CN107511164B - Y molecular sieve catalyst, preparation method and application - Google Patents

Y molecular sieve catalyst, preparation method and application Download PDF

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CN107511164B
CN107511164B CN201610440823.5A CN201610440823A CN107511164B CN 107511164 B CN107511164 B CN 107511164B CN 201610440823 A CN201610440823 A CN 201610440823A CN 107511164 B CN107511164 B CN 107511164B
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molecular sieve
alkali
sieve catalyst
sio
silica
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CN107511164A (en
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杨为民
王振东
孙洪敏
张斌
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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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    • 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
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Catalysts (AREA)

Abstract

The invention relates to a Y molecular sieve catalyst, a preparation method and application thereof. The Y molecular sieve catalyst comprises the following components in parts by weight: a) 92-99 parts of a Y molecular sieve; b) 1-8 parts of a silica-alumina gel binder; the silica-alumina gel binder is obtained by the step of contacting a silicon source, an aluminum source and an alkali.

Description

Y molecular sieve catalyst, preparation method and application
Technical Field
The invention relates to a Y molecular sieve catalyst, a preparation method and application thereof.
Background
The Y-type molecular sieve has a three-dimensional twelve-membered ring channel structure, the aperture is about 0.74 nanometer, the Y-type molecular sieve has proper acidity and low price, is beneficial to the diffusion of reactant molecules in the molecular sieve channels and the reaction on an acid center, and is widely applied to the reactions of catalytic cracking, hydrocracking, hydrotreating, the alkylation of benzene and olefin, the transalkylation of benzene and polyalkylbenzene and the like, so the research on the Y-type molecular sieve has wide application prospect and academic research value. Currently, hydrothermal treatment is generally used in industry to produce intracrystalline mesopores, by which the microporous pore channels of the molecular sieve are shortened and more pore openings are exposed, so as to improve the accessibility of the active center of the molecular sieve and achieve the ultra-stable level (by improving the thermal stability of Y zeolite through increasing the silica-alumina ratio), obtain ultra-stable Y (usy).
The catalyst prepared by taking the Y molecular sieve or USY as an active component is successfully applied to a process for preparing ethylbenzene by benzene and ethylene liquid phase alkylation and a process for preparing ethylbenzene by benzene and polyethylbenzene transalkylation.
In particular, in order to meet the requirements of industrial application, the molecular sieve is mixed with additives such as a binder and a pore-forming agent to be molded to prepare a catalyst with certain size, shape and strength. However, the addition of the binder more covers the active sites of the molecular sieve and limits the content of the molecular sieve as an active component in the catalyst, generally below 80 mass%. Thus, the number of active centers in a commercial shaped Y molecular sieve catalyst is much lower than the Y molecular sieve before shaping.
In order to overcome the problems of binder-free Y molecular sieve catalysts containing less active centers, document CN102039150B discloses a method for preparing a binder-free Y molecular sieve catalyst, which converts the binder into Y molecular sieve by gas phase crystallization. However, the time required for crystal transformation is long (20-300 hours), so that the strength of the catalyst is reduced, and the requirement of industrial application cannot be met; meanwhile, 5 mass% of the binder remained in the obtained catalyst.
The inventors of the present invention found that catalyst strength has a significant effect on catalytic performance. In the reactions of preparing ethylbenzene by liquid-phase alkylation of benzene and ethylene and preparing ethylbenzene by liquid-phase transalkylation of benzene and polyethylbenzene, the higher the compressive strength of the catalyst is, the better the compressive strength is, and the proper compressive strength needs to be found to ensure the catalytic performance of the catalyst.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, silica sol and alumina are used as binders, so that the catalyst has the defects of overhigh strength, low molecular sieve content and low catalytic activity when the binder is used in a large amount, and the catalyst has low strength and serious pulverization when the binder is used in a small amount; and the time required for the secondary crystallization is long. The invention provides a novel Y molecular sieve catalyst. The catalyst takes silica-alumina gel as a binder, can realize the molding of a molecular sieve by using a very small amount of the binder, directly prepare a Y molecular sieve catalyst with the molecular sieve content of not less than 95 percent, can obtain the catalyst with high strength and good activity without secondary crystallization, meets the requirements of the reaction of preparing ethylbenzene by liquid-phase transalkylation of benzene and polyethylbenzene and preparing ethylbenzene by liquid-phase alkylation of benzene and ethylene on the catalyst, and is suitable for large-scale industrial production.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a Y molecular sieve catalyst comprises the following components in parts by weight:
a) 92-99 parts of a Y molecular sieve;
b) 1-8 parts of a silica-alumina gel binder;
the silica-alumina gel binder is obtained by the step of contacting a silicon source, an aluminum source and alkali; silicon source of SiO2Calculated by Al as the aluminum source2O3Alkali to silicon molar ratio alkali to SiO20 to 0.3, Si/Al molar ratio SiO2/Al2O3＝25～85。
In the technical scheme, the alkali-silicon molar ratio is preferably alkali/SiO20.02 to 0.3, more preferably alkali/SiO20.03 to 0.22, and alkali/SiO is more preferable20.04 to 0.18, most preferably alkali/SiO2＝0.06～0.12。
In the technical scheme, the preferred molar ratio of silicon to aluminum is SiO2/Al2O325 to 60, more preferably SiO2/Al2O3＝30～50。
In the above technical scheme, the silicon source is selected from silica sol, fuming silica gel, water glass or has a general formula of Y4-nSiXnAt least one of the silicon-containing compounds of (a); general formula Y4-nSiXnIn the formula, n is an integer of 1-4, Y is alkanyl, preferably methyl, ethyl or propyl; x is selected from Cl, methoxy OMe, ethoxy OEt or trimethylsiloxy OSiMe3. The silicon source is preferably at least one of silica sol and fumed silica.
In the above technical solution, the aluminum source is at least one selected from sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate and aluminum chloride.
In the above technical solution, the alkali is at least one selected from quaternary ammonium bases and bases having an alkali metal element or an alkaline earth metal element as a cation; the quaternary ammonium base is selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N, N, N-trimethyladamantyl ammonium hydroxide or dimethyldiethylammonium hydroxide. The base is preferably at least one of NaOH or KOH.
In the technical scheme, the content of the Y molecular sieve is preferably 95-99 parts by weight, and more preferably 96-99 parts by weight; the content of the silica-alumina gel binder is preferably 1-5 parts, and more preferably 1-4 parts.
In the technical scheme, the compressive strength of the Y molecular sieve catalyst is 60-120N/cm, preferably 65-100N/cm, and more preferably 65-90N/cm.
In the technical scheme, the grain diameter of the Y molecular sieve is 60 nanometers to 1 micron.
In the technical scheme, the Si/Al molar ratio SiO of the Y molecular sieve2/Al2O3＝4.5～40。
In the technical scheme, the catalyst comprises 0-0.5 parts of phosphorus in parts by weight.
In the technical scheme, the catalyst comprises 0-0.5 parts of rare earth metal elements in parts by weight.
In the above technical solution, the rare earth metal element is at least one selected from yttrium, lanthanum, cerium, or neodymium.
The content of each component in the Y molecular sieve is based on the roasted Y molecular sieve.
The invention also provides a preparation method of the Y molecular sieve catalyst. The method comprises the following steps:
a) providing a synthesized Y molecular sieve;
b) directly molding the synthetic Y molecular sieve, a silicon source, an aluminum source and alkali to obtain the Y molecular sieve catalyst;
wherein the silicon source is selected from silica sol, fuming silica gel, water glass or Y4-nSiXnAt least one of the silicon-containing compounds of (a); general formula Y4-nSiXnWherein n is an integer of 1 to 4, Y is an alkanyl group, X is selected from Cl, methoxy OMe, ethoxy OEt or trimethylsiloxy OSiMe3；
The aluminum source is selected from at least one of sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate or aluminum chloride;
the alkali is at least one of quaternary ammonium alkali and alkali taking alkali metal elements or alkaline earth metal elements as cations;
silicon source of SiO2Calculated by Al as the aluminum source2O3Alkali to silicon molar ratio alkali to SiO20 to 0.3, Si/Al molar ratio SiO2/Al2O3＝25～85。
In the technical scheme, the alkali-silicon molar ratio is preferably alkali/SiO20.02 to 0.3, more preferably alkali/SiO20.03 to 0.22, and alkali/SiO is more preferable20.04 to 0.18, most preferably alkali/SiO2＝0.06～0.12。
In the technical scheme, the preferred molar ratio of silicon to aluminum is SiO2/Al2O325 to 60, more preferably SiO2/Al2O3＝30～50。
In the above technical scheme, general formula Y4-nSiXnIn the above formula, Y is preferably a methyl group, an ethyl group or a propyl group.
In the above technical solution, the silicon source is preferably at least one of silica sol and fumed silica.
In the above technical solution, the quaternary ammonium hydroxide is selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N-trimethyladamantyl ammonium hydroxide or dimethyldiethylammonium hydroxide.
In the above technical solution, the alkali is preferably at least one of NaOH and KOH.
In the technical scheme, the grain diameter of the Y molecular sieve is 60 nanometers to 1 micron.
In the technical scheme, the Si/Al molar ratio SiO of the Y molecular sieve2/Al2O3＝4.5～40。
In the method of the invention, sodium aluminate (the composition of sodium aluminate is Al)2O3And Na2O in the form) is an aluminium source, alkali is introduced, and no additional alkali source is added. However, when an aluminum salt selected from aluminum hydroxide, aluminum sulfate, aluminum nitrate or aluminum chloride is used as an aluminum source, an alkali source is added. The alkali-silicon molar ratio is calculated by the following method: the molar ratio of alkali to silicon is equal to the molar ratio of alkali in the aluminum source to silicon in the silicon source + the molar ratio of alkali in the alkali source to silicon in the silicon source. For example, when silica sol is used as the silicon source, sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 wt.%) is an aluminum source and sodium hydroxide is an alkali source, the alkali to silica molar ratio is 2 x the amount of sodium oxide species in sodium aluminate/the amount of silica species in silica sol + the amount of sodium hydroxide species/the amount of silica species in silica sol; when silica sol is used as a silicon source, aluminum nitrate is used as an aluminum source, and sodium hydroxide is used as an alkali source, the molar ratio of alkali to silicon is equal to the amount of sodium hydroxide per the amount of silicon in the silica sol. This alkali is also calculated after firing, and the aluminum hydroxide and aluminum salt after firing are Al2O3, which is equivalent to no alkali, so additional alkali is required. And the calcined sodium aluminate shows Al2O3 and Na2O, so that no extra alkali is used.
The synthesized Y molecular sieve in the method is the Y molecular sieve which is synthesized according to a hydrothermal crystallization method well known in the field and is not roasted to remove the template agent. For example, the Y molecular sieve in the as-synthesized state can be obtained by crystallizing a mixture of a silicon compound, an aluminum compound, a base and water, and separating and drying the solid product. Wherein the molar ratio of the silicon compound, the aluminum compound, the alkali and the water is as follows: 1 (0.05-0.25), (0.2-0.80), (6-50), preferably 1 (0.1-0.2), (0.3-0.6), (10-30). The hydrothermal crystallization conditions include: the crystallization temperature is 80-120 ℃, and preferably 90-100 ℃; the crystallization time is 10 hours to 5 days, preferably 15 hours to 48 hours. The silicon compound is selected from at least one of silicic acid, silica gel, silica sol, tetraalkyl silicate, sodium silicate, water glass or white carbon black; the aluminum compound is selected from at least one of aluminum hydroxide, sodium aluminate, aluminum alkoxide, aluminum nitrate, aluminum sulfate, kaolin or montmorillonite; the alkali is selected from alkali taking alkali metal or alkaline earth metal as cation.
In the method of the present invention, the direct molding of the synthesized Y molecular sieve, the silicon source, the aluminum source and the alkali may be an extrusion molding method. Wherein, a pore-forming agent can be added, and the pore-forming agent is selected from at least one of sesbania powder, methyl cellulose and polyether (such as polyethylene glycol, P123 and F127). The mass ratio of the silicon oxide to the pore-forming agent in the synthesized Y molecular sieve is 1 (0.005-0.2), and preferably 1 (0.01-0.1). The formed catalyst is a cylinder with the length of 0.3-1.2 cm, the cross section of the cylinder is circular, square, clover, annular or star-shaped, and the maximum radial dimension of the cross section is 0.08-0.3 cm. The catalyst can also be subjected to ammonium exchange and water vapor treatment.
The preparation method of the P-containing catalyst comprises the following steps: according to the weight portion, 1 portion of Y molecular sieve catalyst is contacted with 5 to 50 portions of phosphoric acid with the mass fraction of 0.1 to 15 percent, preferably 0.3 to 5 percent, for 1 to 10 hours at the temperature of 20 to 100 ℃, and a solid product is separated, dried and roasted to obtain the Y molecular sieve catalyst containing P. P can improve the stability of the catalyst acid center.
The preparation method of the rare earth element-containing catalyst comprises the following steps: contacting 1 part of Y molecular sieve catalyst with 5-50 parts of rare earth metal salt aqueous solution with the mass fraction of 0.1-10%, preferably 0.3-5% for 1-10 hours at 20-100 ℃, separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst containing the rare earth element. Rare earth metals can adjust the acid properties.
The Y molecular sieve catalyst provided by the invention has good catalytic performance in the reactions of preparing ethylbenzene by liquid phase alkylation of benzene and ethylene and preparing ethylbenzene by transalkylation of benzene and polyethylbenzene, and can be used as an alkylation catalyst to be applied to the reactions of preparing ethylbenzene by liquid phase alkylation of benzene and ethylene and preparing ethylbenzene by transalkylation of benzene and polyethylbenzene.
The inventor of the invention finds that in the prior art, silica sol or alumina is used as a binder, and when the binder is used in a large amount, the catalyst has the disadvantages of high strength, low molecular sieve content and low catalytic activity; the catalyst has low strength and serious pulverization when the binder is used for a small amount. The time for preparing the molecular sieve without the binding agent by secondary crystallization is long; also, although the prior art claims that the binderless molecular sieve produced by the second crystallization has high compressive strength, the inventors of the present invention have found that in the fixed bed reaction of ethylbenzene produced by the liquid phase alkylation of benzene with ethylene and ethylbenzene produced by the transalkylation of benzene with polyethylbenzene, the higher the compressive strength of the catalyst is, the better. When the catalyst has a crushing strength of more than 120N/cm, for example, 130N/cm, the catalytic performance of the catalyst is remarkably lower than that of a catalyst having a crushing strength of 120N/cm. Therefore, the inventor of the present invention found that the compressive strength of the Y molecular sieve catalyst for preparing ethylbenzene by the liquid phase alkylation reaction of benzene and ethylene and preparing ethylbenzene by the transalkylation of benzene and polyethylbenzene should be controlled within 60-120N/cm, preferably 65-100N/cm, more preferably 65-99N/cm, and still more preferably 81-99N/cm. In order to obtain the Y molecular sieve catalyst with such compressive strength, the inventor of the present invention found that when a silicon source (such as silica sol) and an aluminum source (such as sodium aluminate) are subjected to a chemical reaction under an alkaline condition to generate silica-alumina gel in situ, the reaction process is very rapid, only 5 minutes are needed to ensure that the reaction is complete, the viscosity of the generated silica-alumina gel is high, and the molecular sieve is crosslinked together. According to the characteristic of the silica-alumina gel, the silica-alumina gel is used as the binder, the catalyst can be molded only by the binder of which the weight is not more than 5 percent, and the compressive strength of the obtained catalyst is higher than 60N/cm, preferably 60-120N/cm, so that the catalyst is particularly suitable for being used as a catalyst for preparing ethylbenzene through liquid phase alkylation reaction of benzene and ethylene and preparing ethylbenzene through transalkylation of benzene and polyethylbenzene, and a better technical effect is achieved.
The Y molecular sieve catalyst and the silicon-aluminum ratio of the molecular sieve are determined by a chemical analysis method.
In the Y molecular sieve catalyst, the compressive strength of the molecular sieve is tested by adopting a pressure tester to the calcined catalyst, and the test method comprises the following steps: selecting catalyst particles with the length L of 0.4-0.6 cm, transversely placing the catalyst particles on a test platform, gradually increasing the pressure until the catalyst is crushed, automatically recording the pressure F (Newton, N) applied when the catalyst is crushed by an instrument, and obtaining the ratio (F/L) of F to L as the compressive strength of the single catalyst. The compressive strength of 10 catalysts was tested and the average value was taken as the compressive strength of the catalyst.
The method for calculating the content of the binder in the Y molecular sieve catalyst comprises the following steps: the weight of the synthesized Y molecular sieve after being roasted for 5 hours at 550 ℃ in an air atmosphere is A, and the weight of a silicon source, an aluminum source and an alkali source used in direct molding after being roasted for 5 hours at 550 ℃ in an air atmosphere is B, so that the content of the binder is B/(A + B). times.100%.
Drawings
Fig. 1 is an XRD spectrum of the Y molecular sieve catalyst prepared [ example 1 ]. As can be seen from the spectrogram, the diffraction peak is consistent with the characteristic diffraction peak of the Y molecular sieve.
Detailed Description
[ example 1 ]
a) Preparation of a synthetic Y molecular sieve: the method is characterized in that water glass, aluminum sulfate octadecahydrate, sodium hydroxide and water are used as synthesis raw materials, and the raw materials are prepared according to the following material ratio (molar ratio):
SiO2/Al2O3＝8
NaOH/SiO2＝0.50
H2O/SiO2＝18
after being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 24 hours at 100 ℃ under the condition of stirring. And filtering, washing and drying after crystallization to obtain the synthetic Y molecular sieve. The weight loss rate of the synthesized Y molecular sieve was tested to be 8.2 wt% by calcining at 550 ℃ for 5 hours in an air atmosphere.
b) Using alkaline silica Sol (SiO)240.0 wt%) as silicon source and sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 weight percent) as an aluminum source, 0.25 g of sodium aluminate, 45.5 g of the synthetic Y molecular sieve in the step a) and 0.5616 g of sesbania powder are uniformly mixed, and alkaline silica Sol (SiO) is added240.0 wt.%) 4.5 g. Si/Al molar ratio SiO2/Al2O328.5, alkali to silicon molar ratio alkali to SiO2A strand-shaped molecular sieve catalyst precursor I having a Y molecular sieve content of 95.4 wt%, a binder content of 4.6 wt%, and a circular cross section was prepared by extrusion molding ═ 0.094.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at 90 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst.
The XRD spectrum of the product is shown in figure 1. The compressive strength of the Y molecular sieve catalyst is 82N/cm.
[ example 2 ]
As in [ example 1 ], except that:
b) mixing synthetic Y molecular sieve 56.5 g and alkaline silica Sol (SiO)240.0 wt.%), 4.5 g, 1.05 g of sesbania powder, sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 wt.%) 0.25 g of silica to alumina molar ratio SiO2/Al2O328.5, alkali to silicon molar ratio alkali to SiO2A precursor of a molecular sieve catalyst having a stripe shape with a Y molecular sieve content of 96.3 wt%, a binder content of 3.7 wt%, and a clover cross section was prepared by extrusion molding ═ 0.094.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at the temperature of 60 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 82N/cm.
[ example 3 ]
As in [ example 1 ], except that:
b) 72.8 g of synthetic Y molecular sieve and alkaline silica Sol (SiO)240.0 wt.%), 4.5 g, 1.05 g of sesbania powder, sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 wt.%) 0.25 g was mixed well. Si/Al molar ratio SiO2/Al2O328.5, alkali to silicon molar ratio alkali to SiO2A precursor of a molecular sieve catalyst having a molecular sieve Y content of 97.1 wt%, a binder content of 2.9 wt%, and a clover cross-section was prepared by extrusion molding ═ 0.094.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at the temperature of 60 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 69N/cm.
[ example 4 ]
As in [ example 1 ], except that:
b) mixing synthetic Y molecular sieve 56.5 g and alkaline silica Sol (SiO)240.0 wt.%), 4.5 g, 1.05 g of sesbania powder, sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 wt.%) 0.17 g was mixed well. Si/Al molar ratio SiO2/Al2O341.9, alkali to silicon molar ratio alkali to SiO2A precursor of a molecular sieve catalyst having a stripe shape with a Y molecular sieve content of 96.4 wt%, a binder content of 3.6 wt%, and a clover cross section was prepared by extrusion molding ═ 0.064.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at the temperature of 60 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 76N/cm.
[ example 5 ]
As in [ example 1 ], except that:
b) 72.8 g of synthetic Y molecular sieve and fumed Silica (SiO)297.0 wt.%) 2.0 g, sesbania powder 1.5 g, sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 wt.%) 0.3 g was mixed well. Si/Al molar ratio SiO2/Al2O325.6, alkali to silicon molar ratio alkali to SiO2A strand-shaped molecular sieve catalyst precursor having a Y molecular sieve content of 96.8 wt%, a binder content of 3.2 wt%, and a clover cross-section was prepared by extrusion molding ═ 0.105.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at the temperature of 60 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 71N/cm.
[ example 6 ]
As in [ example 1 ], except that:
b) 54.6 g of synthetic Y molecular sieve and alkaline silica Sol (SiO)240.0 wt.%) 2.425 g fumed Silica (SiO)297.0 wt.%) 1.0 g, sesbania powder 1.5 g, aluminium sulphate (Al)2(SO4)3·18H2O，Al2O315.2 wt.%) 0.868 g, and 0.135 g of sodium hydroxide (NaOH 96.0 wt.%) were mixed well. Si/Al molar ratio SiO2/Al2O325, alkali to silicon molar ratio alkali to SiO2A precursor of a molecular sieve catalyst having a molecular sieve Y content of 95.8 wt%, a binder content of 4.2 wt%, and a cross-section of clover was prepared by extrusion molding ═ 0.129.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at the temperature of 60 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 67N/cm.
[ example 7 ]
As in [ example 1 ], except that:
b) 59.6 g of synthetic Y molecular sieve and alkaline silica Sol (SiO)240.0 wt.%), 4.5 g, 1.05 g of sesbania powder, sodium aluminate (Al)2O343.0 wt.%, Na2O35.0 wt.%), 0.25 g, and 0.02 g sodium hydroxide (NaOH 96.0 wt.%) were mixed well. Si/Al molar ratio SiO2/Al2O328.5, alkali to silicon molar ratio alkali to SiO20.115 percent of Y molecular sieve by extrusion moldingThe amount was 96.3 wt%, the binder content was 3.7 wt%, and the cross section was clover-leaf strip-shaped molecular sieve catalyst precursor.
c) Roasting the Y molecular sieve catalyst precursor I prepared in the step b) for 6 hours at 550 ℃ in an air atmosphere to obtain a Y molecular sieve catalyst precursor II.
d) Contacting the Y molecular sieve catalyst precursor II prepared in the step c) with ammonium nitrate solution with the mass fraction of 15% for 3 times and 1 hour each time at the temperature of 60 ℃, and separating, drying and roasting a solid product to obtain the Y molecular sieve catalyst. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 86N/cm.
[ example 8 ]
As in [ example 1 ], except that:
b) 0.05 g of sodium hydroxide, silica-alumina molar ratio SiO, was added2/Al2O328.5, alkali to silicon molar ratio alkali to SiO2A molecular sieve catalyst precursor in the form of a strand having a Y molecular sieve content of 95.3 wt%, a binder content of 4.7 wt%, and a circular cross-section was prepared by extrusion molding ═ 0.146.
The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 88N/cm.
[ example 9 ]
As in [ example 1 ], except that:
b) adding sodium hydroxide and controlling the mole ratio of silicon to aluminum (SiO)2/Al2O360, alkali to silicon molar ratio alkali to SiO2A strand-shaped molecular sieve catalyst precursor having a Y molecular sieve content of 96.9 wt%, a binder content of 3.1 wt%, and a circular cross-section was prepared by extrusion molding ═ 0.10.
The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 77N/cm.
[ example 10 ]
As in [ example 1 ], except that:
a) the material ratio (molar ratio) of the reaction mixture is as follows:
SiO2/Al2O3＝10
NaOH/SiO2＝0.6
H2O/SiO2＝20
the weight loss rate of the synthesized Y molecular sieve was tested to be 7.4 wt%.
b) Si/Al molar ratio SiO2/Al2O328.5, alkali to silicon molar ratio alkali to SiO2A precursor of a molecular sieve catalyst having a stripe shape with a circular cross section and a Y molecular sieve content of 97.1 wt%, a binder content of 2.9 wt% was prepared by extrusion molding ═ 0.094.
The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 82N/cm.
[ example 11 ]
Similarly, (example 1) except that 30 g of the Y molecular sieve catalyst prepared in the step d) is contacted with 300 g of phosphoric acid with the mass fraction of 2% at 30 ℃ for 3 hours, and the solid product is separated, dried and roasted to obtain the Y molecular sieve catalyst containing P. The P content was 0.1% by weight. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 80N/cm.
[ example 12 ]
Similarly, (example 1) except that 30 g of the Y molecular sieve catalyst prepared in the step d) is contacted with 450 g of lanthanum nitrate aqueous solution with the mass fraction of 3% at 75 ℃ for 2 hours, and the solid product is separated, dried and roasted to obtain the Y molecular sieve catalyst containing the lanthanum element. Lanthanum content was determined by ICP to be 0.17 wt%. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 85N/cm.
[ example 13 ]
Similarly [ example 11 ], except that 20 g of the Y molecular sieve catalyst containing P was further contacted with 300 g of lanthanum nitrate aqueous solution with a mass fraction of 3% at 95 ℃ for 2 hours, and the solid product was separated, dried and calcined to obtain the Y molecular sieve catalyst containing P and lanthanum elements. The lanthanum content was determined by ICP to be 0.2 wt%. The XRD pattern of the product was similar to that of FIG. 1. The compressive strength of the Y molecular sieve catalyst is 78N/cm.
[ COMPARATIVE EXAMPLE 1 ]
Similarly [ example 1 ], except that silica sol was used as the binder:
b) mixing synthetic Y molecular sieve 45.5 g and alkaline silica Sol (SiO)240.0 wt%) 5.04 g and sesbania powder 0.5616 g, and extrusion molding to prepare a precursor of a strip-shaped molecular sieve catalyst with the Y molecular sieve content of 95.4 wt%, the binder content of 4.6 wt% and the cross section of clover.
The XRD spectrum of the product is shown in figure 1. The compressive strength of the Y molecular sieve catalyst is 32N/cm.
[ COMPARATIVE EXAMPLE 2 ]
The same as [ example 1 ] except that alumina was used as the binder:
b) mixing synthetic Y molecular sieve 45.5 g and alumina (Al)2O396 wt%) 2.1 g and sesbania powder 0.5616 g, and extrusion molding to prepare a precursor of a strip-shaped molecular sieve catalyst with the Y molecular sieve content of 95.4 wt%, the binder content of 4.6 wt% and the cross section of clover.
The XRD spectrum of the product is shown in figure 1. The compressive strength of the Y molecular sieve catalyst is 41N/cm.
[ COMPARATIVE EXAMPLE 3 ]
The binderless Y molecular sieve catalyst was prepared according to the method of document CN 102039150B: will be provided with
[ example 1 ] 60 g of the Y molecular sieve synthesized in the method is uniformly mixed with 30 g of fumed silica, 0.11 g of sodium aluminate and 10 g of calcium carbonate, extruded into strips, dried at 80 ℃ for 3h, crystallized in water vapor at 130 ℃ for 200h, taken out, dried at 120 ℃ for 3h, calcined at 400 ℃ for 2h, and calcined at 550 ℃ for 3h to obtain the Y molecular sieve catalyst.
The XRD spectrum of the product is similar to that of figure 1, the content of the molecular sieve in the product is 98.5 weight percent, and the compressive strength is 178N/cm.
[ example 14 ]
The catalyst in [ example 1 ] was used in a continuous fixed bed benzene and diethylbenzene transalkylation reaction under the following conditions: the temperature is 165 ℃, the pressure is 3.5MPa, the mass ratio of the benzene to the diethylbenzene is 2, and the total airspeed is 3.5h-1After the reaction was continued for 3 hours, the diethylbenzene conversion was 75.6%.
[ COMPARATIVE EXAMPLE 4 ]
Will be described in [ comparative example 3 ]The catalyst is used for the continuous fixed bed benzene and diethylbenzene transalkylation reaction, and the reaction conditions are as follows: the temperature is 165 ℃, the pressure is 3.5MPa, the mass ratio of benzene to diethylbenzene is 2, and the ethylene mass space velocity is 3.5h-1After 3 hours of continuous reaction, the ethylene conversion was only 46.3%.

Claims (20)

1. A Y molecular sieve catalyst comprises the following components in parts by weight:
a) 92-99 parts of a Y molecular sieve;
b) 1-8 parts of a silica-alumina gel binder;
the silica-alumina gel binder is obtained by the step of contacting a silicon source, an aluminum source and alkali; silicon source of SiO2Calculated by Al as the aluminum source2O3Alkali to silicon molar ratio alkali to SiO20 to 0.3, Si/Al molar ratio SiO2/Al2O3＝25～50；
The Si-Al molar ratio SiO of the Y molecular sieve2/Al2O34.5-40 percent; the compressive strength of the Y molecular sieve catalyst is 65-99N/cm;
the Y molecular sieve catalyst is prepared by the following method, including:
a) providing a synthesized Y molecular sieve;
b) and directly molding the synthetic Y molecular sieve, a silicon source, an aluminum source and alkali to obtain the Y molecular sieve catalyst.
2. The Y molecular sieve catalyst of claim 1, wherein the alkali to silica molar ratio alkali to SiO2＝0.02～0.3。
3. The Y molecular sieve catalyst of claim 2, wherein the alkali to silica molar ratio alkali to SiO2＝0.03～0.22。
4. The Y molecular sieve catalyst of claim 3, wherein the alkali to silica molar ratio alkali to SiO2＝0.04～0.18。
5. Y is as defined in claim 1The subsieve catalyst is characterized in that the silicon source is selected from silica sol, fuming silica gel, water glass or Y4-nSiXnAt least one of the silicon-containing compounds of (a); general formula Y4-nSiXnWherein n is an integer of 1 to 4, Y is an alkanyl group, X is selected from Cl, methoxy OMe, ethoxy OEt or trimethylsiloxy OSiMe3；
The aluminum source is selected from at least one of sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate or aluminum chloride;
the alkali is at least one of quaternary ammonium alkali and alkali taking alkali metal elements or alkaline earth metal elements as cations.
6. The Y molecular sieve catalyst of claim 5, wherein the molecular sieve of formula Y4-nSiXnIn the formula, Y is methyl, ethyl or propyl; the quaternary ammonium base is selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N, N, N-trimethyladamantyl ammonium hydroxide or dimethyldiethylammonium hydroxide.
7. The Y molecular sieve catalyst of claim 1, wherein the content of the Y molecular sieve is 95-99 parts by weight, and the content of the silica-alumina gel binder is 1-5 parts by weight.
8. The Y molecular sieve catalyst of claim 7, wherein the content of the Y molecular sieve is 96-99 parts by weight, and the content of the silica-alumina gel binder is 1-4 parts by weight.
9. The Y molecular sieve catalyst of claim 1, wherein the source of silicon is selected from at least one of silica sol or fumed silica; the alkali is at least one of NaOH or KOH.
10. The Y molecular sieve catalyst of claim 1, wherein the Y molecular sieve has a crystallite diameter of from 60 nm to 1 micron.
11. The Y molecular sieve catalyst of claim 1, wherein the compressive strength of the Y molecular sieve catalyst is from 65 to 90N/cm.
12. The Y molecular sieve catalyst of claim 1, wherein the catalyst comprises 0 to 0.5 parts by weight phosphorus.
13. The Y molecular sieve catalyst of claim 1, wherein the catalyst comprises 0 to 0.5 parts by weight of a rare earth metal element.
14. The Y molecular sieve catalyst of claim 13, wherein the rare earth metal element is selected from at least one of yttrium, lanthanum, cerium, or neodymium.
15. A preparation method of a Y molecular sieve catalyst comprises the following steps:
a) providing a synthesized Y molecular sieve;
b) directly molding the synthetic Y molecular sieve, a silicon source, an aluminum source and alkali to obtain the Y molecular sieve catalyst;
wherein the silicon source is selected from silica sol, fuming silica gel, water glass or Y4-nSiXnAt least one of the silicon-containing compounds of (a); general formula Y4-nSiXnWherein n is an integer of 1 to 4, Y is an alkanyl group, X is selected from Cl, methoxy OMe, ethoxy OEt or trimethylsiloxy OSiMe3；
The aluminum source is selected from at least one of sodium aluminate, aluminum hydroxide, aluminum sulfate, aluminum nitrate or aluminum chloride;
the alkali is at least one of quaternary ammonium alkali and alkali taking alkali metal elements or alkaline earth metal elements as cations;
silicon source of SiO2Calculated by Al as the aluminum source2O3Alkali to silicon molar ratio alkali to SiO20 to 0.3, Si/Al molar ratio SiO2/Al2O3＝25～85。
16. The method of claim 15, wherein the mole ratio of alkali to silica is alkali to SiO2＝0.02～0.3。
17. The method of claim 16, wherein the mole ratio of alkali to silica is alkali to SiO2＝0.03～0.22。
18. The method of claim 17, wherein the mole ratio of alkali to silica is alkali to SiO2＝0.04～0.18。
19. The method of claim 15, wherein the molar ratio of silica to alumina is SiO2/Al2O3＝25～60。
20. The Y molecular sieve catalyst of any one of claims 1 to 14, or the Y molecular sieve catalyst synthesized by the method of any one of claims 15 to 19, is applied to the reaction of liquid phase transalkylation of benzene and polyethylbenzene to prepare ethylbenzene, and liquid phase alkylation of benzene and ethylene to prepare ethylbenzene.
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