CN112642393A - Y molecular sieve and preparation method thereof - Google Patents

Y molecular sieve and preparation method thereof Download PDF

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CN112642393A
CN112642393A CN201910957812.8A CN201910957812A CN112642393A CN 112642393 A CN112642393 A CN 112642393A CN 201910957812 A CN201910957812 A CN 201910957812A CN 112642393 A CN112642393 A CN 112642393A
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molecular sieve
sodium
oal
osi
sio
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CN112642393B (en
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高宁宁
王辉国
刘宇斯
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • 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
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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

Abstract

Y molecular sieve and SiO of Y molecular sieve2/Al2O3The molar ratio is 3.5-5.5, and Si (OAl) in the framework structure4And Si (OSi)1(OAl)3The sum of the structural tetrahedra being not more than 12 mol%, Si (OSi)2(OAl)2And Si (OSi)3(OAl)1Sum of structural tetrahedrons not less than 81 mol%, Si (OSi)4The structural tetrahedral content is not more than 7 mol%. The Y molecular sieve is used for adsorbing and separating meta-xylene from mixed carbon octa-arene and has higher adsorption selectivity and adsorption capacity.

Description

Y molecular sieve and preparation method thereof
Technical Field
The invention relates to a silicon-aluminum molecular sieve and a preparation method thereof, in particular to a Y molecular sieve and a preparation method thereof.
Background
Molecular sieves are crystalline materials with special framework structures, and are widely used in the fields of separation, catalysis and the like due to uniform microporous pore passages, adjustable acidity and good ion exchange performance. At present, a Y molecular sieve is mostly used as an active component of a meta-xylene adsorption separation adsorbent in industry, and the crystallinity, the silica/alumina molar ratio, the framework structure chemical composition, the grain size, the internal pore structure and the like of the Y molecular sieve can obviously influence the adsorption capacity, the adsorption selectivity and the mass transfer performance of the adsorbent.
US4306107 discloses a process for separating meta-xylene and ethylbenzene from mixed carbon octa-aromatics. The method adopts NaY zeolite as an active component of an adsorbent, toluene as a desorbent, and utilizes the characteristics of the NaY zeolite that the adsorption capacity to m-xylene is strongest, p-xylene and o-xylene are medium, and ethylbenzene is weakest to introduce mixed carbon-eight aromatic hydrocarbon into a simulated moving bed for countercurrent operation, so that m-xylene, p-xylene, o-xylene and ethylbenzene are respectively obtained at different positions of the simulated moving bed.
US4326092 discloses a method for separating meta-xylene from mixed carbon-eight aromatics, wherein a NaY zeolite with a molar ratio of silica to alumina of 4.5-5.0 is used to prepare an adsorbent, so that higher meta-xylene selectivity can be obtained.
US5900523 reports that NaY zeolite with a molar ratio of silica to alumina of 4.0-6.0 is used as an adsorbent of an active component, the water content is 1.5-2.5 mass% in terms of a ignition loss at 500 ℃, indane is used as a desorbent, and m-xylene is subjected to liquid phase adsorption separation at 100-150 ℃, so that a good separation effect is achieved.
CN1939883A discloses a method for separating m-xylene from a carbon eight aromatic hydrocarbon isomer, which comprises the step of preparing an adsorbent by using NaY zeolite with the molar ratio of silicon oxide to aluminum oxide being 5-6, wherein the water content of the zeolite is 0-8% by mass, the adsorption temperature is 25-250 ℃, and the adsorbent is selected from tetralin and alkylated derivatives thereof.
CN1050595C reports an adsorbent using Y zeolite with cation sites occupied by sodium and lithium ions as active components, and is used for liquid phase adsorption separation of meta-xylene from mixed carbon eight aromatic hydrocarbons, and higher meta-xylene selectivity is obtained. Wherein, lithium ions occupy 5 to 35 percent of exchangeable sites of the zeolite, and the water content of the adsorbent is 1.5 to 3.0 percent by mass calculated by the ignition loss at 500 ℃.
CN102167652A discloses an adsorbent for adsorbing and separating m-xylene from mixed C-eight aromatic hydrocarbons, and the active component is Y zeolite with cation exchange sites occupied by sodium and strontium ions, so that a good separation effect is achieved.
Disclosure of Invention
The invention aims to provide a Y molecular sieve and a preparation method thereof, wherein the Y molecular sieve is used for adsorbing and separating m-xylene from mixed C-eight aromatic hydrocarbons and has higher adsorption selectivity and adsorption capacity.
SiO of the Y molecular sieve provided by the invention2/Al2O3The molar ratio is 3.5-5.5, and Si (OAl) in the framework structure4And Si (OSi)1(OAl)3The sum of the structural tetrahedra being not more than 12 mol%, Si (OSi)2(OAl)2And Si (OSi)3(OAl)1Sum of structural tetrahedrons not less than 81 mol%, Si (OSi)4The structural tetrahedral content is not more than 7 mol%.
In the framework structure of the Y molecular sieve, Si (OSi)2(OAl)2And Si (OSi)3(OAl)1The structure has more tetrahedron content, and the adsorption selectivity of the m-xylene can be obviously improved.
Drawings
FIG. 1 is an XRD spectrum of a Y molecular sieve prepared in accordance with example 1 of the present invention.
FIG. 2 is a schematic representation of the Y molecular sieve prepared in example 1 of the present invention29And (3) a Si solid nuclear magnetic resonance spectrum.
FIG. 3 is a schematic representation of the Y molecular sieve prepared in comparative example 129And (3) a Si solid nuclear magnetic resonance spectrum.
Detailed Description
The framework structure of the Y molecular sieve is characterized in that Si and Si, Si and Al are connected through Si-O-Si and Si-O-Al, the tetrahedron formed contains five different structures, and the tetrahedron can be represented by a general formula Si (OSi)4-n(OAl)nIn the formula, n is 0, 1, 2, 3, 4, and tetrahedrons containing a "— O — Al" bond have different electrical properties between aluminum and silicon, which results in adsorption electrical properties of the molecular sieve. Generally, the amount of Si-O-Al increases as the silica-alumina ratio of the framework of the molecular sieve decreases. However, in the Y molecular sieve skeleton structure obtained by a different synthesis method, Si (OSi) was present on the premise that the silicon-aluminum ratio of the molecular sieve skeleton was substantially equal4-n(OAl)nThe content of the various tetrahedra shown differs. In the invention, during the synthesis process of the molecular sieve, polybasic carboxylate ions capable of forming complexes with Al are added, so that more Si (OSi) can be formed in the framework of the Y molecular sieve2(OAl)2And Si (OSi)3(OAl)1The structure is tetrahedral, which is beneficial to improving the adsorption selectivity of the meta-xylene of the Y molecular sieve.
SiO of the Y molecular sieve of the invention2/Al2O3The mol ratio is preferably 4-5, and the grain size of the Y molecular sieve is preferably 0.4-1.5 microns.
Preferably, in the framework structure of the Y molecular sieve provided by the invention, Si (OAl)4And Si (OSi)1(OAl)3The sum of structural tetrahedrons is 5-12 mol%, Si (OSi)2(OAl)2And Si (OSi)3(OAl)1The sum of structural tetrahedra being 84 to 94 mol%, Si (OSi)4The structural tetrahedron content is 0.1 to 5 mol%.
The preparation method of the Y molecular sieve comprises the following steps:
(1) mixing a silicon source, an aluminum source, water and sodium hydroxide, wherein the molar ratio of the materials is SiO2/Al2O3＝10～25，Na2O/SiO2＝0.6～1.8，H2O/SiO2Aging the mixture at 0-60 ℃ for 1-72 hours to prepare a guiding agent,
(2) uniformly mixing a silicon source, an aluminum source, the directing agent prepared in the step (1), sodium polycarboxylic acid and water to form a molecular sieve synthesis system, wherein the molar ratio of the materials is as follows: SiO 22/Al2O3＝8.5～13.5，Na2O/SiO2＝0.35～0.85，H2O/SiO 220 to 80 sodium polycarboxylic acid/Al2O30.05 to 0.30% of Al contained in the added directing agent2O3With Al contained in the molecular sieve synthesis system2O3The molar ratio of (a) to (b) is 2 to 10%,
(3) and (3) carrying out hydrothermal crystallization on the molecular sieve synthesis system in the step (2) at 90-150 ℃ for 8-48 hours, and washing and drying the crystallized solid to obtain the Y molecular sieve.
The aluminum source of the invention is preferably one or more of low-alkalinity sodium metaaluminate solution, alumina, aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum nitrate and sodium aluminate, and preferably low-alkalinity sodium metaaluminate solution. Al in the low-alkalinity sodium metaaluminate solution2O37 to 15 mass% of Na2The O content is 7 to 20 mass%.
The silicon source is selected from one or more of ethyl orthosilicate, silica sol, water glass, sodium silicate, silica gel and white carbon black, and the silica sol or the water glass is preferred.
The step (1) of the invention is used for synthesizing the directing agent, and the molar ratio of the materials is preferably SiO2/Al2O3＝12～20，Na2O/SiO2＝0.6～1.5，H2O/SiO2The aging temperature is 10-30 ℃, the aging temperature is preferably 10-45 ℃, and the time is preferably 10-30 hours.
In the invention, the molecular sieve synthesis system is prepared in the step (2), and in the synthesis system, the molar ratio of each material is preferably as follows: SiO 22/Al2O3＝8.5～12，Na2O/SiO2＝0.35～0.6，H2O/SiO 220 to 50 sodium polycarboxylic acid/Al2O30.05 to 0.30% of Al contained in the added directing agent2O3With Al contained in the molecular sieve synthesis system2O3The molar ratio of (A) to (B) is preferably 3 to 7%. The sodium polycarboxylic acid has 2-5 carbon atoms and 2-3 contained carboxylic acid radicals, or the sodium polycarboxylic acid has 3-5 carbon atoms and 2-3 contained carboxylic acid radicals and contains hydroxyl. The sodium polycarboxylic acid without hydroxyl groups can be sodium oxalate, and the sodium polycarboxylic acid with hydroxyl groups can be sodium citrate, sodium tartrate or sodium malate. The sodium polycarboxylic acid is preferably one or more of sodium oxalate, sodium citrate, sodium tartrate and sodium malate.
In the step (3), a molecular sieve synthesis system is subjected to hydrothermal crystallization to prepare the molecular sieve, wherein the hydrothermal crystallization temperature is preferably 90-130 ℃, and the hydrothermal crystallization time is preferably 10-40 hours, and more preferably 20-30 hours. The drying temperature of the solid obtained after crystallization after washing is preferably 70-100 ℃, and the time is preferably 2-20 hours.
The Y molecular sieve is suitable for adsorbing and separating meta-xylene from mixed carbon octa-arene. The desorbent used for adsorptive separation is preferably toluene.
The adsorption selectivity and the adsorption and desorption rates of the components of the adsorption purpose are important indexes for evaluating the performance of the adsorbent. The selectivity is the ratio of the concentrations of the two components in the adsorption phase to the concentrations of the two components in the non-adsorption phase at adsorption equilibrium. The adsorption equilibrium refers to the state when no component net transfer occurs between the adsorption phase and the non-adsorption phase after the mixed carbon-eight aromatic hydrocarbon contacts with the adsorbent. The adsorption selectivity is calculated as follows:
Figure BDA0002227925140000031
wherein C and D represent the two components to be separated, ACAnd ADRespectively represents the concentrations of C, D two components in the adsorption phase at the adsorption equilibrium, UCAnd UDRespectively, the concentrations of C, D in the non-adsorbed phase at adsorption equilibrium. When the selectivity beta of the two components is approximately equal to 1.0, the adsorption capacity of the adsorbent to the two components is equivalent, and the components which are preferentially adsorbed are not present. When β is greater or less than 1.0, it indicates that one component is preferentially adsorbed. Specifically, when beta is>At 1.0, the adsorbent preferentially adsorbs the C component; when beta is<At 1.0, the adsorbent preferentially adsorbs the D component. In terms of ease of separation, adsorption separation is easier to perform as β value is larger. The absorption and desorption speed is high, the dosage of the absorbent and the desorbent is reduced, the product yield is improved, and the operation cost of the absorption and separation device is reduced.
The invention uses a dynamic pulse experimental device to measure the adsorption selectivity and the adsorption and desorption rates of the m-xylene. The device comprises a feeding system, an adsorption column, a heating furnace, a pressure control valve and the like. The adsorption column is a stainless steel tube with phi 6 multiplied by 1800 mm, and the loading of the adsorbent is 50 ml. The inlet at the lower end of the adsorption column is connected with a feeding and nitrogen system, and the outlet at the upper end is connected with a pressure control valve and then connected with an effluent collector. The desorbent composition used for the experiment was 30 vol% toluene (T) and 70 vol% n-heptane (NC)7) The pulse liquid consists of 5 vol% of Ethylbenzene (EB), Paraxylene (PX), Metaxylene (MX), Orthoxylene (OX) and n-nonane(NC9) And 75% by volume of the desorbent described above.
The method for measuring the adsorption selectivity comprises the following steps: and filling the weighed adsorbent into an adsorption column, vibrating, filling, and dehydrating and activating at 160-280 ℃ in nitrogen flow. Then introducing a desorption agent to remove gas in the system, raising the pressure to 0.8MPa and the temperature to 145 ℃, stopping introducing the desorption agent, and keeping the pressure for 1.0 hour－1The pulse feeding liquid of 8 ml is introduced at the volume space velocity, then the introduction of the pulse liquid is stopped, the desorption agent is introduced at the same space velocity for desorption, 3 drops of desorption liquid samples are taken every 2 minutes, and the composition is analyzed by gas chromatography. Taking the feed volume of the desorbent for desorption as the abscissa, NC9And the concentrations of the EB, PX, MX and OX components are used as vertical coordinates, and desorption curves of the components are drawn. NC as tracer9Not adsorbed, the first peak, which gives the dead volume of the adsorption system. And taking the middle point of the half-peak width of the tracer as a zero point, and determining the feeding volume of the desorbent from the middle point of the half-peak width of each component of EB, PX, MX and OX to the zero point, namely the net retention volume. The ratio of the net retention volumes of the two components is the adsorption selectivity beta. For example, the ratio of the net retention volume of MX to the net retention volume of EB is the adsorption selectivity of MX to EB, and is recorded as betaMX/EB。
The selectivity between the extract component and the desorbent is also an important performance index for the cyclic continuous use of the adsorbent, and can be determined by further analysis of the desorption curve of the extract component in a pulse test. The volume of desorbent required to raise the MX concentration in the effluent from 10% to 90% at the leading edge of the pulsed desorption profile for MX is defined as the adsorption rate SA]10-90The volume of desorbent required to decrease the MX concentration from 90% to 10% after the desorption curve is defined as the desorption rate [ S ]D]90-10. Ratio of the two [ S ]D]90-10/[SA]10-90I.e. can be characterized as the adsorption selectivity beta between MX and desorbent (T)MX/T. If beta isMX/TLess than 1.0 means that the adsorbent has too strong an adsorption capacity for the desorbent, which is detrimental to the adsorption process, if beta isMX/TA value of more than 1.0 indicates that the adsorption capacity for the desorbent is too weak, which makes the desorption process difficultThe ideal condition is betaMX/TApproximately equal to or slightly greater than 1.0.
The present invention is illustrated in detail below by way of examples, but the present invention is not limited thereto.
In the example, the toluene gas phase adsorption experiment is adopted to determine the adsorption capacity of the molecular sieve, and the specific operation method comprises the following steps: toluene-laden nitrogen (toluene partial pressure 0.5MPa) was contacted with a mass of molecular sieve at 35 ℃ until toluene reached adsorption equilibrium. And calculating the adsorption capacity of the molecular sieve to be detected according to the mass difference of the molecular sieve before and after toluene adsorption by the following formula.
Figure BDA0002227925140000051
Wherein C is adsorption capacity, and the unit is milligram/gram; m is1The mass of the molecular sieve to be detected before toluene adsorption is carried out, and the unit is gram; m is2The unit is the mass of the molecular sieve to be detected after toluene adsorption.
Example 1
(1) Preparation of an aluminium source
200kg of aluminum hydroxide, 232.15kg of sodium hydroxide and 652.33kg of deionized water are added into a reaction kettle, heated to 100 ℃, and stirred for 6 hours to form clear and transparent low-alkalinity sodium metaaluminate solution serving as an aluminum source. Al in the aluminum source2O3The content was 11.87 mass%, Na2O content 16.59 mass% and Na2O and Al2O3Is 2.3.
(2) Preparation of directing agent
Under stirring, 3.81kg of sodium hydroxide, 8.86kg of deionized water, 4.48kg of the aluminum source prepared in step (1) and 23.24kg of water glass (SiO in water glass)2The content of Na was 20.17 mass%2O content of 6.32 mass%, the same applies hereinafter) was added to the reaction vessel, and the molar ratio of each material was SiO2/Al2O3＝15，Na2O/SiO2＝1.07，H2O/SiO2Then, the mixture was allowed to stand at 35 ℃ for 16 hours to obtain a targeting agent.
(3) Preparation of Y molecular sieves
50.74kg of water glass, 42.51kg of deionized water, 7.56kg of the directing agent prepared in step (2), and 8.66kg of aluminum sulfate (containing 6.73 mass% of Al) were stirred together2O3) 11.01kg of the low-alkalinity sodium metaaluminate solution prepared in the step (1) and 0.13kg of sodium oxalate are added into a reaction kettle, wherein the molar ratio of the materials is SiO2/Al2O3＝9.5，Na2O/SiO2＝0.43，H2O/SiO 230 sodium oxalate/Al2O30.05% of Al contained in the directing agent2O3Al contained in the synthesis system with Y molecular sieve2O3Is 5%.
Transferring the molecular sieve synthesis system into a closed reaction kettle, carrying out hydrothermal crystallization at 100 ℃ for 28 hours, filtering, washing the obtained solid with deionized water until the pH of the filtrate is 8-9, drying at 80 ℃ for 12 hours to obtain a Y molecular sieve, wherein the serial number of the Y molecular sieve is A, the grain size of the crystal grain is 0.9 micron, the XRD spectrogram is shown in figure 1,29the nuclear magnetic resonance spectrum of Si is shown in FIG. 2, and the content of tetrahedra with various structures in the framework structure and the framework SiO of the molecular sieve are obtained from FIG. 22/Al2O3The molar ratio is shown in Table 1, and the toluene adsorption capacity is shown in Table 2.
(4) Evaluation of Performance
Tabletting, forming, crushing and screening the Y molecular sieve A to obtain particles of 300-850 mu m, and evaluating the xylene adsorption selectivity by adopting a pulse test, wherein the results are shown in Table 2.
Example 2
A Y molecular sieve was prepared as in example 1, except that in the step (3), 50.74kg of water glass, 42.51kg of deionized water, 7.56kg of the directing agent prepared in the step (2), 8.66kg of aluminum sulfate, 11.01kg of the low alkalinity sodium metaaluminate solution prepared in the step (1) and 0.39kg of sodium oxalate were added to a reaction vessel under stirring to obtain a Y molecular sieve synthesis system in which the molar ratio of the materials was SiO2/Al2O3＝9.5，Na2O/SiO2＝0.43，H2O/SiO230 sodium oxalate/Al2O30.15% of Al contained in the directing agent2O3Al contained in the synthesis system with Y molecular sieve2O3The mol ratio of the molecular sieve B is 5 percent, the molecular sieve synthesis system is transferred into a closed reaction kettle, and the Y molecular sieve B is obtained after hydrothermal crystallization, filtration, washing by deionized water and drying, wherein the grain diameter of the crystal grain is 0.8 micron29Content of tetrahedron with various structures in framework structure obtained by Si solid nuclear magnetic resonance analysis and molecular sieve framework SiO2/Al2O3The molar ratio is shown in Table 1, and the toluene adsorption capacity and the m-xylene adsorption selectivity are shown in Table 2.
Example 3
A Y molecular sieve was prepared as in example 1, except that in the step (3), 50.74kg of water glass, 42.51kg of deionized water, 7.56kg of the directing agent prepared in the step (2), 8.66kg of aluminum sulfate, 11.01kg of the low alkalinity sodium metaaluminate solution prepared in the step (1) and 0.65kg of sodium oxalate were charged into a reaction vessel under stirring to obtain a Y molecular sieve synthesis system in which the molar ratio of the materials was SiO2/Al2O3＝9.5，Na2O/SiO2＝0.43，H2O/SiO230 sodium oxalate/Al2O30.25% of Al contained in the directing agent2O3Al contained in the synthesis system with Y molecular sieve2O3The mol ratio of the molecular sieve C is 5 percent, the molecular sieve synthesis system is transferred into a closed reaction kettle, and then the Y molecular sieve C is obtained after hydrothermal crystallization, filtration, washing by deionized water and drying, the grain diameter of the crystal grain is 0.7 micron, the method adopts29Content of tetrahedron with various structures in framework structure obtained by Si solid nuclear magnetic resonance analysis and molecular sieve framework SiO2/Al2O3The molar ratio is shown in Table 1, and the toluene adsorption capacity and the m-xylene adsorption selectivity are shown in Table 2.
Example 4
Y molecular sieve was prepared as in example 1, except that in step (3) 0.56kg of sodium tartrate was used in place of sodium oxalate to obtain Y molecular sieve D having a crystal grain size of 1.0. mu.m, using29Content of tetrahedron with various structures in framework structure obtained by Si solid nuclear magnetic resonance analysis and molecular sieve framework SiO2/Al2O3The molar ratio is shown in Table 1, and the toluene adsorption capacity and the m-xylene adsorption selectivity are shown in Table 2.
Example 5
A Y molecular sieve was prepared as in example 1, except that in the step (3), 50.74kg of water glass, 40.96kg of deionized water, 7.56kg of the directing agent prepared in the step (2), 12.88kg of aluminum sulfate, 8.61kg of the low alkalinity sodium metaaluminate solution prepared in the step (1) and 0.65kg of sodium oxalate were charged into a reaction vessel under stirring to obtain a Y molecular sieve synthesis system in which the molar ratio of the materials was SiO2/Al2O3＝9.5，Na2O/SiO2＝0.35，H2O/SiO230 sodium oxalate/Al2O30.25% of Al contained in the directing agent2O3Al contained in the synthesis system with Y molecular sieve2O3The mol ratio of the molecular sieve is 5 percent, the molecular sieve synthesis system is transferred into a closed reaction kettle, and the Y molecular sieve E is obtained after hydrothermal crystallization, filtration, washing by deionized water and drying, wherein the grain diameter of the crystal grain is 1.2 microns29Content of tetrahedron with various structures in framework structure obtained by Si solid nuclear magnetic resonance analysis and molecular sieve framework SiO2/Al2O3The molar ratio is shown in Table 1, and the toluene adsorption capacity and the m-xylene adsorption selectivity are shown in Table 2.
Comparative example 1
The Y molecular sieve was prepared according to the method of example 1, except that in the step (3) of preparing the molecular sieve synthesis system, sodium oxalate was not added to obtain Y molecular sieve F having a crystal grain size of 1.0. mu.m,29the Si solid nuclear magnetic resonance spectrum is shown in FIG. 3, and the content of tetrahedra with various structures in the framework structure and the framework SiO of the molecular sieve are obtained from FIG. 32/Al2O3The molar ratio is shown in Table 1, and the toluene adsorption capacity is shown in Table 2.
TABLE 1
Figure BDA0002227925140000071
n-4 denotes Si (OAl)4N-3 denotes Si (OSi) (OAl)3N-2 denotes Si (OSi)2(OAl)2N-1 represents Si (OSi)3(OAl) wherein n-0 represents Si (OSi)4
TABLE 2
Figure BDA0002227925140000081

Claims (11)

1. Y molecular sieve and SiO of Y molecular sieve2/Al2O3The molar ratio is 3.5-5.5, and Si (OAl) in the framework structure4And Si (OSi)1(OAl)3The sum of the structural tetrahedra being not more than 12 mol%, Si (OSi)2(OAl)2And Si (OSi)3(OAl)1Sum of structural tetrahedrons not less than 81 mol%, Si (OSi)4The structural tetrahedral content is not more than 7 mol%.
2. The molecular sieve of claim 1, wherein the Y molecular sieve has the framework structure of Si (OAl)4And Si (OSi)1(OAl)3The sum of structural tetrahedrons is 5-12 mol%, Si (OSi)2(OAl)2And Si (OSi)3(OAl)1The sum of structural tetrahedra being 84 to 94 mol%, Si (OSi)4The structural tetrahedron content is 0.1 to 5 mol%.
3. The molecular sieve of claim 1, wherein the Y molecular sieve has a crystallite size of 0.4 to 1.5 microns.
4. A method of making the Y molecular sieve of claim 1, comprising the steps of:
(1) mixing a silicon source, an aluminum source, water and sodium hydroxide, wherein the molar ratio of the materials is SiO2/Al2O3＝10～25，Na2O/SiO2＝0.6～1.8，H2O/SiO2Aging the mixture at 0-60 ℃ for 1-72 hours to prepare a guiding agent,
(2) uniformly mixing a silicon source, an aluminum source, the directing agent prepared in the step (1), sodium polycarboxylic acid and water to form a molecular sieve synthesis system, wherein the molar ratio of the materials is as follows: SiO 22/Al2O3＝8.5～13.5，Na2O/SiO2＝0.35～0.85，H2O/SiO220 to 80 sodium polycarboxylic acid/Al2O30.05 to 0.30% of Al contained in the added directing agent2O3With Al contained in the molecular sieve synthesis system2O3The molar ratio of (a) to (b) is 2 to 10%,
(3) and (3) carrying out hydrothermal crystallization on the molecular sieve synthesis system in the step (2) at 90-150 ℃ for 8-48 hours, and washing and drying the crystallized solid to obtain the Y molecular sieve.
5. The method of claim 4, wherein the aluminum source is selected from the group consisting of low alkalinity sodium metaaluminate solution, alumina, aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum nitrate and sodium aluminate.
6. A process according to claim 4, characterized in that the Al content of the low alkalinity sodium metaaluminate solution is2O37 to 15 mass% of Na2The O content is 7 to 20 mass%.
7. The method according to claim 4, wherein the silicon source is one or more selected from the group consisting of tetraethoxysilane, silica sol, water glass, sodium silicate, silica gel and white carbon black.
8. The process according to claim 4, wherein the sodium polycarboxylic acid in the step (2) has 2 to 5 carbon atoms and contains 2 to 3 carboxylate groups.
9. The process according to claim 4, wherein the sodium polycarboxylic acid in the step (2) has 3 to 5 carbon atoms and contains 2 to 3 carboxylate groups and hydroxyl groups.
10. The method according to claim 4, wherein the sodium polycarboxylic acid in step (2) is one or more of sodium oxalate, sodium citrate, sodium tartrate and sodium malate.
11. The method according to claim 4, wherein the hydrothermal crystallization temperature of the molecular sieve synthesis system in step (3) is 90-130 ℃ and the time is 10-40 hours.
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