CN111115657A - Molecular sieve material with alkaline molecules enriched on surface layer, and preparation method and application thereof - Google Patents

Molecular sieve material with alkaline molecules enriched on surface layer, and preparation method and application thereof Download PDF

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CN111115657A
CN111115657A CN201811285689.1A CN201811285689A CN111115657A CN 111115657 A CN111115657 A CN 111115657A CN 201811285689 A CN201811285689 A CN 201811285689A CN 111115657 A CN111115657 A CN 111115657A
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molecular sieve
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surface layer
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basic
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CN111115657B (en
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孙毯毯
徐舒涛
魏迎旭
刘中民
韩晶峰
桑石云
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Dalian Institute of Chemical Physics of CAS
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    • Y02P30/40—Ethylene production

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Abstract

The application discloses a molecular sieve material with a surface layer enriched with alkaline molecules, a preparation method thereof and application of the molecular sieve material in preparation of olefin through conversion of an oxygen-containing compound. The molecular sieve material with the enriched alkaline molecules on the surface layer comprises alkaline molecules M; the mole fraction n of the alkaline molecules M on the surface layer of the molecular sieve materialM surHigher than the basic moleculeMole fraction n in the bulk phase of the molecular sieve materialM total. The molecular sieve material with the surface layer enriched with alkaline molecules can change the diffusion performance of molecules in the molecular sieve, change the product distribution in the reaction of preparing olefin by converting oxygen-containing compounds and achieve the aim of regulating and controlling the product selectivity.

Description

Molecular sieve material with alkaline molecules enriched on surface layer, and preparation method and application thereof
Technical Field
The application relates to a molecular sieve material with a surface layer enriched with alkaline molecules, a preparation method thereof and application thereof in a reaction for preparing olefin from an oxygen-containing compound, belonging to the field of catalysis.
Background
The low-carbon olefins (ethylene, propylene and butylene) are important organic chemical raw materials and play a significant role as important intermediate products in the modern petrochemical industry. China is rich in coal and less in oil, and the olefin production with naphtha as a main raw material is seriously limited by raw material supply, so that the requirement of rapid economic development can not be completely met. The Methanol To Olefin (MTO) technology enables coal chemical products to be directly butted with downstream petrochemical enterprises, so that the economic benefit of the coal chemical enterprises is improved, basic raw materials are provided for the downstream petrochemical enterprises, and the economic development is greatly promoted.
The catalyst is the core of research and development of methanol-to-olefin technology, and researchers developed methanol-to-olefin catalysts based on molecular sieve acid catalysis from early-stage silicoaluminophosphate molecular sieves to SAPO-series silicoaluminophosphate molecular sieves. Researchers of the institute of chemical and physical sciences of the Chinese academy of sciences have developed a fluidized bed DMTO technology aiming at the characteristics of high selectivity and short service life of low-carbon olefin of the SAPO-34 catalyst (WO2008019593A1 and WO2008025247A 1). The fluidized bed DMTO technology fully utilizes the advantage of high selectivity of the low-carbon olefin caused by the SAPO-34 eight-membered ring orifice, simultaneously utilizes the cyclic regeneration process to keep the catalytic reaction activity, and has good commercial value, thereby being popularized in a large scale in the whole country. In a fluidized bed reactor, there is a distribution of catalyst particles at different residence times; in the MTO reaction, catalyst particles staying in a reactor for a certain time or pre-deposited carbon catalyst particles have certain carbon deposition as a reaction active center and provide diffusion limitation on products, so that the selectivity of low-carbon olefin is high and can reach 80-90%; the fresh fluidized bed MTO catalyst does not have organic matter carbon deposit as an active center and provides diffusion limitation, so that the selectivity of low-carbon olefin in the initial reaction stage is low, the selectivity of ethylene and propylene on the fresh catalyst is only about 60 percent, and the selectivity is 20 percent lower than the highest low-carbon olefin of the carbon deposit catalyst. Due to the presence of fresh catalyst, active catalyst and the distribution of catalyst that is about to be deactivated in the fluidized bed reactor, the total low carbon olefin selectivity is only 80% during the fluidized bed cycle. Therefore, the performance of commercial fluidized bed catalysts, especially the initial low carbon olefin selectivity, still leaves room for improvement.
In view of the extremely strong diffusion limitation of the molecular sieve on the reaction product of preparing the olefin from the methanol, researchers propose a method for utilizing the regenerated carbon residue and the pre-deposited carbon in order to improve the initial low-carbon olefin selectivity of the catalyst. The patent CN104672044B, WO2015081489a1, proposes the idea of pre-carbon deposition. The method utilizes the limitation of carbon deposition enhancing pore channels converted from a part of methanol or olefin products with high carbon number to products, improves the selectivity of the initial low-carbon olefin to a certain extent, but has the cost of losing a part of reaction raw materials or products, and has high requirements on the operation process and certain technical difficulty.
Disclosure of Invention
According to one aspect of the present application, a molecular sieve material enriched in basic molecules at the surface layer is provided. Alkaline molecules are introduced into the surface layer of the molecular sieve for modification, so that Bronsted acid sites on the surface layer of the molecular sieve are occupied, and the diffusion performance and the reaction performance of the molecular sieve are improved, so that the diffusion performance of a catalytic reaction product in the molecular sieve is changed, and the method can be used for solving the problems of low carbon selectivity and low ethylene selectivity of a catalyst in the prior art of preparing olefin from methanol.
The molecular sieve material with the surface layer enriched with alkaline molecules can change the diffusion performance of molecules in the molecular sieve, change the product distribution in the reaction of preparing olefin by converting oxygen-containing compounds and achieve the aim of regulating and controlling the product selectivity.
The molecular sieve material with the enriched alkaline molecules on the surface layer contains alkaline molecules M;
the mole fraction n of the alkaline molecules M on the surface layer of the molecular sieve materialM surHigher than the mole fraction n of the basic molecules in the bulk phase of the molecular sieve materialM total。
The mole fraction of basic molecules in the bulk phase of the M molecular sieve material is the overall mole fraction of basic molecules M in the molecular sieve material.
The alkaline molecules M are enriched on the surface layer of the particles of the molecular sieve material, and the content of the alkaline molecules M is gradually reduced along the surface layer of the particles of the molecular sieve material towards the inside.
Alternatively, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total≥2。
Alternatively, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total＝2～100。
Alternatively, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total＝2～10。
Alternatively, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total＝2～6。
Alternatively, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalThe upper limit of the ratio is selected from 2.5, 3, 3.19, 3.28, 3.4, 3.8, 4, 4.25, 4.75, 5, 5.5, 6, 8, 10, 20, 50, 80, or 100; the lower limit is selected from 2, 2.5, 3, 3.19, 3.28, 3.4, 3.8, 4, 4.25, 4.75, 5, 5.5, 6, 8, 10, 20, 50, or 80.
Optionally, the basic molecule M is selected from at least one of organic basic molecules.
Optionally, the basic molecule M is selected from at least one of nitrogen-containing, phosphorus-containing, carbon-containing basic molecules.
Optionally, the basic molecule M is selected from at least one of pyridine, trimethylphosphine, triethylphosphine, acetone, acetonitrile.
Alternatively, the basic molecule M is trimethyl phosphine oxide and acetonitrile.
Optionally, the molecular sieve in the molecular sieve material with the surface layer rich in alkaline molecules is selected from at least one of SAPO-17 molecular sieve, SAPO-18 molecular sieve, SAPO-34 molecular sieve, SAPO-35 molecular sieve, SAPO-44 molecular sieve, SAPO-56 molecular sieve, SAPO-47 molecular sieve, DNL-6 molecular sieve and SSZ-13 molecular sieve.
According to another aspect of the present application, a method for preparing a molecular sieve material with a surface layer enriched with basic molecules is provided.
The preparation method of the molecular sieve material with the surface layer enriched with alkaline molecules comprises the following steps:
a) heating the molecular sieve at 300-500 ℃ under a vacuum condition to obtain a sample I;
b) heating a mixture containing the sample I, the alkaline molecules and the auxiliary agent under a sealed condition to obtain a sample II;
c) and heating the sample II under a vacuum condition to obtain the molecular sieve material with the surface layer enriched with alkaline molecules.
Optionally, the molecular sieve in step a) is a template-removing molecular sieve.
Optionally, the molecular sieve in step a) is a molecular sieve subjected to calcination to remove the template agent.
Optionally, the heating time in the step a) is 1-48 h.
Optionally, the upper limit of the temperature of the heating in step a) is selected from 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃ or 500 ℃; the lower limit is selected from 300 deg.C, 320 deg.C, 350 deg.C, 380 deg.C, 400 deg.C, 420 deg.C, 450 deg.C or 480 deg.C.
Optionally, the heating temperature in the step a) is 400-420 ℃.
Optionally, the molar ratio of the basic molecule M to the adjuvant in step b) is 0.01-100.
Alternatively, the upper limit of the molar ratio of the basic molecule M and the adjuvant in step b) is selected from 0.1, 0.5, 0.8, 0.9, 0.95, 0.98, 1, 1.2, 1.5, 1.8, 2, 5, 10, 20, 30, 50, 80 or 100; the lower limit is selected from 0.01, 0.1, 0.5, 0.8, 0.9, 0.95, 0.98, 1, 1.2, 1.5, 1.8, 2, 5, 10, 20, 30, 50, or 80.
Optionally, the molar amount of the basic molecule M in the step b) is 0.01 to 100 times of the amount of the Bronsted acid contained in the sample I.
Alternatively, the molar amount of the basic molecule M in step b) is such that the upper limit of the amount of Bronsted acid contained in the sample I is selected from 0.1, 0.5, 0.8, 0.9, 0.95, 0.98, 1, 1.2, 1.5, 1.8, 2, 5, 10, 20, 30, 50, 80 or 100; the lower limit is selected from 0.01, 0.1, 0.5, 0.8, 0.9, 0.95, 0.98, 1, 1.2, 1.5, 1.8, 2, 5, 10, 20, 30, 50, or 80.
Optionally, the molar amount of the basic molecule M in the step b) is 1-2 times of the amount of the Bronsted acid contained in the sample I.
Optionally, the molar ratio of the basic molecule M to the adjuvant in the step b) is 1-2.
Optionally, the adjuvant in step b) is selected from at least one of carbon dioxide, water, hydrogen chloride, methane, ethane.
Optionally, the adjuvants in step b) are carbon dioxide and ethane.
Optionally, the heating temperature in the step b) is 30-600 ℃, and the heating time is 0.1-100 h.
Optionally, the upper limit of the temperature of the heating in step b) is selected from 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, 380 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃ or 600 ℃; the lower limit is selected from 30 deg.C, 50 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 250 deg.C, 380 deg.C, 300 deg.C, 320 deg.C, 350 deg.C, 380 deg.C, 400 deg.C, 420 deg.C, 450 deg.C, 480 deg.C, 500.
Optionally, the upper limit of the time of heating in step b) is selected from 0.5h, 1h, 1.5h, 2.0h, 2.5h, 3.0h, 4.0h, 5.0h, 6.0h, 8.0h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h or 90 h; the lower limit is selected from 0.1h, 0.5h, 1h, 1.5h, 2.0h, 2.5h, 3.0h, 4.0h, 5.0h, 6.0h, 8.0h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h or 90 h;
optionally, the heating temperature in the step b) is 100-600 ℃, and the heating time is 0.1-12 h.
Optionally, the heating temperature in step c) is 150-300 ℃.
Optionally, the upper limit of the temperature of the heating in step c) is selected from 150 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃, 280 ℃ or 300 ℃; the lower limit is selected from 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 250 deg.C or 280 deg.C.
Optionally, the heating time in step c) is the time for removing the basic molecule M physically adsorbed by the auxiliary agent and the molecular sieve. Specifically, the time varies depending on the amounts of the adjuvant and the basic molecule M added.
Optionally, the vacuum condition in step a) and step c) is a pressure of 10-3～10-5Pa。
As an embodiment, the method comprises the steps of:
1) roasting the molecular sieve, then loading the molecular sieve into a dehydration tube, and heating the molecular sieve to 300-500 ℃ under a vacuum-pumping condition to obtain a sample I; the molecular sieve is a molecular sieve for removing part of the template agent and/or a molecular sieve for removing all the template agent;
2) introducing alkaline molecules and an auxiliary agent into the dehydration tube filled with the sample I in the step 1), and sealing the dehydration tube;
3) heating the sealed dehydration tube obtained in the step 2) to obtain a sample II;
4) and (3) heating the sample II prepared in the step 3) under a vacuum condition to remove the auxiliary agent and the physically adsorbed alkaline molecules, so as to obtain the molecular sieve material with the surface layer enriched with the alkaline molecules.
As an embodiment, the method comprises the steps of:
a1) roasting the molecular sieve, then loading the molecular sieve into a dehydration tube, and heating the molecular sieve to 300-500 ℃ under a vacuum-pumping condition to remove adsorbates such as water adsorbed by the molecular sieve, thereby obtaining a sample I; the molecular sieve is a molecular sieve for removing part of the template agent and/or a molecular sieve for removing all the template agent;
b1) introducing a certain amount of basic molecules and adjuvants into the dehydration tube loaded with the sample I in the step a1), and sealing the dehydration tube;
c1) heating the sealed dehydration tube obtained in the step b1) in a muffle furnace to obtain the molecular sieve material with the surface layer enriched with alkaline molecules;
d1) heat-treating the molecular sieve material enriched in basic molecules on the surface layer prepared in step c1) under vacuum to remove the auxiliary agent and the physically adsorbed basic molecules.
In one embodiment, the dehydration tube of step a1) is made of glass, quartz or steel material.
Optionally, in the step) under the vacuum condition, the desorption temperature for heating and removing adsorbates such as water and the like adsorbed on the surface layer of the molecular sieve is 400-420 ℃.
In one embodiment, the molar ratio of the basic molecule and the auxiliary in step b1) is 0.01 to 100.
In one embodiment, the amount of the basic molecule in step b1) is 0.01 to 100 times the amount of Bronsted acid in the molecular sieve sample.
In one embodiment, the adjuvant in step b1) is carbon dioxide (CO)2) Water (H)2O), hydrogen chloride (HCl), methane (CH)4) Ethane (CH)3CH3) Any one or more of them are mixed.
As an embodiment, the molecular sieve in the molecular sieve material with the surface layer rich in alkaline molecules is at least one selected from SAPO-17 molecular sieve, SAPO-18 molecular sieve, SAPO-34 molecular sieve, SAPO-35 molecular sieve, SAPO-44 molecular sieve, SAPO-56 molecular sieve, SAPO-47 molecular sieve, DNL-6 molecular sieve and SSZ-13 molecular sieve.
In one embodiment, the temperature in the muffle furnace in the step c1) is 30-600 ℃, and the treatment time is 0.1-100 h.
Optionally, the treatment temperature is more than or equal to 100 ℃, and the treatment time is less than or equal to 12 h.
As an embodiment, the heating temperature of the desorption assistant and the physisorbed basic molecules in the step d1) is 150 to 300 ℃.
According to yet another aspect of the present application, the basic molecular modified molecular sieve catalyst prepared by the present invention is used in a reaction for producing olefins by converting oxygenates.
Optionally, the molecular sieve catalyst containing basic molecules is applied to the reaction of preparing olefin from methanol and/or dimethyl ether.
In one embodiment, the reactor for the application of the molecular sieve with the enriched basic molecules on the surface layer in the reaction for preparing olefin from oxygen-containing compounds is at least one selected from a fluidized bed, a fixed bed and a moving bed.
In the present application, the "vacuum condition" is 10-3～10-5Pa。
The beneficial effects that this application can produce include:
1) the molecular sieve material with the surface layer enriched with alkaline molecules improves the diffusion performance and the reaction performance of the molecular sieve by introducing alkaline molecule modification to the surface layer of the molecular sieve, thereby changing the diffusion performance of a catalytic reaction product in the molecular sieve material, and being capable of being used for solving the problems of low selectivity of low-carbon olefin and low selectivity of ethylene in the early stage of catalyst reaction in the existing methanol-to-olefin technology.
2) The preparation method of the molecular sieve material with the surface layer enriched with the alkaline molecules is simple in process, easy for large-scale industrial production and easy for accurate control of the loading amount of the alkaline molecules.
3) The catalyst and the modified catalyst for preparing olefin from oxygen-containing compound are provided by the application. The surface layer is enriched with alkaline molecules, the use of the catalyst can change the diffusion performance of the molecules in the catalyst, and the catalyst is used for the reaction of preparing olefin from methanol, and has higher low-carbon olefin selectivity and ethylene selectivity at the initial stage; and the selectivity of the low-carbon olefin at the highest selectivity (before deactivation) and the selectivity of ethylene are equivalent to those before modification.
4) The catalyst and the modified catalyst for preparing olefin from oxygen-containing compound have excellent structural stability.
Drawings
FIG. 1 shows blank SAPO-34 samples and sample 3#Wherein (a) is a fluorescence image of a blank SAPO-34 sample, and (b) is sample 3#Fluorescence imaging of (1).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The SAPO-18 molecular sieves used in the examples were prepared according to the procedures described in the Catal. letters, 1994,241 reference, unless otherwise specified; SAPO-34 molecular sieves were purchased from Nankai catalyst works; the DNL-6 molecular sieve was prepared according to the method in chem. mater.2011,23,1406; the molecular sieves are not directly used after special treatment.
The analysis method in the examples of the present application is as follows:
the morphology of a Scanning Electron Microscope (SEM) and the elemental analysis of an energy dispersive X-ray spectrum (EDX) adopt a Hitachi SU8020 type desk-top scanning electron microscope.
The elemental composition was determined using a Philips Magix 2424X-ray fluorescence Analyzer (XRF). The bulk mole fraction of the sample was obtained from the XRF data.
Magnetic resonance analysis was performed using an Infinity plus 600WB solid-state nuclear magnetic spectrometer from Bruker, Germany, using a 4mm HXY MAS probe at a magnetic field strength of 14.1T.
The fluorescence spectrum analysis adopts an ultra-high resolution fluorescence spectrometer of Nikon N-SIM system, and the laser excitation wavelength is 405 nm.
Example 1 sample 1#Preparation, characterization and reaction evaluation of
Sample preparation: and roasting the SAPO-34 molecular sieve for 4H at 550 ℃ in an air atmosphere to obtain the H-type molecular sieve (H-SAPO-34). Placing 0.5g of the roasted SAPO-34 molecular sieve in a glass dehydration tube under vacuum condition (<10-3Pa), dehydrating at 420 ℃ for 12 h. Pyridine and the molecular sieve Bronsted acid in the same amountAuxiliary water with the same amount of molecular sieve Bronsted acid is respectively placed in dehydration tubes in liquid nitrogen, then the dehydration tube valves are closed to form a closed space, and the sealed space is placed in a muffle furnace for treatment at 300 ℃ for 4 hours after standing for 1 hour at room temperature. Taking out, treating at 200 ℃ for 2h under vacuum condition to remove auxiliary agent and physically adsorbed alkaline molecules, and obtaining the molecular sieve material sample with the surface layer enriched with alkaline molecules, and recording as sample 1#。
Preparation of blank SAPO-34 molecular Sieve sample the same as sample 1#Except that the basic molecule and the adjuvant are not added.
Catalyst characterization: the mole fractions of basic molecules in the surface layer and the bulk phase of the catalyst sample are respectively measured by adopting EDX, XRF and solid nuclear magnetism, and the adsorption quantity of the basic molecules is determined, and the results are shown in the table 1; the distribution of basic molecules in the catalyst was determined by ultra-high resolution fluorescence spectroscopy, and the results are shown in fig. 1. Sample 1#，nM sur/nM total＝4.75。
TABLE 1 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
1# 41.8 8.8 0.46
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
The fluorescence spectrum result shows that the blank SAPO-34 molecular sieve sample which does not adsorb pyridine has no fluorescence signal, and the profile can be only barely seen, as shown in a (a) diagram in FIG. 1. Catalyst sample 3 after pyridine modification#There is a strong fluorescence signal and it can be clearly seen that pyridine is mainly distributed in the outer shell layer of the molecular sieve crystal, as shown in (b) of fig. 1.
And (3) reaction evaluation: 475 ℃ C, fixed bed, 0.1g catalyst, 2h-1And sampling after feeding for 2min, and analyzing by adopting an online gas chromatography, wherein the reaction results are shown in Table 2.
TABLE 2 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 1#
CH4 1.7 3.2
C2H4 23.1 54.7
C2H6 0.3 0.9
C3H6 47.3 31.0
C3H8 4.3 1.36
C4 15.5 6.5
C5 6.9 2.1
C6 0.9 0.3
Sel.(C2 ＝+C3 ＝) 70.4 85.7
Note: 1. reaction 2min data.
As can be seen from table 2: modified 1 compared with unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 15.3 percent.
Example 2 sample 2#Preparation, characterization and reaction evaluation of
Sample preparation: according to the method of example 1, the molecular sieve material sample with the enriched alkaline molecules on the surface layer is obtained by only adjusting the treatment temperature in the muffle furnace to 200 ℃ and the other steps are the same, and the sample is recorded as sample 2#。
Catalyst characterization: the same as in example 1, the characterization results are shown in Table 3. Sample 2#，nM sur/nM total＝4。
TABLE 3 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
2# 13.2 3.3 0.19
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism;
and (3) reaction evaluation: the reaction results are shown in Table 4, in the same manner as in example 1.
TABLE 4 initial reaction results for methanol conversion to olefins
Figure BDA0001848980090000091
Figure BDA0001848980090000101
Note: 1. reaction 2min data.
Slave watchIn 4, it can be seen that: modified 2 compared with unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 10.2 percent.
Example 3 sample 3#Preparation, characterization and reaction evaluation of
Sample preparation: according to the method of example 1, the molecular sieve material sample with the enriched alkaline molecules on the surface layer is obtained by adjusting the treatment temperature to 100 ℃ in the muffle furnace and the other steps are the same, and the sample is marked as sample 3#。
Catalyst characterization: the same as in example 1, the characterization results are shown in Table 5. Sample 3#，nM sur/nM total＝3。
TABLE 5 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
3# 3.3 1.1 0.06
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the reaction results are shown in Table 6, as in example 1.
TABLE 6 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 3#
CH4 1.7 2.3
C2H4 23.1 39.3
C2H6 0.3 0.5
C3H6 47.3 39.6
C3H8 4.3 1.8
C4 15.5 11.9
C5 6.9 4.1
C6 0.9 0.5
Sel.(C2 ＝+C3 ＝) 70.4 78.9
Note: 1. reaction 2min data.
As can be seen from table 6: modified 3 compared with unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 8.5 percent.
Example 4 sample 4#Preparation, characterization and reaction evaluation of
Sample preparation: following the procedure of example 1, the same procedure was followed except for replacing an equal amount of pyridine with an equal amount of trimethylphosphine to obtain a sample of the molecular sieve material enriched in basic molecules on the surface layer, which is designated as sample 4#。
Catalyst characterization: the same as in example 1, the characterization results are shown in Table 7. Sample No. 4#，nM sur/nM total＝3.4。
TABLE 7 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
4# 18.7 5.5 0.17
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the reaction results are shown in Table 8, in the same manner as in example 1.
TABLE 8 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 4#
CH4 1.7 3.4
C2H4 23.1 54.5
C2H6 0.3 0.8
C3H6 47.3 31.2
C3H8 4.3 1.3
C4 15.5 6.3
C5 6.9 2.3
C6 0.9 0.3
Sel.(C2 ＝+C3 ＝) 70.4 85.7
Note: 1. reaction 2min data.
As can be seen from table 8: modified 4 compared with unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 15.3 percent.
Example 5 sample 5#Preparation, characterization and reaction evaluation of
Sample preparation: according to the method of example 1, the same amount of pyridine is changed into the same amount of trimethylphosphine, the temperature of the treated material in a muffle furnace is adjusted to 200 ℃, other steps are the same, and the molecular sieve material sample with the surface layer enriched with alkaline molecules is obtained and is marked as sample 5#。
Catalyst characterization: the same example 1, the characterization results are shown in Table 9. Sample No. 5#，nM sur/nM total＝3。
TABLE 9 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
5# 9.9 3.3 0.08
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism;
and (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 10.
TABLE 10 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 5#
CH4 1.7 2.9
C2H4 23.1 45.5
C2H6 0.3 0.5
C3H6 47.3 36.1
C3H8 4.3 1.4
C4 15.5 9.8
C5 6.9 3.5
C6 0.9 0.3
Sel.(C2 ＝+C3 ＝) 70.4 81.6
Note: 1. reaction 2min data.
As can be seen from table 10: modified 5 compared to unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 10.2 percent.
Example 6 sample 6#Preparation, characterization and reaction evaluation of
Sample preparation: according to the method of example 1, the same amount of pyridine is changed into the same amount of trimethylphosphine, the temperature of the muffle furnace is adjusted to 100 ℃, other steps are the same, and the molecular sieve material sample with the surface layer enriched with alkaline molecules is obtained and is recorded as sample 6#。
Catalyst characterization: the results of characterization are shown in Table 11, as in example 1. Sample No. 6#，nM sur/nM total＝2。
TABLE 11 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
6# 2.2 1.1 0.03
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 12.
TABLE 12 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 6#
CH4 1.7 2.5
C2H4 23.1 39.1
C2H6 0.3 0.4
C3H6 47.3 39.8
C3H8 4.3 1.7
C4 15.5 11.7
C5 6.9 4.3
C6 0.9 0.5
Sel.(C2 ＝+C3 ＝) 70.4 78.9
Note: 1. reaction 2min data.
As can be seen from table 12: modified 6 compared with unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 8.5 percent.
Example 7 sample 7#Preparation, characterization and reaction evaluation of
Sample preparation: the molecular sieve was replaced with DNL-6 and the other steps were the same as in example 1 to obtain a sample of the molecular sieve material enriched in basic molecules on the surface layer, which was designated as sample 7#。
Catalyst characterization: same as example 1, tableThe results of characterization are shown in Table 13. Sample 7#，nM sur/nM total＝5。
TABLE 13 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
7# 45.1 9.9 0.56
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism;
and (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 14.
TABLE 14 initial reaction results for methanol conversion to olefins
Figure BDA0001848980090000131
Figure BDA0001848980090000141
Note: 1. reaction 2min data.
As can be seen from table 14: modified 7 compared to unmodified H-DNL-6#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 11.4 percent.
Example 8 sample 8#Preparation, characterization and reaction evaluation of
Sample preparation: the procedure of example 1 was followed, replacing the molecular sieve with DNL-6 and the same amount of pyridine with the same amount of trimethylphosphine, and the other steps were the same, to obtain a sample of the molecular sieve material enriched in basic molecules on the surface layer, designated as sample 8#。
Catalyst characterization: the results of characterization are shown in Table 15, as in example 1. Sample 8#，nM sur/nM total＝4.25。
TABLE 15 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
8# 18.7 4.4 0.22
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in example 1 are shown in Table 16.
TABLE 16 initial reaction results for methanol conversion to olefins
Product distribution1 H-DNL-6 8#
CH4 2.3 1.5
C2H4 23.0 41.2
C2H6 0.9 0.2
C3H6 45.2 40.3
C3H8 5.3 3.5
C4 13.5 9.3
C5 7.6 3.9
C6 2.2 0.1
Sel.(C2 ＝+C3 ＝) 68.2 81.5
Note: 1. reaction 2min data.
As can be seen from table 16: modified 8 compared to unmodified H-DNL-6#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 13.3 percent.
Example 9 sample 9#Preparation, characterization and reaction evaluation of
Sample preparation: according to the method of the embodiment 1, the molecular sieve is replaced by SAPO-18, other steps are the same, and the molecular sieve material sample with the surface layer being enriched with alkaline molecules is obtained and recorded as the sample 9#。
Catalyst characterization: the results of characterization are shown in Table 17, as in example 1. Sample 9#，nM sur/nM total＝3.8。
TABLE 17 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
9# 20.9 5.5 0.28
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 18.
TABLE 18 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-18 9#
CH4 3.7 4.2
C2H4 18.7 26.6
C2H6 4.0 2.6
C3H6 38.2 39.5
C3H8 7.8 7.5
C4 15.6 10.6
C5 8.7 6.9
C6 3.3 2.1
Sel.(C2 ＝+C3 ＝) 56.9 66.1
Note: 1. reaction 2min data.
As can be seen from table 18: modified 9 compared to unmodified H-SAPO-18#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 9.2 percent.
Example 10 sample 10#Preparation, characterization and reaction evaluation of
Sample preparation: following the procedure of example 1, the molecular sieves were exchanged for SAPO-18 and the equivalent amount of pyridine was exchanged forThe same amount of trimethylphosphine is obtained, other steps are the same, and the molecular sieve material sample with the surface layer enriched with alkaline molecules is obtained and is recorded as a sample 10#。
Catalyst characterization: the results of characterization are shown in Table 19, as in example 1. Sample 10#，nM sur/nM total＝3.8。
TABLE 19 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
10# 20.9 5.5 0.28
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 20.
TABLE 20 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-18 10#
CH4 3.7 3.9
C2H4 18.7 28.1
C2H6 4.0 3.2
C3H6 38.2 40.5
C3H8 7.8 6.2
C4 15.6 9.8
C5 8.7 6.4
C6 3.3 1.9
Sel.(C2 ＝+C3 ＝) 56.9 68.6
Note: 1. reaction 2min data.
As can be seen from table 20: modified 10 compared to unmodified H-SAPO-18#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 11.7 percent.
Example 11 sample 11#Preparation, characterization and reaction evaluation of
Sample preparation: the molecular sieve was replaced with DMTO fluidized bed catalyst according to the method of example 1, and the other steps were the same, to obtain a sample of the molecular sieve material with the surface layer enriched with basic molecules, which was denoted as sample 11#。
Catalyst characterization: the results of characterization are shown in Table 21, as in example 1. Sample 11#，nM sur/nM total＝3.8。
TABLE 21 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
11# 20.9 5.5 0.28
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 22.
TABLE 22 initial reaction results for methanol conversion to olefins
Product distribution1 DMTO 11#
CH4 1.6 1.1
C2H4 25.0 34.5
C2H6 0.2 0.4
C3H6 41.7 38.9
C3H8 2.3 3.3
C4 14.0 13.6
C5 11.5 5.8
C6 3.4 0.9
Sel.(C2 ＝+C3 ＝) 66.7 73.4
Note: 1. reaction 2min data.
As can be seen from table 22: modified 11 compared to unmodified DMTO fluidized bed catalyst#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 6.7 percent.
Example 12 sample 12#Preparation, characterization and reaction evaluation of
Sample preparation: the procedure of example 1 was followed, replacing the molecular sieve with DMTO fluidized bed catalyst and the same amount of pyridine with the same amount of trimethylphosphine, and the other steps were the same, to obtain a sample of the molecular sieve material enriched in basic molecules on the surface layer, which was designated as sample 12#。
Catalyst characterization: the results of characterization are shown in Table 23, as in example 1. Sample 12#，nM sur/nM total＝3.8。
TABLE 23 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
12# 20.9 5.5 0.28
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in the same manner as in example 1 are shown in Table 24.
TABLE 24 initial reaction results for methanol conversion to olefins
Figure BDA0001848980090000171
Figure BDA0001848980090000181
Note: 1. reaction 2min data.
As can be seen from table 24: modified 12 compared to unmodified DMTO fluidized bed catalyst#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 2.7 percent.
Example 13 sample 13#Preparation, characterization and reaction evaluation of
Sample preparation: following the procedure of example 1, the adjuvant was changed to the same amount of hydrogen chloride and the pyridine was changed to the same amounts of trimethylphosphine oxide and acetonitrile 1: 1, and the other steps are the same, so as to obtain the molecular sieve material sample with the surface layer enriched with alkaline molecules, and the sample is recorded as a sample 13#。
Catalyst characterization: the results of characterization are shown in Table 25, as in example 1. Sample 13#，nM sur/nM total＝3.28。
TABLE 25 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
13# 10.5 3.2 0.18
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in example 1 are shown in Table 26.
TABLE 26 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 13#
CH4 1.6 0.9
C2H4 25.0 30.4
C2H6 0.2 0.4
C3H6 41.7 40.1
C3H8 2.3 3.6
C4 14.0 15.4
C5 11.5 7.3
C6 3.4 1.3
Sel.(C2 ＝+C3 ＝) 66.7 70.5
Note: 1. reaction 2min data.
As can be seen from table 26: modified 13 compared to unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 3.8 percent.
Example 14 sample 14#Preparation, characterization and reaction evaluation of
Sample preparation: the procedure of example 1 was followed, with the adjuvants replaced with equal amounts of carbon dioxide and ethane 1: 1, and replacing pyridine with equal amount of triethyl phosphine oxide, wherein other steps are the same, and obtaining a molecular sieve material sample with the surface layer enriched with alkaline molecules, and recording the sample as a sample 14#。
Catalyst characterization: the results of characterization are shown in Table 27, as in example 1. Sample 14#，nM sur/nM total＝3.19。
TABLE 27 basic molecular distribution and adsorption Capacity
Sample (I) nM sur(％)1 nM total(％)2 Basic molecular adsorption weight (mmol/g)3
14# 15.3 4.8 0.24
Note: 1. determined by EDX; 2. determined by XRF; 3. determined by solid nuclear magnetism.
And (3) reaction evaluation: the results of the reaction in example 1 are shown in Table 28.
TABLE 28 initial reaction results for methanol conversion to olefins
Product distribution1 H-SAPO-34 14#
CH4 1.6 0.5
C2H4 25.0 31.4
C2H6 0.2 0.3
C3H6 41.7 41.1
C3H8 2.3 3.1
C4 14.0 14.4
C5 11.5 6.3
C6 3.4 2.3
Sel.(C2 ＝+C3 ＝) 66.7 72.5
Note: 1. reaction 2min data.
As can be seen from table 28: modified 14 compared to unmodified H-SAPO-34#Sample initial olefin (C)2 ＝+C3 ＝) The selectivity is obviously improved by 5.8 percent.
Example 15 sample 15#～24#Preparation, characterization and reaction evaluation of
Sample preparation: the process according to example 1, with the difference that,
the temperature for dehydration in example 1 was changed to 200 ℃ and the sample obtained was recorded as 15#；
The temperature for dehydration in example 1 was changed to 500 ℃ and the sample obtained was recorded as 16#；
The temperature of the muffle furnace treatment in example 1 was changed to 30 ℃ and the sample obtained was recorded as 17#；
The temperature of the muffle furnace treatment in example 1 was changed to 600 ℃ and the sample obtained was recorded as 18#；
The muffle furnace treatment time in example 1 was changed to 0.1h, and the obtained sample was recorded as 19#；
The muffle furnace treatment time in example 1 was changed to 100h, and the obtained sample was recorded as 20#；
The temperature of the removal aid and the physisorbed basic molecules in example 1 was changed to 150 hours, and the obtained sample was recorded as 21#；
The temperature of the removal aid and the physisorbed basic molecules in example 1 was changed to 300h and the sample obtained was recorded as 22#；
The amount of the adjuvant added in example 1 was changed to 2 times the amount of Bronsted acid of molecular sieve, and the obtained sample was recorded as 23#；
The amount of basic molecule added in example 1 was changed to 2 times the amount of Bronsted acid of the molecular sieve, and the resulting sample was recorded as 24#；
For sample 15#～24#Characterization and performance tests were performed and the results showed that sample 15 was tested#～24#Are all in contact with sample 1#The distribution and adsorption capacity of basic molecules are similar; the initial reaction results for the methanol conversion to olefins are also similar.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims. Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The molecular sieve material with the enriched alkaline molecules on the surface layer is characterized by comprising alkaline molecules M;
the mole fraction n of the alkaline molecules M on the surface layer of the molecular sieve materialM surA mole fraction n higher than that of the basic molecule M in the bulk phase of the molecular sieve materialM total；nMIs the ratio of the amount of material of basic molecules M adsorbed within a particular region of the molecular sieve to the amount of material of the Bronsted acid.
2. The molecular sieve material enriched in basic molecules at surface layer according to claim 1, wherein the mole fraction n of basic molecules M at the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total≥2；
Preferably, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total＝2～100；
Preferably, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total＝2～10；
Preferably, the mole fraction n of the basic molecules M on the surface layer of the molecular sieve materialM surThe mole fraction n of basic molecules in the molecular sieve material phaseM totalRatio nM sur/nM total＝2～6。
3. The molecular sieve material enriched in basic molecules at the surface layer as claimed in claim 1, wherein the basic molecules M are selected from at least one of organic basic molecules.
4. The molecular sieve material enriched in basic molecules at the surface layer as set forth in claim 1, wherein the basic molecules M are selected from at least one of pyridine, trimethylphosphine, triethylphosphine, acetone, and acetonitrile.
5. The molecular sieve material with the surface layer enriched with alkaline molecules as claimed in claim 1, wherein the molecular sieve in the molecular sieve material with the surface layer enriched with alkaline molecules is selected from at least one of SAPO-17 molecular sieve, SAPO-18 molecular sieve, SAPO-34 molecular sieve, SAPO-35 molecular sieve, SAPO-44 molecular sieve, SAPO-56 molecular sieve, SAPO-47 molecular sieve, DNL-6 molecular sieve and SSZ-13 molecular sieve.
6. The method for preparing a molecular sieve material enriched in basic molecules on the surface layer as claimed in any one of claims 1 to 5, comprising the steps of:
a) heating the molecular sieve at 300-500 ℃ under a vacuum condition to obtain a sample I;
b) heating a mixture containing the sample I, the alkaline molecules and the auxiliary agent under a sealed condition to obtain a sample II;
c) and heating the sample II under a vacuum condition to obtain the molecular sieve material with the surface layer enriched with alkaline molecules.
7. The method of claim 6, wherein the molecular sieve in step a) is a template-removing molecular sieve;
preferably, the heating time in the step a) is 1-48 h;
preferably, the heating temperature in the step a) is 400-420 ℃;
preferably, the molar ratio of the basic molecule M to the adjuvant in step b) is 0.01-100;
preferably, the molar amount of the basic molecule M in the step b) is 0.01 to 100 times of the amount of the Bronsted acid contained in the sample I;
preferably, the adjuvant in step b) is selected from at least one of carbon dioxide, water, hydrogen chloride, methane, ethane;
preferably, the heating temperature in the step b) is 30-600 ℃, and the heating time is 0.1-100 h;
preferably, the heating temperature in the step b) is 100-600 ℃, and the heating time is 0.1-12 h;
preferably, the heating temperature in step c) is 150-300 ℃.
8. The method of manufacturing according to claim 6, comprising:
1) roasting the molecular sieve, then loading the molecular sieve into a dehydration tube, and heating the molecular sieve to 300-500 ℃ under a vacuum-pumping condition to obtain a sample I; the molecular sieve is a molecular sieve for removing part of the template agent and/or a molecular sieve for removing all the template agent;
2) introducing alkaline molecules and an auxiliary agent into the dehydration tube filled with the sample I in the step 1), and sealing the dehydration tube;
3) heating the sealed dehydration tube obtained in the step 2) to obtain a sample II;
4) and (3) heating the sample II prepared in the step 3) under a vacuum condition to remove the auxiliary agent and the physically adsorbed alkaline molecules, so as to obtain the molecular sieve material with the surface layer enriched with the alkaline molecules.
9. Use of the molecular sieve material enriched with basic molecules on the surface layer as claimed in any one of claims 1 to 5, the molecular sieve material enriched with basic molecules on the surface layer prepared by the method as claimed in any one of claims 6 to 8 in the reaction of converting oxygenates to olefins.
10. The use of the molecular sieve material enriched in basic molecules on the surface layer as claimed in any one of claims 1 to 5, the molecular sieve material enriched in basic molecules on the surface layer prepared by the method as claimed in any one of claims 6 to 8 in the reaction of producing olefin from methanol and/or dimethyl ether.
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