CN112619697B - Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve - Google Patents

Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve Download PDF

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CN112619697B
CN112619697B CN201910904845.6A CN201910904845A CN112619697B CN 112619697 B CN112619697 B CN 112619697B CN 201910904845 A CN201910904845 A CN 201910904845A CN 112619697 B CN112619697 B CN 112619697B
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molecular sieve
cha
seed crystal
aei
composite
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CN112619697A (en
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丁佳佳
刘红星
陆贤
赵昱
管洪波
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P30/40—Ethylene production

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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a preparation method of a composite AEI/CHA molecular sieve and the prepared composite AEI/CHA molecular sieve. The method adopts at least two CHA structure molecular sieves with defects as seed crystals, wherein the two CHA structure molecular sieves with defects are respectively seed crystal I and seed crystal II; the seed crystal I and the seed crystal II contain micropores, macropores and mesopores; wherein the ratio of the pore volume of the macropores and the mesopores of the seed crystal I to the total pore volume is 8% -14%; the pore volume of the seed crystal II, the macropores and the mesopores accounts for 15% -35% of the total pore volume. The composite AEI/CHA molecular sieve prepared by the method is used as a catalyst in a process for preparing low-carbon olefin from oxygen-containing compounds, and has excellent low-carbon olefin selectivity, particularly higher propylene selectivity and longer service life of the catalyst.

Description

Preparation method of composite AEI/CHA molecular sieve and prepared molecular sieve
Technical Field
The invention relates to a preparation method of a composite AEI/CHA molecular sieve and the prepared molecular sieve.
Background
In 1984, united states corporation of carbide (UCC) invented silicoaluminophosphate molecular sieves (abbreviated as SAPO molecular sieves) having pore sizes of about 0.4 nm. SAPO molecular sieve is prepared from AlO 4 、SiO 4 And PO (PO) 4 Crystal network structure formed by tetrahedra, pore canal in crystal due to Si 4+ Substituted for P 5+ Or Al 3+ The acidity generated is either substituted with metal to generate acidity. The crystal structure of the SAPO-34 molecular sieve is of a CHA type structure, the basic structural units of the molecular sieve are double six-membered rings and CHA cages, the crystal structure of the SAPO-18 molecular sieve is of an AEI structure, and the microporous pore structure of the molecular sieve is similar to the CHA structure. Among the SAPO-series molecular sieves, SAPO-34 molecular sieves are widely used in the modern petroleum processing industry because of their good thermal and hydrothermal stability, moderate acidity, high specific surface area, and highly ordered microporous channels. The molecular sieve is most attractive when applied to the reaction of preparing olefin (MTO) from methanol, and can lead the conversion rate of the methanol to reach 100 percent, the selectivity of ethylene and propylene to exceed 75 percent, C 5 + The content of the components is small, and almost no aromatic hydrocarbon is generated. The SAPO-18 molecular sieve has weaker surface acidity, and shows excellent catalytic performance and longer catalyst stability in the MTO process. The SAPO-18 and the SAPO-34 molecular sieves are compounded to form the SAPO molecular sieve with a eutectic structure, and the eutectic molecular sieve has pore channels and acidity of two crystal phase structures, is used for catalytic reaction and often shows better performance than a single molecular sieve, and can effectively solve the problems of low catalytic activity, low stability and the like of the single molecular sieve caused by single pore diameter. CN101076401a discloses a silicoaluminophosphate molecular sieve comprising intergrown of CHA and AEI structures, which patent is mainly used to determine the ratio of AEI to CHA. CN103878018A discloses a preparation method of small-grain SAPO-18/SAPO-34 eutectic molecular sieve, which has better activity selectivity and stability when applied to the reaction of preparing olefin from methanol. CN103833047A discloses a SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and a preparation method thereof, and the molecular sieve also shows good catalytic activity and excellent performance when being applied to a catalyst for preparing low-carbon olefin from oxygen-containing compoundsIso-propylene and butene selectivity and longer service life.
But the SAPO-18 and SAPO-34 molecular sieves are microporous, and the eutectic molecular sieves formed by the two molecular sieves are microporous molecular sieves. The relatively long and narrow pore canal of the microporous molecular sieve presents serious shape-selective limitation, on one hand, the contact between the raw material molecules and the active center inside the pore canal of the microporous molecular sieve is hindered, on the other hand, the diffusion and mass transfer of reactants, intermediate transition products and final products are limited, the pore canal is easily blocked due to carbon deposition, the catalyst is deactivated, and the exertion of the catalytic performance of the microporous molecular sieve is limited. In order to overcome the defects of single microporous molecular sieve materials, a plurality of researchers prepare novel molecular sieves combining the advantages of various pore channels, namely, the materials such as the multi-level pore structure molecular sieves have two pore channel systems of micropores and mesopores/macropores, so that the diffusion performance of the materials can be greatly improved, the catalytic performance of the materials is improved, and the materials show good catalytic conversion performance in reactions involving macromolecules and reactions requiring rapid diffusion.
For this purpose, a preparation method by adding a mesoporous template to a gel system and then performing hydrothermal synthesis has been proposed. Choi et al report that AlPO with mesoporous structure was synthesized by one-step hydrothermal synthesis using silanized long-chain alkyl quaternary ammonium salt as template agent 4 -n series molecular sieves (Choi M, srivasta va R, ryoo r.chemical Communications,2006, (42): 4380-4382.); subsequently, danilina and Chen Lu et al hydrothermally synthesize SAPO-5 (Danilina N, krumeich F, van Bokhoven J. Journal of Catalysis,2010,272 (1): 37-43.) and SAPO-34 molecular sieves (Chen Lu, wang Runwei, ding Shuang et al. University journal of chemistry,2010; 31 (9): 1693-1696.) with a hierarchical pore structure, respectively, using a multifunctional long chain organosilicon as a silicon source; fan et al can synthesize SAPO-11 molecular sieves (Fan Y, xiao H, shi G, et al journal of Catalysis,2012,285 (1): 251-259) with a rich mesoporous structure under conventional hydrothermal conditions by adding long-chain organophosphines as mesoporous template agents; cui et al synthesized SAPO-34 molecular sieves having a hierarchical pore structure under hydrothermal conditions using polyethylene glycol (PEG) as a mesoporous template agent, and the size of the mesoporous pores could be varied by adjusting the amount of PEG (Cui Y, zhang Q, he J, et al, particle, 2013;11 (4): 468-474.). Yang et alThe silanized surfactant is used as a mesoporous template agent, and a multistage pore structure SAPO-34 is synthesized under the assistance of microwaves, and the result shows that the introduction of microwaves can not only effectively shorten the crystallization time (the crystallization process can be completed only in 2 hours), but also the synthesized product has higher specific surface area and mesoporous volume (Yang S, kim J, chae H, et al materials Research Bulletin,2012;47 (11): 3888-3892.). Although SAPO-34 molecular sieves having a multi-stage pore structure can be prepared by introducing a mesoporous templating agent into the synthesis system of the molecular sieve during the synthesis process, suitable templating agents are not only expensive, but also the process of removing the templating agent is difficult to control.
In order to solve the problems, yang Heqin and the like, a silicoaluminophosphate SAPO molecular sieve integral material with a multi-stage pore structure is prepared by adopting a gas phase crystallization method, and the material has higher catalytic activity in MTO reaction compared with a conventional SAPO-34 molecular sieve (CN 102219237A; yang H, liu Z, gao H, et al, journal of Materials Chemistry,2010;20 (16): 3227-3231). Recently, jin et al have mixed and ground a silicon source, an aluminum source, a phosphorus source and morpholine uniformly, then directly put the solid mixture into an oven, crystallize for 8-24 hours at 200 ℃ under the condition of no solvent, and the obtained product is washed, dried and roasted to obtain SAPO-34 molecular sieves (Jin Y, sun Q, qi G, et al Angewandte Chemie International Edition,2013;125 (35): 9342-9345) with mesoporous structures, which also show better catalytic performance in MTO reactions.
In addition, aiming at the condition of price change of chemical raw material market, an MTO catalyst meeting market conditions is developed so as to use an MTO catalyst with high ethylene yield when the price of ethylene is high and use an MTO catalyst with high propylene yield when the price of propylene is high, thereby maximally improving the profit level of enterprises.
In summary, although the preparation of the hierarchical pore material is a hot spot for research by numerous researchers at present, the existing method for preparing the hierarchical pore SAPO molecular sieve has the defects of complicated operation process, high cost and the like, and the structure of the molecular sieve can be damaged when the mesoporous template agent is removed. In addition, the development of ethylene/propylene tunable MTO catalysts is also an important method for improving the profitability level of enterprise users according to the market demands of chemical raw materials. In view of the above, the preparation cost is reduced, the operation procedure is simplified, and the development of a simple, efficient and controllable novel MTO molecular sieve preparation route has important practical significance.
Disclosure of Invention
The invention provides a preparation method and application of a composite AEI/CHA molecular sieve. The composite AEI/CHA molecular sieve prepared by the method is used as a catalyst in a process for preparing low-carbon olefin from oxygen-containing compounds, and has excellent low-carbon olefin selectivity, particularly higher propylene selectivity and longer service life of the catalyst.
The first aspect of the present invention provides a method for preparing a composite AEI/CHA molecular sieve, wherein at least two CHA molecular sieves with defects are used as seed crystals, and the two CHA molecular sieves with defects are respectively seed crystal I and seed crystal II; the seed crystal I and the seed crystal II contain micropores, macropores and mesopores; wherein the ratio of the pore volume of the macropores and the mesopores of the seed crystal I to the total pore volume is 8% -14%; the pore volume of the seed crystal II, the macropores and the mesopores accounts for 15% -35% of the total pore volume.
In the technical scheme, the mesoporous pore diameter of the seed crystal I is distributed at 2-50 nanometers, and the pore diameter of the macropores is distributed at 50-200 nanometers; the mesoporous aperture of the seed crystal II is distributed at 2-50 nanometers, and the aperture of the macropores is distributed at 300-800 nanometers.
In the technical scheme, the mass ratio of the seed crystal I to the seed crystal II is (15-40): (60 to 85), preferably (20 to 35): (65-80).
In the technical scheme, the seed crystal I adopts the organic acid modifier I to treat and modify the CHA structure molecular sieve for 3-5 hours at the temperature of 30-48 ℃.
In the technical scheme, the seed crystal II adopts the organic acid modifier II to treat and modify the CHA structure molecular sieve for 5 to 8 hours at the temperature of between 70 and 90 ℃.
In the technical scheme, when the seed crystal I is prepared, the concentration of the organic acid in the organic acid modifier I is 0.01-0.09 mol/L.
In the technical scheme, when the seed crystal I is prepared, the mass ratio of the organic acid modifier I to the CHA structure molecular sieve dry basis is (20-50): 1.
in the technical scheme, when the seed crystal II is prepared, the concentration of the organic acid in the organic acid modifier II is 0.10-0.30 mol/L.
In the technical scheme, when the seed crystal II is prepared, the mass ratio of the organic acid modifier II to the CHA structure molecular sieve dry basis is (20-50): 1.
in the above technical scheme, the organic acid modifier is at least one of oxalic acid and citric acid.
In the technical scheme, the CHA structure molecular sieve with defects is obtained from the step of modifying the CHA structure molecular sieve through post-treatment, and defective crystals with different pore structures can be obtained by controlling the treatment conditions. The CHA structure molecular sieve is a microporous CHA structure molecular sieve, can be prepared by a conventional method, and can also be obtained by commercial purchase. The CHA structure molecular sieve can be a dried CHA structure molecular sieve containing the template agent which is completely crystallized, or can be the CHA structure molecular sieve which is subjected to high-temperature roasting to remove the template agent.
In the technical scheme, the preparation method of the composite AEI/CHA molecular sieve comprises the following steps: and adding the seed crystal into gel prepared from a silicon source, an aluminum source, a phosphorus source, a template agent and water, and crystallizing under hydrothermal conditions to obtain the composite AEI/CHA molecular sieve.
In the technical proposal, the aluminum source, the silicon source, the phosphorus source, the template agent and the water are prepared from Al 2 O 3 ：SiO 2 ：P 2 O 5 ：R：H 2 The mole ratio of O is 1: (0.05-1.5): (0.05-1.0): (1-8): (10 to 100), preferably 1: (0.2-1.2): (0.1-0.8): (2-6): (30-80); the total addition amount of the seed crystals I and II is 3% -60% of gel solid content, preferably 8% -50% by mass, wherein R is a template agent.
In the above technical scheme, the aluminum source is at least one of pseudo-boehmite or alumina, the silicon source is at least one of white carbon black or silica sol, the phosphorus source is at least one of phosphoric acid and phosphorous acid, and the template agent is at least two of N, N-diisopropylamine, tetraethylammonium hydroxide and triethylamine.
In the above technical solution, the crystallization conditions under the hydrothermal conditions are as follows: the temperature is 150 to 230 ℃, preferably 170 to 200 ℃, and the time is 10 to 35 hours, preferably 15 to 30 hours.
In the above technical scheme, the method for preparing the CHA/AEI composite molecular sieve may further include at least one of washing, drying and roasting the crystallized product according to actual needs. The washing, drying and roasting are conventional technical means in the field.
In a second aspect the invention provides a composite AEI/CHA molecular sieve prepared by the process described above, wherein the ratio of the mass content of AEI/CHA in the composite AEI/CHA molecular sieve is from 95/5 to 60/40.
In the technical scheme, in the composite AEI/CHA molecular sieve, al 2 O 3 ：P 2 O 5 ：SiO 2 The molar ratio of (2) is 1: (0.2-0.8): (0.1-0.3).
In the technical scheme, the composite AEI/CHA molecular sieve has a micropore, mesopore and macropore structure; the diameter of the micropores is not more than 1 nanometer, preferably 0.3-0.5 nanometer; the diameter of the mesopores is distributed between 8 and 50 nanometers, preferably between 10 and 30 nanometers; the diameter of the macropores is distributed between 50 and 800 nanometers, preferably between 80 and 400 nanometers.
In the technical proposal, the pore volume contributed by the micropores is 0.10cm to 0.35 cm 3 Per gram, preferably 0.18 to 0.25cm 3 /g; the pore volume contributed by the mesopores and the macropores is 0.05-0.40 cm 3 Per gram, preferably 0.10 to 0.30 cm 3 /g.
In the technical scheme, the composite AEI/CHA molecular sieve is in a cubic crystal morphology, and the crystal size is 0.1-2.0 microns.
In a third aspect, the invention provides the use of the composite AEI/CHA molecular sieve in an oxygenate to olefins reaction.
In the above technical scheme, the oxygen-containing compound is selected from methanol, ethanol, n-propanol, isopropanol, C 4-20 At least one of alcohol, methylethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, and dimethyl ketone, preferably methanol and/or dimethyl ether. The olefin comprises ethylene, propylene, or a combination thereof.
In the technical proposal, the invention adopts the composite AEI/CHA molecular sieve to react at the temperature of 200-700 ℃ and the weight hourly space velocity of 1-1000 hours when the oxygen-containing compound is used for preparing olefin -1 The pressure is 0.5 kPa-5 MPa.
The method of the invention synthesizes the composite AEI/CHA molecular sieve based on the defect position guidance in the defect crystal, and has the following advantages:
(1) The invention adopts the seed crystal I and the seed crystal II with different defects to prepare the novel composite AEI/CHA molecular sieve, and has simple operation process and easy implementation;
(2) The technology of preparing olefin from methanol has been developed to date, the yield of diene (ethylene+propylene) is generally 80% -83%, and on the basis, if the yield is increased by 0.5%, the economic benefit will be quite considerable for a ten-thousand-ton device. The composite AEI/CHA molecular sieve prepared by the method of the invention is used as a catalyst active component in the process of preparing olefin by using an oxygen-containing compound, and has good catalytic performance, the yield of diene (ethylene and propylene) can be improved by more than 1 percent, the reaction stability of the catalyst can be obviously improved by more than 10 percent, and a better technical effect is obtained.
(3) The price of the chemical raw material market is constantly changing, and MTO catalysts meeting market conditions are developed so that MTO catalysts with high ethylene yield can be used when the price of ethylene is high, and MTO catalysts with high propylene yield can be used when the price of propylene is high, so that the profit level of enterprises can be maximally improved.
Drawings
FIG. 1 is an XRD spectrum and SEM photograph of a defective crystal prepared according to example 2;
FIG. 2 is an XRD spectrum and SEM photograph of the composite molecular sieve prepared according to example 4;
FIG. 3 is an XRD spectrum and SEM photograph of the molecular sieve prepared according to [ comparative example 1 ];
fig. 4 is an XRD spectrum and SEM photograph of the composite molecular sieve prepared [ comparative example 2 ].
Detailed Description
As an embodiment of the present invention, it should be noted that the protective scope of the present invention is not limited by these specific embodiments, but is defined by the claims.
In the present invention, the pore volume, which is also referred to as pore volume, means the volume of pores of a molecular sieve per unit mass.
In the present invention, the molecular sieve (referred to as a single crystal) has a crystal morphology of a sponge structure, particularly a primary crystal morphology of a sponge structure, when observed with a Scanning Electron Microscope (SEM). The crystal morphology herein refers to the external shape exhibited by a single molecular sieve crystal in the field of view of the scanning electron microscope. The term "as-grown" means a structure which is objectively and directly represented by a molecular sieve after production, and is not a structure which is represented by a molecular sieve after production and then subjected to artificial treatment.
In the invention, XRD data are measured by using a German Brookfield AXS D8 advanced X-ray diffractometer and are used for representing the crystal structure of the molecular sieve and calculating the relative crystallinity; n (N) 2 The adsorption-desorption data are measured by an ASAP-2020 adsorption instrument of the America microphone and are used for measuring the specific surface area, pore volume and pore size distribution of the molecular sieve; the mercury intrusion data and the pore size distribution are measured by a Thermo full-automatic mercury intrusion instrument and are used for representing the macroporous pore size distribution of the molecular sieve; SEM pictures were obtained from the FEI Quanta200F field emission scanning electron microscope of the netherlands for characterizing the morphology of the molecular sieves.
The technical scheme of the invention is further described below through specific examples.
[ example 1 ]
CHA molecular sieves containing only micropores are prepared.
With silica sol (30 wt% SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) Phosphoric acid (85 wt% H) 3 PO 4 ) Respectively a silicon source, an aluminum source and a phosphorus source, and triethylamine NEt 3 Is used as a template agent, and is prepared from the following components,according to SiO 2 ：Al 2 O 3 ：P 2 O 5 ：NEt 3 ：H 2 O=1.0: 1.0:0.6:3:50, standing and aging the mixed gel in a water bath kettle at 15 ℃ for 18 hours, transferring the gel to a reaction kettle for crystallization at 200 ℃ for 48 hours, and cooling, filtering, washing, drying and roasting the crystallized product after the crystallization is finished to obtain the CHA molecular sieve which is marked as A.
XRD characterization results show that the synthesized molecular sieve has characteristic diffraction peaks of the CHA molecular sieve, and the synthesized product is a pure CHA molecular sieve; SEM pictures show that the CHA molecular sieve is cubic crystal with smooth surface.
A has a micropore volume of 0.25cm 3 And/g, wherein the pore diameter of the micropores is distributed at 0.3-0.5 nm.
From the above characterization results, it can be demonstrated that conventional microporous CHA molecular sieves are prepared that are of high crystallinity.
[ example 2 ]
The CHA structure molecular sieve with crystal defects, namely seed crystal I, is prepared.
The starting material was taken from a conventional, microporous-only CHA molecular sieve a prepared as per [ example 1 ].
30g of molecular sieve A is weighed and placed in 0.05mol/L citric acid solution, wherein the dosage of the citric acid solution is 1L, and the mixture is stirred for 4 hours at 40 ℃ and then filtered, washed and dried to obtain a product B.
B as shown in figure 1, the molecular sieve has characteristic diffraction peaks possessed by CHA molecular sieve.
B is shown in a SEM photograph of FIG. 1, the crystals of the molecular sieve have obvious pore structures, and the crystals of the molecular sieve have a large number of defects.
The pore diameter of the micropores of the B is distributed at 0.3-0.5 nm, the pore diameter of the mesopores is distributed at 15-30 nm, and the pore diameter of the macropores is distributed at 80-150 nm.
The pore volume contributed by the micropores was 0.24cm 3 Per g, pore volume of the macro-meso pore contribution of 0.03cm 3 And/g. Thus, the pore volume of the macro-mesopores was 11% of the total pore volume.
According to the characterization result, the prepared CHA molecular sieve with the multi-stage pore structure and crystal defects can be proved.
[ example 3 ]
The CHA structure molecular sieve with crystal defects, namely seed crystal II, is prepared.
The starting material was taken from a conventional, microporous-only CHA molecular sieve a prepared as per [ example 1 ].
30g of molecular sieve A is weighed and placed in 0.2mol/L citric acid solution, wherein the dosage of the citric acid solution is 0.9L, and the mixture is stirred for 6 hours at 80 ℃ and then filtered, washed and dried to obtain a product C.
The XRD spectrum of C is similar to that of B, and the molecular sieve has characteristic diffraction peaks of CHA molecular sieve.
SEM pictures of C are similar to B, with the crystals of the molecular sieve having a distinct pore structure and with the crystals of the molecular sieve having a large number of defects.
The pore diameter of the micropores of the C is distributed at 0.3-0.5 nm, the pore diameter of the mesopores is distributed at 20-40 nm, and the pore diameter of the macropores is distributed at 200-500 nm.
The pore volume contributed by the micropores was 0.20cm 3 Per g, pore volume of large-mesoporous contribution of 0.08cm 3 And/g. Thus, the proportion of the pore volume of the macro-mesopores to the total pore volume is 29%.
According to the characterization result, the prepared CHA molecular sieve with the multi-stage pore structure and crystal defects can be proved.
[ example 4 ]
Preparation of composite AEI/CHA molecular sieves
With silica sol (30 wt% SiO) 2 ) Pseudo-boehmite (70 wt% Al) 2 O 3 ) Phosphoric acid (85 wt% H) 3 PO 4 ) Respectively a silicon source, an aluminum source and a phosphorus source, and N, N-diisopropylethylamine is used as a template agent according to SiO 2 ：Al 2 O 3 ：P 2 O 5 ：C 8 H 19 N：H 2 O=0.6: 1.0:0.9:1.6:55, and finally adding seed crystals I and II prepared according to the methods of example 2 and example 3, the total amount of the seed crystals added being 10% of the solid contentWherein the mass ratio of the seed crystal I to the seed crystal II is 25:75. after adding seed crystals I and II, the mixture was crystallized at 180℃for 24 hours. After crystallization, cooling, filtering and washing the crystallized product, drying at 120 ℃ for 6 hours, and roasting at 550 ℃ for 5 hours to obtain the composite AEI/CHA molecular sieve, which is marked as D.
The XRD spectrum of D is shown in FIG. 2, and it can be seen from FIG. 2 that the synthesized molecular sieve has characteristic diffraction peaks of the CHA/AEI molecular sieve, which indicates that the synthesized product is a composite molecular sieve, and the XRD quantification method shows that the percentage of AEI structure molecular sieve in the composite molecular sieve is 93% and the percentage of CHA molecular sieve is 7%.
The SEM photograph of D is shown in fig. 2, the molecular sieve has a cubic morphology, and a large number of holes are visible in the crystal.
D, the pore diameter of the micropores is distributed at 0.3-0.5 nm, the pore diameter of the mesopores is distributed at 8-30 nm, and the pore diameter of the macropores is distributed at 80-300 nm; the pore volume contributed by the micropores was 0.20cm 3 Per g, the pore volume of the mesoporous contribution is 0.08cm 3 Per g, the macropore contributing pore volume is 0.13cm 3 /g。
According to XRD pattern, SEM picture and N 2 The results of physical adsorption and mercury intrusion characterization are sufficient to demonstrate that the prepared multi-stage pore structure composite AEI/CHA molecular sieve with a spongy structure cube morphology is prepared, wherein the ratio of AEI/CHA is 93/7.
[ example 5 ]
Preparation of composite AEI/CHA molecular sieves
As in example 4, except that seed crystals I and II were used as template removed after calcination, the resulting product was designated E.
The XRD spectrum of E is similar to that of FIG. 2, and the percentage of AEI molecular sieve in the composite molecular sieve is 91% and the percentage of CHA molecular sieve in the composite molecular sieve is 9% as determined by XRD quantification. .
E SEM photograph is similar to FIG. 2, the molecular sieve has a cubic morphology, and a large number of holes are visible in the crystal.
E micropore diameter is distributed at 0.3-0.5 nm, mesoporous pore diameter is distributed at 15-25 nm, and macroporous pore diameter is distributed at 100-250 nm; pore volume contributed by micropores0.18cm 3 Per g, the pore volume of the mesoporous contribution is 0.10cm 3 Per g, the macropore contributing pore volume is 0.15cm 3 /g。
According to XRD pattern, SEM picture and N 2 The results of physical adsorption and mercury intrusion characterization are sufficient to demonstrate that the prepared multi-stage pore structure composite AEI/CHA molecular sieve with a spongy structure cube morphology is prepared, wherein the ratio of AEI/CHA is 91/9.
[ example 6 ]
Preparation of composite AEI/CHA molecular sieves
As in [ example 4 ], the addition amount of the defective crystals was 20% of the solid content, and the resultant product was designated as F.
The XRD spectrum of F is similar to that of FIG. 2, and the percentage of AEI molecular sieve in the composite molecular sieve is 85% and the percentage of CHA molecular sieve in the composite molecular sieve is 15% as determined by XRD quantification.
The SEM photograph of F is similar to fig. 2, the molecular sieve is in a cubic morphology, and a large number of holes are visible in the crystal.
F, the pore diameter of the micropores is distributed at 0.3-0.5 nm, the pore diameter of the mesopores is distributed at 20-30 nm, and the pore diameter of the macropores is distributed at 120-300 nm; the pore volume contributed by the micropores was 0.21cm 3 Per g, the pore volume of the mesoporous contribution is 0.12cm 3 Per g, the macropore contributing pore volume is 0.13cm 3 /g。
According to XRD pattern, SEM picture and N 2 The results of physical adsorption and mercury intrusion characterization are sufficient to demonstrate that the prepared multi-stage pore structure composite AEI/CHA molecular sieve with a spongy morphology is prepared, wherein the ratio of AEI/CHA is 85/15.
[ example 7 ]
Preparation of composite AEI/CHA molecular sieves
Similarly [ example 4 ], except that the addition amount of the defective crystal was 40% of the solid content, the resultant product was designated as G.
The XRD spectrum of G is similar to that of FIG. 2, and the percentage of AEI molecular sieve in the composite molecular sieve is 68% and the percentage of CHA molecular sieve in the composite molecular sieve is 32% as determined by XRD quantification.
The SEM photograph of G is similar to fig. 2, the molecular sieve is cubic in morphology, and a large number of holes are visible in the crystal.
G micropore diameter is distributed at 0.3-0.5 nm, mesoporous pore diameter is distributed at 10-30 nm, and macroporous pore diameter is distributed at 100-400 nm; the pore volume contributed by the micropores was 0.19cm 3 Per g, the pore volume of the mesoporous contribution is 0.13cm 3 Per g, the macropore contributing pore volume is 0.16cm 3 /g。
According to XRD pattern, SEM picture and N 2 The results of physical adsorption and mercury intrusion characterization are sufficient to demonstrate that the prepared multi-stage pore structure composite AEI/CHA molecular sieve with a spongy morphology is prepared, wherein the ratio of AEI/CHA is 68/32.
[ example 8 ]
Preparation of composite AEI/CHA molecular sieves
As in example 4, except that the mass ratio of seed I to seed II was added was 32:68, the resulting product is designated H.
The XRD spectrum of H is similar to that of FIG. 2, and the percentage of AEI molecular sieve in the composite molecular sieve is 92% and the percentage of CHA molecular sieve in the composite molecular sieve is 8% by XRD quantification.
The SEM photograph of H is similar to fig. 2, the molecular sieve is in a cubic morphology, and a large number of holes are visible in the crystal.
The pore diameter of the H micropores is distributed at 0.3-0.5 nm, the pore diameter of the mesopores is distributed at 10-23 nm, and the pore diameter of the macropores is distributed at 100-350 nm; the pore volume contributed by the micropores was 0.21cm 3 Per g, the pore volume of the mesoporous contribution is 0.06cm 3 Per g, the macropore contributing pore volume is 0.10cm 3 /g。
According to XRD pattern, SEM picture and N 2 The results of physical adsorption and mercury intrusion characterization are sufficient to demonstrate that the prepared multi-stage pore structure composite AEI/CHA molecular sieve with a spongy morphology is prepared, wherein the ratio of AEI/CHA is 68/32.
Comparative example 1
As in [ example 4 ], except that no seed crystal was added during the synthesis, the resulting product was designated as I.
The XRD spectrum of I is shown in figure 3, which shows that the synthesized molecular sieve has the characteristic diffraction peak of the molecular sieve with AEI structure.
The SEM photograph of I is shown in FIG. 3, and the crystals of the molecular sieve are cubic, the grain size is 1-2 microns, and the surface is smooth.
I micropore diameter is distributed at 0.3-0.5 nm, and micropore volume contributed by micropores is 0.23cm 3 And/g, no obvious mesoporous and macroporous pore size distribution exists.
According to XRD spectra, SEM pictures and N 2 Physical adsorption characterization results prove that the prepared molecular sieve is a cubic AEI molecular sieve only containing micropores.
Comparative example 2
As in example 5, except that defect-free CHA seeds prepared in example 1 were added during the synthesis, the resulting product was designated J.
The XRD spectrum of J is shown in FIG. 4, and it can be seen from FIG. 4 that the synthesized molecular sieve has characteristic diffraction peaks of the AEI/CHA molecular sieve, which indicates that the synthesized product is a composite molecular sieve, and the XRD quantification method shows that the percentage of the AEI structure molecular sieve in the composite molecular sieve is 92% and the percentage of the CHA molecular sieve is 8%.
The SEM photograph of J is shown in FIG. 4, and the crystals of the molecular sieve are cubic, the grain size is 0.5-1 micron, and the surface of the crystals of the molecular sieve is smooth.
The pore diameter of the micropores of J is distributed at 0.3-0.5 nanometers, and no meso/macropores are distributed. The pore volume contributed by the micropores was 0.23cm 3 /g。
According to XRD spectra, SEM pictures and N 2 The results of the physical adsorption characterization are sufficient to demonstrate that the composite AEI/CHA molecular sieves are produced as cubes.
[ example 9 ]
The molecular sieves obtained in examples 4 to 8 and comparative examples 1 to 2 were each tabletted to obtain a catalyst for a methanol-to-olefin reaction. The reactor is a stainless steel pipe by adopting a fixed bed catalytic reaction device, and the process conditions used for investigation are as follows: catalyst loading 2.0g, reaction temperature 460℃and weight space velocity 3h -1 The pressure was 0.1MPa, and the evaluation results are shown in Table 1. As can be seen from Table 1, the use of the composite molecular sieve of the present invention in MTO reaction can significantly improve the yield of diene, and the catalyst has good stability.
TABLE 1
Note that: in the present invention, each product yield is by mass.
[ example 10 ]
The molecular sieve D obtained in the example 4 was tabletted, crushed to 40 to 60 mesh, and MTO catalytic performance was evaluated using a fixed bed reactor under the following process conditions: the catalyst loading was 0.3g, which was activated by nitrogen at 500℃for 2.0 hours and then cooled to 400 ℃. Methanol is carried by nitrogen, the flow rate of the nitrogen is 15mL/min, and the weight space velocity of the methanol is 2.0h -1 The resulting product was analyzed by gas chromatography and the catalyst life was 900min with a diene yield of 89.54%, with an ethylene yield of 54.37% and a propylene yield of 35.17%.

Claims (16)

1. A preparation method of a composite AEI/CHA molecular sieve, wherein at least two CHA molecular sieves with defects are used as seed crystals, and the two CHA molecular sieves with defects are respectively seed crystal I and seed crystal II; the seed crystal I and the seed crystal II contain micropores, macropores and mesopores; wherein the ratio of the pore volume of the macropores to the mesopores of the seed crystal I to the total pore volume is 8% -14%; the ratio of the pore volume of the macropores to the mesoporous accounts for 15% -35% of the total pore volume of the seed crystal II; the seed crystal I adopts an organic acid modifier I to treat and modify the CHA structure molecular sieve for 3-5 hours at the temperature of 30-48 ℃; the seed crystal II is treated with an organic acid modifier II at 70-90 ℃ for 5-8 hours to modify the CHA structure molecular sieve;
the preparation method of the composite AEI/CHA molecular sieve comprises the following steps: and adding the seed crystal into gel prepared from a silicon source, an aluminum source, a phosphorus source, a template agent and water, and crystallizing under hydrothermal conditions to obtain the composite AEI/CHA molecular sieve.
2. The method of manufacturing according to claim 1, characterized in that: in the preparation of the seed crystal I, the concentration of the organic acid in the organic acid modifier I is 0.01-0.09 mol/L; in the preparation of the seed crystal II, the concentration of the organic acid in the organic acid modifier II is 0.10-0.30 mol/L.
3. The preparation method according to claim 1 or 2, characterized in that: when the seed crystal I is prepared, the mass ratio of the organic acid modifier I to the CHA structure molecular sieve dry basis is (20-50): 1, a step of; when the seed crystal II is prepared, the mass ratio of the organic acid modifier II to the CHA structure molecular sieve dry basis is (20-50): 1.
4. a method of preparation according to claim 1 or 3, characterized in that: the organic acid modifier is at least one of oxalic acid and citric acid.
5. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the seed crystal I to the seed crystal II is (15-40): (60-85).
6. The method of manufacturing according to claim 5, wherein: the mass ratio of the seed crystal I to the seed crystal II is (20-35): (65-80).
7. The method of manufacturing according to claim 1, characterized in that: the aluminum source, the silicon source, the phosphorus source, the template agent and the water are prepared from Al 2 O 3 ：SiO 2 ：P 2 O 5 ：R：H 2 The mole ratio of O is 1: (0.05-1.5): (0.05-1.0): (1-8): (10-100), wherein the total addition amount of the seed crystals I and II is 3-60% of the solid content of the gel, and R is taken as a template agent by mass.
8. The method of manufacturing according to claim 7, wherein: the aluminum source, the silicon source, the phosphorus source, the template agent and the water are prepared from Al 2 O 3 ：SiO 2 ：P 2 O 5 ：R：H 2 The mole ratio of O is 1: (0.2 to 1.2): (0.1 to 0.8): (2-6): (30-80), wherein the total addition amount of the seed crystals I and II is 8-50% of the solid content of the gel, and R is calculated by massIs a template agent.
9. The method of manufacturing according to claim 1, characterized in that: the aluminum source is at least one of pseudo-boehmite or aluminum oxide, the silicon source is at least one of white carbon black or silica sol, the phosphorus source is at least one of phosphoric acid and phosphorous acid, and the template agent is at least two of N, N-diisopropylamine, tetraethylammonium hydroxide and triethylamine.
10. The method of manufacturing according to claim 1, characterized in that: the crystallization conditions under the hydrothermal conditions are as follows: the temperature is 150-230 ℃ and the time is 10-35 hours.
11. The method of manufacturing according to claim 10, wherein: the crystallization conditions under the hydrothermal conditions are as follows: the temperature is 170-200 ℃ and the time is 15-30 hours.
12. A composite AEI/CHA molecular sieve prepared by the process of any one of claims 1 to 11, wherein the ratio of the mass content of AEI/CHA in the composite AEI/CHA molecular sieve is 95/5 to 60/40.
13. The molecular sieve of claim 12, wherein: the composite AEI/CHA molecular sieve has a micropore, mesopore and macropore structure; the diameter of the micropores is not more than 1 nanometer, the diameter of the mesopores is distributed at 8-50 nanometers, and the diameter of the macropores is distributed at 50-800 nanometers;
the pore volume contributed by the micropores is 0.10-0.35 cm 3 Per gram, the pore volume contributed by mesopores and macropores is 0.05-0.40 cm 3 /g.
14. The molecular sieve of claim 13, wherein: the diameter of the micropores is 0.3-0.5 nanometers, the diameter of the mesopores is 10-30 nanometers, and the diameter of the macropores is 80-400 nanometers;
the pore volume contributed by the micropores is 0.18-0.25 cm 3 Per gram, the mesopore and macropore contributing pore volume is 0.100.30 cm 3 /g.
15. The molecular sieve of claim 12, wherein: the composite AEI/CHA molecular sieve is in a cubic crystal morphology, and the crystal size is 0.1-2.0 microns.
16. The use of the AEI/CHA composite molecular sieve of any one of claims 12 to 15 in an oxygenate to olefins reaction.
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