular sieve, wherein the weight percentage of the AEI molecular sieve is 1-99%; the ERI molecular sieve has the weight percentage content of 1-99%, and the XRD diffraction pattern of the ERI molecular sieve has diffraction peaks at the positions of 7.58 +/-0.2, 9.685 +/-0.1, 13.33 +/-0.05, 15.39 +/-0.1, 16.54 +/-0.02, 16.94 +/-0.05, 19.67 +/-0.01, 20.29 +/-0.1, 20.95 +/-0.1, 21.26 +/-0.01, 21.74 +/-0.1, 22.43 +/-0.1, 26.82 +/-0.1, 31.20 +/-0.1, 31.70 +/-0.05, 33.42 +/-0.05, 35.76 +/-0.1 and 42.06 +/-0.1 in terms of 2 theta.
In the technical scheme, preferably, the composite structure molecular sieve contains 5-95 wt% of the AEI molecular sieve based on the weight percentage of the AEI/ERI composite structure molecular sieve; the weight percentage of the ERI molecular sieve is 5-95%.
In the technical scheme, more preferably, the composite structure molecular sieve contains 30-75 wt% of the AEI molecular sieve based on the weight percentage of the AEI/ERI composite structure molecular sieve; the weight percentage of the ERI molecular sieve is 25-70%.
The invention also provides a synthesis method of the AEI/ERI composite structure molecular sieve, which comprises the following steps:
a. firstly, mixing an aluminum source and a solvent to form a solution A, and dividing the solution A into two parts to be marked as a solution A1And solution A2；
b. Adding a part of phosphorus source, silicon source and template agent for synthesizing AEI molecular sieve into A1Obtaining solution A in the medium solution1’；
c. Adding the rest of phosphorus source, silicon source, organic template agent and additive needed by synthesizing ERI molecular sieve into A2Obtaining solution A in the solution2’；
d. Mixing the solution A1' with solution A2' separately Pre-crystallization treatment, followed by solution A1' with solution A2' mixing to form a crystallized mixture;
e. and d, crystallizing the crystallized mixture obtained in the step d, and filtering, washing, drying and roasting the product.
In the above technical scheme, preferably, the solution A is prepared in the step d1' with solution A2Respectively placing the solution A at 40-80 ℃ for pre-crystallization treatment for 0.5-5 h, and then carrying out the solution A1' with solution A2Uniformly mixing, and stirring for 0.5-5 h in a sealed manner at 85-110 ℃ to form a uniform crystallized mixture.
In the technical scheme, preferably, the crystallized mixture obtained in the step d is crystallized for 5-55 hours at 100-200 ℃, the product is dried at 80-120 ℃ after being filtered and washed, and then the temperature is raised to 400-600 ℃, and the product is roasted for 4-12 hours at constant temperature.
In the above technical scheme, preferably, in the step b, the solution A is obtained by fully stirring for 0.5-5 h1'; in the step c, fully stirring for 0.5-5 h to obtain a solution A2’。
In the above technical solution, preferably, the molar ratio of the raw materials used is: n (Si/Al) is 0 to 100, n (P/Al) is 0.01 to 100, n (templating agent T/Al) is 1 to 500, and n (solvent S/Al) is 10 to 1000.
In the above technical solution, preferably, the molar ratio of the raw materials used is: n (Si/Al) is 0-10, n (P/Al) is 0.1-10, n (template agent T/Al) is 5-100, and n (solvent S/Al) is 30-300; solution A in step a1And solution A2The weight ratio of (A) to (B) is 0.1-10: 1; and (c) the phosphorus source used in the step (b) accounts for 5-95% of the total phosphorus source by mass. In the above technical solution, more preferably, the molar ratio of the raw materials used is: n (Si/Al) is 0-3, n (P/Al) is 0.2-2, n (template agent T/Al) is 10-50, and n (solvent S/Al) is 60-200; solution A in step a1And solution A2The weight ratio of (A) to (B) is 0.2-5: 1; and (c) the phosphorus source used in the step (b) accounts for 15-85% of the total phosphorus source by mass.
In the above embodiment, the aluminum source is preferably at least one selected from the group consisting of aluminates, meta-aluminates, aluminum hydroxides, aluminum oxides, and aluminum-containing minerals; the phosphorus source is selected from at least one of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the silicon source is at least one of organic silicon, amorphous silica, silica sol, solid silica, silica gel, diatomite and water glass;
in the above technical solution, preferably, the aluminum source is at least one selected from aluminates and meta-aluminates; the phosphorus source is orthophosphoric acid; the silicon source is at least one of amorphous silica, silica sol or solid silica;
in the above technical solution, preferably, the template agent required for preparing the AEI molecular sieve includes at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine, ethylamine; the organic template agent required for preparing the ERI molecular sieve is organic amine and is selected from at least one of 1, 10-phenanthroline, 2-bipyridine, 4-bipyridine, piperazine, cyclohexylamine, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine and ethylamine; the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, ethanol, ethylene glycol and water.
In the above technical solution, preferably, the template agent required for preparing the AEI molecular sieve comprises at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, and triethylamine; the organic template agent required for preparing the ERI molecular sieve is organic amine and is selected from at least one of 1-cyclohexylamine, di-n-propylamine and diisopropylamine; the solvent is at least one of N, N-dimethylformamide, ethanol and water.
The invention also provides application of the AEI/ERI composite molecular sieve as a catalyst, preferably, the AEI/ERI composite molecular sieve is used in reactions of methanol to hydrocarbons, synthesis gas to hydrocarbons and olefin cracking.
In the technical scheme, the AEI/ERI composite molecular sieve catalyst is applied to the reaction of preparing hydrocarbon from methanol; preferably, the reaction conditions for preparing hydrocarbons by methanol conversion 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 0.1～15h-1。
In the technical scheme, the AEI/ERI composite molecular sieve catalyst is applied to the reaction of preparing hydrocarbons from synthesis gas; the reaction conditions for producing hydrocarbons from synthesis gas are preferably as follows: using synthetic gas as raw material H20.5-1 of/CO, 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。
In the technical scheme, the AEI/ERI composite molecular sieve catalyst is applied to hydrocarbon cracking reaction; preferably, the cracking reaction conditions are as follows: the reaction temperature is 500-650 ℃, the weight ratio of the diluent to the raw material is 0-1: 1, and the liquid phase airspeed is 1-30 h-1The reaction pressure is-0.05 to 0.2 MPa. The hydrocarbon preferably comprises at least one olefin, more preferably at least one C4And the above olefins.
The AEI/ERI composite molecular sieve provided by the invention has the pore channel structural characteristics and the acidic characteristics of two molecular sieves, and shows a good synergistic effect. The optimal pore structure and the proper acidity of the composite molecular sieve are obtained by changing the proportion of two phases in the composite molecular sieve through in-situ regulation and optimization of synthesis conditions, the composite molecular sieve is used for the reaction process of preparing hydrocarbon through methanol conversion, the conversion rate of methanol is 100 percent in the set evaluation condition range, the one-way selectivity of ethylene and propylene can reach 77.6 percent at most, the selectivity ratio (ethylene/propylene) is adjustable in the range of 0.5-1.5, the catalyst has good stability, and better technical effects are obtained; the method is used for the reaction process of preparing olefin from synthesis gas, and the highest CO conversion rate can reach 35.5 percent and C is within the set evaluation condition range2-C4The selectivity of olefin can reach 55 percent at most, the selectivity ratio (ethylene/propylene) is adjustable within the range of 0.7-1.4, and a better technical effect is achieved; the method is used for olefin cracking reaction, and the single-pass selectivity of the olefin and the propylene in the cracking product can reach 50.6% at most within the set evaluation condition range, so that a better technical effect is achieved.
Drawings
FIG. 1 is an XRD pattern of an AEI/ERI composite structure molecular sieve;
FIG. 2 is an SEM photograph of an AEI/ERI composite structure molecular sieve;
Detailed Description
[ example 1 ]
Synthesis of AEI/ERI composite structure molecular sieve
10332.66g of aluminum nitrate [ Al (NO) were weighed3)3·9H2O, purity more than or equal to 98 wt.%, 27.54mol]Dissolving in 7765.25mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 63% and 37%, and marking as a solution A1And solution A212001.89g of acidic silica sol [ SiO ]2，40wt.％，80.01mol]6878.55g of phosphoric acid [ H ]3PO4Purity not less than 85 wt.%, 59.66mol]And 10983.12g of tetramethylammonium hydroxide [ TMAOH,25 wt.%, 30.12 mol%]Charging A1Stirring the solution for 5 hours to obtain a solution A1'; 922.37g of phosphoric acid [ H ]3PO4,85wt.％,8.00mol]1033.64g of acidic silica sol [ SiO ]2，40wt.％，6.89mol]And 2208.03g of cyclohexylamine [ HCHA, 99 wt.%, 22.26mol ]]Charging A2Stirring the solution for 2 hours to obtain a solution A2'; mixing the solution A1' with solution A2' Pre-crystallization treatment at 40 ℃ for 5h, then solution A1' with solution A2Uniformly mixing, and stirring for 5 hours in a sealed way at 85 ℃; and (3) crystallizing the stirred mixture at 115 ℃ for 50h, filtering and washing the product, drying the product at 110 ℃ for 5h, heating to 400 ℃, and roasting at constant temperature for 12h to obtain the product, namely AEC-1. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: the content of AEI molecular sieve in AEC-1 molecular sieve is 62.3% and ERI content is 37.7% as shown by ICP test and XRD analysis, S is 1: 3.16: 2.35: 1.91: 50.42.
[ example 2 ]
Synthesis of AEI/ERI composite structure molecular sieve
210.51g of aluminum isopropoxide [ Al (iPr) ]were weighed out3Purity is more than or equal to 99 wt.%, 1.03mol]Dissolving in 966.35mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 45% and 55%, and marking as a solution A1And solution A2201.98g of white carbon black SiO2，99wt.％，3.37mol]80.69g of ammonium dihydrogen phosphate [ NH ]4H2PO4，0.70mol]And 213.61g of ethylenediamine [ DEA, 3.56mol]Charging A1Stirring the solution for 2.9h to obtain a solution A1'; 101.34g of ammonium dihydrogen phosphate [ NH ]4H2PO4，0.88mol]220.39g of white carbon black SiO2，99wt.％，3.67mol]And 76.35g of piperazine [ PIP, 0.88mol]Charging A2Stirring the solution for 1.1h to obtain a solution A2'; mixing the solution A1' with solution A2' placing the solution A at 80 ℃ for pre-crystallization for 0.5h respectively, and then1' with solution A2Uniformly mixing, and stirring for 0.5h at 110 ℃ in a sealed manner; and (3) crystallizing the stirred mixture at 200 ℃ for 5h, filtering and washing the product, drying the product at 80 ℃ for 8h, heating to 550 ℃, and roasting at constant temperature for 6h to obtain the product, namely AEC-2. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: the content of AEI molecular sieve in AEC-2 molecular sieve is 43.9% and ERI content is 56.1% as shown by ICP test and XRD analysis, S is 1: 6.83: 1.53: 4.31: 52.13.
[ example 3 ]
Synthesis of AEI/ERI composite structure molecular sieve
13.75g of aluminum nitrate [ Al (NO) was weighed3)3·9H2O, purity more than or equal to 99 wt.%, 0.04mol]Dissolving the mixture in 122.11mL of deionized water, uniformly stirring, dividing the solution into two parts by mass, namely 19% and 81%, and marking as a solution A and a solution A299.31g of an acidic silica sol [ SiO ]2，40wt.％，0.66mol]66.42g of phosphoric acid [ H ]3PO4,85wt.％,0.58mol]And 22.38g tetraethylammonium hydroxide [ TEAOH,50 wt.%, 0.06 mol%]Charging A1Stirring the solution for 1.2h to obtain a solution A1'; 16.88g of phosphoric acid [ H ]3PO4，85wt.％，0.15mol]100.69g of acidic silica sol [ SiO ]2,40wt.％,0.67mol]And 211.56g of tetrabutylammonium bromide [ TPABr, 0.67mol]Charging A2Stirring the solution for 0.5h to obtain a solution A2'; mixing the solution A1' with solution A2' Pre-crystallization treatment at 60 ℃ for 3.2h respectively, and then the solution A1' with solution A2' uniformly mixing the components of the mixture,stirring for 3.9h at 90 ℃ in a sealed manner; and (3) crystallizing the stirred mixture at 165 ℃ for 28h, filtering and washing the product, drying the product at 80 ℃ for 9h, heating to 550 ℃, and roasting at constant temperature for 5h to obtain the product, namely AEC-3. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: the content of AEI molecular sieve in the AEC-3 molecular sieve is 18.3 percent and the ERI content is 81.7 percent as shown by ICP test and XRD analysis when the S is 1: 33.25: 18.25: 369.
[ example 4 ]
Synthesis of AEI/ERI composite structure molecular sieve
29085.71g of aluminum sulfate [ Al ] were weighed2(SO4)3·18H2O, purity ≥ 98 wt.%, 46.64mol]Dissolving in 88156.99mL deionized water, stirring uniformly, dividing the solution into two parts by mass, respectively 80% and 20%, and marking as solution A1And solution A221911.63g of white carbon black SiO2，99wt.％，365.19mol]10032.86g of phosphoric acid [ H ]3PO4，85％wt.，88.38mol]And 32222.89g of tetraethylammonium bromide [ TEABr, 87.02mol]Charging A1Stirring the solution for 0.5h to obtain a solution A1'; 15332.96g of phosphoric acid [ H ]3PO4,85％wt.,132.99mol]1288.33g of white carbon black SiO2,99wt.％,21.47mol]968.68g of ethylamine [ EA,21.53 mol%]And 1820.94g of cyclohexylamine [ HCHA,18.37mol]Charging A2Stirring the solution for 2 hours to obtain a solution A2'; mixing the solution A1' with solution A2' hydrothermal treatment at 75 ℃ for 2.6 hours, respectively, after which solution A was1' with solution A2Uniformly mixing, and stirring for 1.5 hours in a closed manner at 100 ℃; and (2) crystallizing the stirred mixture at 185 ℃ for 10 hours, filtering and washing the product, drying the product at 110 ℃ for 6 hours, heating to 600 ℃, and roasting at constant temperature for 4 hours to obtain a product, namely AEC-4, wherein the stoichiometric ratio of reactants of the system is as follows: al: si: p: t: the content of AEI molecular sieve in AEC-4 molecular sieve is 78.9% and ERI content is 21.1% as shown by ICP test and XRD analysis, S is 1: 8.29: 4.75: 2.72: 109.54.
[ example 5 ]
Synthesis of AEI/ERI composite structure molecular sieve
1110.69g of aluminum isopropoxide [ Al (iPr) ]were weighed out3Purity is more than or equal to 99 wt.%, 5.44mol]Dissolving in 4211.98mL deionized water, stirring uniformly, dividing the solution into two parts by mass, 11% and 89% respectively, and marking as solution S1And solution S2560.12g of white carbon black SiO2，99％wt.，9.33mol]1031.31g of diammonium hydrogen phosphate [ (NH)4)2HPO4，7.81mol]And 1038.22g of tetraethylammonium hydroxide [ TEAOH,25 wt.%, 1.27 mol%]Charging A1Stirring the solution for 2.5h to obtain a solution A1'; 737.65g of diammonium hydrogen phosphate [ (NH)4)2HPO4，5.58mol]312.93g of white carbon black SiO2，99％wt.，5.21mol]201.33g of di-n-propylamine [ DPA, 1.99mol and 676.35g of piperazine [ PIP, 7.85 mol%]]Charging A2Stirring the solution for 12 hours to obtain a solution A2'; mixing the solution A1' with solution A2' Pre-crystallization treatment at 55 deg.C for 4.1h, respectively, and then the solution A1' with solution A2Uniformly mixing, and stirring for 4 hours in a closed manner at 90 ℃; and (3) crystallizing the stirred mixture at 100 ℃ for 55h, filtering and washing the product, drying the product at 100 ℃ for 7.5h, heating to 500 ℃, and roasting at constant temperature for 8h to obtain the product, namely AEC-5. The stoichiometric ratio of reactants of the system is as follows: al: si: p: t: the content of AEI molecular sieve in AEC-5 molecular sieve is 8.6% and ERI content is 92.4% as shown by ICP test and XRD analysis, S is 1: 2.67: 2.46: 2.04: 41.77.
[ examples 6 to 20 ]
According to the method of example 5, the raw materials are shown in table 1, the AEI/ERI composite structure molecular sieves are synthesized by controlling different proportions of the reaction materials (table 2), and the proportions of AEI and ERI in the materials are shown in table 3.
TABLE 1
Figure BDA0001841676770000081
Figure BDA0001841676770000091
TABLE 2
Figure BDA0001841676770000092
Figure BDA0001841676770000101
[ example 21 ]
Application of AEI/ERI composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
And (3) roasting the AEC-6 molecular sieve synthesized in the example 6 at 550 ℃ for 4 hours, cooling to room temperature, tabletting, breaking, and screening to obtain particles of 12-20 meshes for later use. Methanol is used as a raw material, a fixed bed reactor with the diameter of 15 mm is used, the mass space velocity is 2.5h at the temperature of 400 DEG C-1When evaluated under the condition of the pressure of 1.55MPa, the yield of ethylene and propylene reaches 52.9 percent, and the selectivity ratio (ethylene/propylene) is 0.78, thereby obtaining better technical effects.
TABLE 3
Sample numbering AEI content (%) ERI content (% by weight)
AEC-6 51.6 48.4
AEC-7 99.0 1.0
AEC-8 77.7 22.3
AEC-9 64.9 35.1
AEC-10 25.0 75.0
AEC-11 1.0 99.0
AEC-12 61.5 38.5
AEC-13 75.0 25.0
AEC-14 95.0 5.0
AEC-15 55.2 44.8
AEC-16 13.8 86.2
AEC-17 88.1 11.9
AEC-18 37.0 63.0
AEC-19 44.0 56.0
AEC-20 5.0 95.0
[ example 22 ]
The AEI/ERI composite structure molecular sieve is applied to the reaction of preparing hydrocarbon by converting methanol.
The AEC-9 molecular sieve synthesized in the example 9 is taken, the catalyst is prepared by the catalyst preparation method of the example 21, 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 0.09h at 449 DEG C-1When the pressure is evaluated under the condition of 0.01MPa, the yield of ethylene and propylene reaches 55.5 percent, and the selectivity ratio (ethylene/propylene) is 0.47, so that the better technical effect is achieved.
[ example 23 ]
Application of AEI/ERI composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The AEC-6 molecular sieve synthesized in example 16 was used to prepare the catalyst by the catalyst preparation method of example 21, methanol was used as the raw material, a fixed bed reactor with a diameter of 15 mm was used, and the mass space velocity was 14.9h at 475 deg.C-1When the pressure is evaluated under the condition of 9.9MPa, the yield of ethylene and propylene reaches 66.8 percent, and the selectivity ratio (ethylene/propylene) is 1.67, so that a better technical effect is achieved.
[ example 24 ]
Application of AEI/ERI composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The AEC-17 molecular sieve synthesized in example 17 was used to prepare the catalyst by the catalyst preparation method of example 21, methanol was used as the raw material, a fixed bed reactor with a diameter of 15 mm was used, and the mass space velocity was 7.2h at 549 deg.C-1When evaluated under the condition of the pressure of 2.7MPa, the yield of ethylene and propylene reaches 71.2 percent, and the selectivity ratio (ethylene/propylene) is 0.38, thereby obtaining better technical effects.
[ example 25 ]
Application of AEI/ERI composite structure molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The AEC-19 molecular sieve synthesized in example 19 was used to prepare the catalyst by the catalyst preparation method of example 21, methanol was used as the raw material, a fixed bed reactor with a diameter of 15 mm was used, and the mass space velocity was 4.6h at 589 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 0.92, which resulted in a good technical effect.
[ COMPARATIVE EXAMPLE 1 ]
The catalyst prepared by the catalyst preparation method of example 21 was evaluated according to the method of example 23, and the yields of ethylene and propylene were 11.6%.
AEI preparation: tetraethyl sodium hydroxide (TEAOH) was added to pseudo-boehmite (Al)2O3) Stirring the solution for 120min, and adding phosphoric acid solution (H) to the solution3PO485 wt%), and continuously stirring for 30min, and then putting into a stainless steel reaction kettle with a polytetrafluoroethylene lining. Crystallizing at 140 deg.C for 5 d.
[ COMPARATIVE EXAMPLE 2 ]
The catalyst prepared by the catalyst preparation method of example 21 was obtained from the self-made ERI molecular sieve, and the ethylene and propylene yields were up to 21.9% when evaluated in the manner of example 23.
Preparing ERI: the phosphoric acid solution (H) was stirred at room temperature3PO485% wt) aluminum isopropoxide (Al (iPr)3) Adding water into the solution, stirring for 60min, adding cyclohexylamine (HC)HA), stirring for 60min, adding tetraethyl ammonium hydroxide solution (TEAOH, 25% wt.), stirring for 30min, and placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining. Crystallizing at 200 deg.C for 1 d.
[ COMPARATIVE EXAMPLE 3 ]
The catalyst prepared by the catalyst preparation method of example 21 was evaluated according to the method of example 23, and the yields of ethylene and propylene reached 29.5%.
[ COMPARATIVE EXAMPLE 4 ]
Application of mechanical mixing AEI and ERI molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The self-made AEI molecular sieve and the self-made ERI molecular sieve were mechanically mixed according to the ratio of the two molecular sieves of example 10, and evaluated in the same manner as in example 21, and the yields of ethylene and propylene were 47.6% and the selectivity ratio (ethylene/propylene) was 1.26.
[ COMPARATIVE EXAMPLE 5 ]
Application of mechanical mixing AEI and ERI molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The self-made AEI molecular sieve and the self-made ERI molecular sieve were mechanically mixed according to the ratio of the two molecular sieves of example 13, and evaluated in the same manner as in example 21, and the yields of ethylene and propylene were 45.9%, and the selectivity ratio (ethylene/propylene) was 0.73.
[ COMPARATIVE EXAMPLE 6 ]
Application of mechanical mixing AEI and ERI molecular sieve in reaction for preparing hydrocarbon by methanol conversion
The self-made AEI and ERI molecular sieves were mechanically mixed according to the ratio of the two molecular sieves of example 5, and evaluated in the same manner as in example 21, and the ethylene and propylene yields reached 46.3% with an selectivity ratio (ethylene/propylene) of 1.41.
[ example 26 ]
The AEI/ERI composite molecular sieve is applied to the reaction of preparing hydrocarbon from synthesis gas.
The AEC-15 molecular sieve synthesized in the example 15 is taken, calcined for 4 hours at 550 ℃, then tableted, crushed and sieved, particles of 20-40 meshes are taken, and the mass ratio of the catalyst filler is ZnCrOx/AEC ═ 1.0 (Zn)CrOx represents a mixture of zinc oxide and chromium oxide to prepare an oxide-molecular sieve catalyst for later 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 200 ℃, the pressure is 0.11MPa, and the space velocity is 395h-1Composition of syngas H21/CO: 1, conversion of CO 31.5%, where C2＝-C4＝The selectivity was 51.8%, and the selectivity ratio (ethylene/propylene) was 0.91.
[ example 27 ]
The AEI/ERI composite molecular sieve is applied to the reaction of preparing hydrocarbon from synthesis gas.
A catalyst was prepared by the catalyst preparation method of example 26 using the AEC-18 molecular sieve synthesized in example 18. The process conditions are as follows: the reaction temperature is 350 ℃, the pressure is 1.1MPa, and the space velocity is 19.9h-1Composition of syngas H20.75% of/CO: 1, conversion of CO 35.5%, where C2＝-C4＝The selectivity was 54.4% and the selectivity ratio (ethylene/propylene) was 1.16.
[ example 28 ]
The AEI/ERI composite molecular sieve is applied to the reaction of preparing hydrocarbon from synthesis gas.
A catalyst was prepared by the catalyst preparation method of example 26 using the AEC-10 molecular sieve synthesized in example 10. The process conditions are as follows: the reaction temperature is 400 ℃, the pressure is 9.9MPa, and the space velocity is 1998h-1Composition of syngas H20.48 for/CO: 1, conversion of CO 24.1%, where C2＝-C4＝The selectivity was 48.5% and the selectivity ratio (ethylene/propylene) was 1.32.
[ example 29 ]
The AEI/ERI composite molecular sieve is applied to the reaction of preparing hydrocarbon from synthesis gas.
A catalyst was prepared by the catalyst preparation method of example 26 using the AEC-8 molecular sieve synthesized in example 8. The process conditions are as follows: the reaction temperature is 239 ℃, the pressure is 7.47MPa, and the space velocity is 998h-1Composition of syngas H20.66/CO: 1, conversion of CO 30.3%, where C2 ＝-C4 ＝Selectivity 49.2%, selectivity ratio (ethylene/propylene) ═0.69。
[ COMPARATIVE EXAMPLE 7 ]
The conversion of CO, from a homemade AEI molecular sieve evaluated in the manner of example 26, was 15.7%, where C2 ＝-C4 ＝The selectivity is 18.3 percent
[ COMPARATIVE EXAMPLE 8 ]
The conversion of CO, taken from the home made ERI molecular sieve and evaluated in the manner of example 26, was 12.2%, where C2 ＝-C4 ＝The selectivity was 17.6%.
[ example 30 ]
Application of AEI/ERI composite structure molecular sieve in olefin cracking reaction
Selecting the AEC-2 molecular sieve synthesized in the example 2, preparing the catalyst by adopting the catalyst preparation method of the example 21, and controlling the reaction temperature to 658 ℃, the reaction pressure to be 0.03MPa and the weight space velocity to be 1.46h-1The results are shown in Table 6.
[ COMPARATIVE EXAMPLE 9 ]
Taking SiO2/Al2O3A catalyst prepared from mordenite having a molar ratio of 9.8 using the catalyst preparation method of example 21 was evaluated in the same manner as in example 30 and the results are shown in Table 6.
[ COMPARATIVE EXAMPLE 10 ]
Taking SiO2/Al2O3A catalyst prepared by the method for preparing the catalyst of example 21 was evaluated as in example 30 and found to have a molar ratio of zeolite beta of 33.2, as shown in Table 6.
[ COMPARATIVE EXAMPLE 11 ]
Taking SiO2/Al2O3A catalyst prepared by the catalyst preparation method of example 21 and having a Y zeolite molar ratio of 11.5 was evaluated in the same manner as in example 30, and the results are shown in Table 6.
[ COMPARATIVE EXAMPLE 12 ]
Taking SiO2/Al2O3A catalyst prepared from a ZSM-5 molecular sieve having a molar ratio of 53.9 by the method for preparing the catalyst of example 21 was evaluated in the same manner as in example 30, and the results are shown in Table 6.
TABLE 6
Figure BDA0001841676770000141
Figure BDA0001841676770000151

Claims (9)

1. An AEI/ERI composite structure molecular sieve is used as a catalyst in the reaction of preparing olefin from synthesis gas, wherein the AEI/ERI composite structure molecular sieve has two phases of an AEI molecular sieve and an ERI molecular sieve, and an XRD diffraction pattern of the AEI/ERI composite structure molecular sieve has diffraction peaks at 7.58 +/-0.2, 9.685 +/-0.1, 13.33 +/-0.05, 15.39 +/-0.1, 16.54 +/-0.02, 16.94 +/-0.05, 19.67 +/-0.01, 20.29 +/-0.1, 20.95 +/-0.1, 21.26 +/-0.01, 21.74 +/-0.1, 22.43 +/-0.1, 26.82 +/-0.1, 31.20 +/-0.1, 31.70 +/-0.05, 33.42 +/-0.05, 35.76 +/-0.1 and 42.06 +/-0.1;
the composite structure molecular sieve comprises 30-75% of AEI molecular sieve by weight; the weight percentage content of the ERI molecular sieve is 25-70%;
the synthesis method of the AEI/ERI composite structure molecular sieve comprises the following steps: the molar ratio of the used raw materials is as follows: Si/Al = 0-100, P/Al = 0.01-100, template agent T/Al = 1-500, solvent S/Al = 10-1000,
a. mixing an aluminum source and a solvent to form a solution A, and dividing the solution A into two parts to be marked as a solution A1And solution A2；
b. Adding a part of phosphorus source, silicon source and template agent for synthesizing AEI molecular sieve into A1Obtaining solution A in the medium solution1’；
c. Adding the rest of phosphorus source, silicon source, organic template agent and additive needed by synthesizing ERI molecular sieve into A2In solution to obtain solution A2’；
d. Mixing the solution A1' with solution A2' separately Pre-crystallization treatment, followed by solution A1' with solution A2' mixing to form a crystallized mixture;
e. and d, crystallizing the crystallized mixture obtained in the step d, and filtering, washing, drying and roasting the product.
2. Use according to claim 1, characterized in that the molar ratios of the raw materials used are: Si/Al = 0-10, P/Al = 0.1-10, template agent T/Al = 5-100, and solvent S/Al = 30-300; solution A in step a1And solution A2The weight ratio of (A) to (B) is 0.1-10: 1; and (c) the phosphorus source used in the step (b) accounts for 5-95% of the total phosphorus source by mass.
3. Use according to claim 1, characterized in that the molar ratios of the raw materials used are: Si/Al = 0-3, P/Al = 0.2-2, template agent T/Al = 10-50, and solvent S/Al = 60-200; solution A in step a1And solution A2The weight ratio of (A) to (B) is 0.2-5: 1; and (c) the phosphorus source used in the step (b) accounts for 15-85% of the total phosphorus source by mass.
4. The use according to claim 1, wherein the aluminium source is selected from at least one of aluminates, meta-aluminates, aluminium hydroxides and aluminium oxides; the phosphorus source is selected from at least one of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the silicon source is at least one selected from the group consisting of silicone, silica sol, solid silica, silica gel, diatomaceous earth, and water glass.
5. Use according to claim 1, characterised in that the aluminium source is an aluminium-containing mineral.
6. Use according to claim 1, wherein the silicon source is amorphous silica.
7. The use of claim 1 wherein the template required for the preparation of the AEI molecular sieve comprises at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine, ethylamine; the organic template agent required for preparing the ERI molecular sieve comprises organic amine, and is selected from at least one of 1, 10-phenanthroline, 2-bipyridine, 4-bipyridine, piperazine, cyclohexylamine, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine and ethylamine; the solvent includes at least one of N, N-dimethylformamide, N-dimethylacetamide, ethanol, ethylene glycol, and water.
8. The use according to claim 1, wherein the aluminium source is selected from at least one of aluminates and metaaluminates; the phosphorus source comprises orthophosphoric acid; the silicon source is at least one selected from silica sol and solid silica; the template agent required by the AEI molecular sieve is selected from at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide and triethylamine; the organic template agent required for preparing the ERI molecular sieve is organic amine and is selected from at least one of 1-cyclohexylamine, di-n-propylamine and diisopropylamine; the solvent is at least one of N, N-dimethylformamide, ethanol and water.
9. Use according to claim 1, wherein step d consists in dissolving A in solution A1' with solution A2Respectively placing the solution A at 40-80 ℃ for pre-crystallization treatment for 0.5-5 h, and then carrying out the solution A1' with solution A2Uniformly mixing, and stirring for 0.5-5 h in a closed manner at 85-110 ℃ to form a uniform crystallized mixture; and d, crystallizing the crystallized mixture obtained in the step d at 100-200 ℃ for 5-55 hours, filtering and washing the product, drying the product at 80-120 ℃, heating to 400-600 ℃, and roasting at constant temperature for 4-12 hours.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2003035549A1 (en) * 2001-10-23 2003-05-01 Exxonmobil Chemical Patents Inc. Synthesis of silicoaluminophosphates
CN101314135A (en) * 2008-06-27 2008-12-03 吉林大学 Method for preparing double-catalysis center molecular sieve nucleocapsid material with hydrothermal/solvent-thermal system
CN107777699A (en) * 2016-08-30 2018-03-09 中国石油化工股份有限公司 The composite molecular sieves of ZSM 11/SSZ 13 and its synthetic method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003035549A1 (en) * 2001-10-23 2003-05-01 Exxonmobil Chemical Patents Inc. Synthesis of silicoaluminophosphates
CN101314135A (en) * 2008-06-27 2008-12-03 吉林大学 Method for preparing double-catalysis center molecular sieve nucleocapsid material with hydrothermal/solvent-thermal system
CN107777699A (en) * 2016-08-30 2018-03-09 中国石油化工股份有限公司 The composite molecular sieves of ZSM 11/SSZ 13 and its synthetic method

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