CN112429745A - H-type MCM-22 molecular sieve and preparation method and application thereof - Google Patents

H-type MCM-22 molecular sieve and preparation method and application thereof Download PDF

Info

Publication number
CN112429745A
CN112429745A CN201910791355.XA CN201910791355A CN112429745A CN 112429745 A CN112429745 A CN 112429745A CN 201910791355 A CN201910791355 A CN 201910791355A CN 112429745 A CN112429745 A CN 112429745A
Authority
CN
China
Prior art keywords
molecular sieve
hours
boron
type mcm
mcm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910791355.XA
Other languages
Chinese (zh)
Other versions
CN112429745B (en
Inventor
金少青
孙洪敏
沈震浩
王达锐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201910791355.XA priority Critical patent/CN112429745B/en
Publication of CN112429745A publication Critical patent/CN112429745A/en
Application granted granted Critical
Publication of CN112429745B publication Critical patent/CN112429745B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses an H-type MCM-22 molecular sieve and a preparation method and application thereof. The H-type MCM-22 molecular sieve has an X-ray diffraction pattern with diffraction peaks at the 2 theta positions of 7.2 +/-0.09 degrees, 8.0 +/-0.10 degrees, 9.6 +/-0.07 degrees, 12.7 +/-0.10 degrees, 14.4 +/-0.07 degrees, 15.8 +/-0.08 degrees, 20.0 +/-0.11 degrees, 22.7 +/-0.15 degrees, 25.1 +/-0.15 degrees, 26.1 +/-0.12 degrees and 26.9 +/-0.13 degrees; the external surface area is 270-500 m2(ii)/g; the thickness of the lamella is 2.5-20 nm. The H-type MCM-22 molecular sieve provided by the invention has the advantages of high external surface area and lamella thickness not more than 20 nm.

Description

H-type MCM-22 molecular sieve and preparation method and application thereof
Technical Field
The invention relates to an H-type MCM-22 molecular sieve and a preparation method and application thereof, belonging to the field of molecular sieve inorganic materials.
Background
The MCM-22 molecular sieve is a silicon-aluminum molecular sieve material which is synthesized by researchers of the American Mobil company in the eighties of the last century and has a topological structure of MWW, and has two sets of independent pore channel systems: one set is a two-dimensional sine ten-membered ring channel in the layer, and the effective pore diameter is 0.41nm x 0.51 nm; the other set is an interlayer twelve-membered ring super cage with the size of 0.71nm x 0.71nm x 1.81nm, and is communicated with the outside through a ten-membered ring window with the pore size of 0.40nm x 0.55 nm. In addition, the molecular sieve also has a bowl-shaped twelve-membered ring half supercage located on the outer surface of the molecular sieve crystal. Due to good thermal stability, hydrothermal stability and unique acid property, the H-type MCM-22 molecular sieve plays an important role in industrial catalysis, and the catalyst prepared by taking the H-type MCM-22 molecular sieve as an active component is successfully applied to a process for preparing ethylbenzene by liquid-phase alkylation of benzene and ethylene and a process for preparing cumene by liquid-phase alkylation of benzene and propylene.
As the size of benzene molecules exceeds 0.5nm, the benzene molecules are difficult to enter the pore channels of the H-type MCM-22 molecular sieve, and benzene alkylation reaction mainly occurs on an open outer surface twelve-membered ring semi-super cage, so that the H-type MCM-22 molecular sieve is required to have higher outer surface area and thinner lamella thickness. The thickness of the lamella of the single-layer MCM-22 molecular sieve is 2.5nm, and the calculation shows that the theoretical external surface area of the single-layer MCM-22 molecular sieve is 517m2/g (chem.sci.,2015,6, 6320). In practice, however, the synthesized MCM-22 molecular sieve forms a multi-layer three-dimensional structure after being calcined due to strong hydrogen bonding between layers, the thickness of the layers exceeds 30nm, and the external surface area of the molecular sieve is not more than 120m2(J.Catal.,2000,191,218). The MCM-22 molecular sieve is stripped in the post-treatment layer, so that the MCM-22 molecular sieve can be thinned and the external surface area of the molecular sieve can be effectively improved, but the method relates to operations such as cetyl trimethyl ammonium bromide swelling, tetrapropyl ammonium hydroxide treatment and the like, the process is complex, and the cost is lowHigher, has certain destructive effect on the structure of the molecular sieve, and can not realize industrial application.
Meanwhile, in the conventional method, a silicon source, an aluminum source, an inorganic alkali source, an organic structure directing agent and water are uniformly mixed and subjected to hydrothermal crystallization for a certain time to prepare the MCM-22 molecular sieve (CN00116529.1, CN201210218349.3), but the mole fraction of aluminum is only in the range of 3.3-6.6%. In addition, due to the addition of the inorganic alkali source, the prepared MCM-22 molecular sieve contains a large amount of alkali metal or alkaline earth metal ions, has no acidity and cannot be used for acid-catalyzed reactions. For these MCM-22 molecular sieves, ammonium ion exchange must be carried out for many times by ammonium salts such as ammonium nitrate or ammonium chloride, and alkali metal or alkaline earth metal ions must be exchanged for ammonium ions, and then the molecular sieves are converted into H-type MCM-22 molecular sieves by roasting, so that the molecular sieves have excellent acid catalytic performance. However, the ammonium ion exchange process is not only complicated, but also produces a large amount of ammonium-nitrogen waste water, which is very unfavorable for industrial production.
From the above, the preparation of high external surface area, thin-layer H-type MCM-22 molecular sieve still faces certain problems and challenges. From the perspective of industrial production and application, the development of a simple and feasible method for preparing the H-type MCM-22 molecular sieve with high external surface area and a thin layer has important significance.
Disclosure of Invention
The invention aims to solve the technical problems of low external surface area and lamella thickness of an H-type MCM-22 molecular sieve, and provides the H-type MCM-22 molecular sieve which has the advantages of high external surface area and lamella thickness of no more than 20 nm.
The second technical problem to be solved by the invention is to solve the problems of complicated production steps and the need of multiple ammonium ion exchange in the prior art, which causes the discharge of a large amount of ammonium nitrogen wastewater, and provide a novel preparation method of the H-type MCM-22 molecular sieve.
The invention aims to solve the technical problem of providing the application of the H-type MCM-22 molecular sieve in the benzene alkylation reaction.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: h-type MCM-22 molecular sieve, its X-ray diffractionDiffraction peaks appear at 2 theta of 7.2 +/-0.09 °, 8.0 +/-0.10 °, 9.6 +/-0.07 °, 12.7 +/-0.10 °, 14.4 +/-0.07 °, 15.8 +/-0.08 °, 20.0 +/-0.11 °, 22.7 +/-0.15 °, 25.1 +/-0.15 °, 26.1 +/-0.12 ° and 26.9 +/-0.13 °; the external surface area is 270-500 m2A/g, preferably 300 to 500m2(ii)/g; the thickness of the lamella is 2.5 to 20nm, preferably 2.5 to 10 nm.
Further, the mole fraction of aluminum in the H-type MCM-22 molecular sieve is 0.1-10%, preferably 1-10%; the boron mole fraction is 0.1-10%, preferably 0.1-3%.
Further, the H-type MCM-22 molecular sieve does not contain alkali metals or alkaline earth metals.
Further, there is an overlap in the X-ray diffraction patterns at 8.0 ± 0.10 °, 9.6 ± 0.07 ° of 2 θ.
In order to solve the second technical problem, the invention provides a preparation method of the H-type MCM-22 molecular sieve, which comprises the following steps:
(1) contacting water, organic amine, a boron source, a silicon source and organic silicon to form gel, and performing hydrothermal crystallization treatment to obtain the B-MWW molecular sieve;
(2) carrying out boron removal treatment on the B-MWW molecular sieve obtained in the step (1);
(3) and (3) carrying out aluminum supplement treatment on the product obtained in the step (2) to obtain the H-type MCM-22 molecular sieve.
Further, in the step (1), SiO is used as the silicon source according to the molar ratio2Counting: organosilicon: source of boron as B2O3Counting: organic amine: h2O is 1: w: x: y: and z, uniformly mixing water, organic amine, a boron source, a silicon source and organic silicon into glue, and carrying out hydrothermal crystallization to obtain the B-MWW molecular sieve, wherein w is 0.01-0.15, x is 0.2-3, y is 0.2-3, z is 10-50, preferably w is 0.02-0.1, x is 0.5-2, y is 0.5-2, and z is 20-40. Wherein, the material obtained after the hydrothermal crystallization can be subjected to conventional post-treatment processes such as centrifugation, washing, drying, roasting and the like according to requirements.
Further, the hydrothermal crystallization conditions in the step (1) are as follows: the rotating speed is 1-100 rpm, the crystallization temperature is 110-190 ℃, the crystallization time is 1-10 days, and the following steps are preferably performed: the rotating speed is 10-50 rpm, the crystallization temperature is 130-170 ℃, and the crystallization time is 3-8 days; the drying conditions in the step (1) are as follows: drying at 60-120 ℃ for 1-24 hours, preferably: drying for 6-18 hours at 80-100 ℃; the roasting conditions in the step (1) are as follows: roasting at 450-650 ℃ for 4-12 hours in air or oxygen atmosphere, preferably: roasting for 6-10 hours at 500-600 ℃ in air or oxygen atmosphere.
Further, the step (2) is specifically: mixing the B-MWW molecular sieve obtained in the step (1) with n mol/L acid solution according to the mass ratio of 1: m, mixing, carrying out boron removal treatment, and drying to obtain a boron-removed B-MWW molecular sieve; wherein n is 0.01-10, m is 10-80, preferably n is 0.1-6, and m is 10-50. Wherein, the material obtained by the boron removal treatment can adopt the conventional post-treatment processes, such as centrifugation, washing and the like, before being dried.
Further, the boron removing conditions in the step (2) are as follows: treating at 30-150 ℃ for 1-48 hours, preferably: treating for 6-36 hours at 50-120 ℃; the drying conditions in the step (2) are as follows: drying at 60-120 ℃ for 1-24 hours, preferably: drying for 6-18 hours at 80-100 ℃.
Further, the step (3) is specifically: and (3) mixing the boron-removed B-MWW molecular sieve obtained in the step (2) with an aluminum source and deionized water according to the mass ratio of 1: a: b, mixing, and performing aluminum supplement treatment to obtain the H-type MCM-22 molecular sieve; wherein a is 0.05-1, b is 10-80, preferably a is 0.1-0.5, and b is 10-50. Wherein, the materials obtained by the aluminum supplement treatment can be subjected to conventional post-treatment processes such as centrifugation, washing, drying, roasting and the like according to requirements.
Further, the aluminum supplementing conditions in the step (3) are as follows: treating at 30-150 ℃ for 1-48 hours, preferably: treating for 6-36 hours at 50-120 ℃; the drying conditions in the step (3) are as follows: drying at 60-120 ℃ for 1-24 hours, preferably: drying for 6-18 hours at 80-100 ℃; the roasting conditions in the step (3) are as follows: roasting at 450-650 ℃ for 4-12 hours in air or oxygen atmosphere, preferably: roasting for 6-10 hours at 500-600 ℃ in air or oxygen atmosphere.
Further, the silicon source is selected from at least one of gas-phase method silicon dioxide, silica sol or ethyl orthosilicate; the boron source is selected from at least one of boric acid or boron oxide, and the organic amine is selected from at least one of piperidine or hexamethyleneimine; the organic silicon is selected from at least one of dimethyldiethoxysilane, dimethyldichlorosilane, dimethylchlorobromosilane, dimethylethylchlorosilane, dimethylisopropylchlorosilane, dimethylphenylchlorosilane, trimethylchlorosilane, triethylchlorosilane, methylphenylvinylchlorosilane or diphenyldichlorosilane; the acid solution is at least one of nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid or oxalic acid solution; the aluminum source is at least one selected from aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum oxide and aluminum isopropoxide.
Further, the silicon source is selected from at least one of gas-phase method silicon dioxide, silica sol or ethyl orthosilicate; the boron source is selected from boric acid, and the organic amine is selected from at least one of piperidine or hexamethyleneimine; the organic silicon is selected from at least one of dimethyl diethoxysilane, dimethyl dichlorosilane, dimethyl chlorobromosilane or diphenyl dichlorosilane; the acid solution is at least one of nitric acid, hydrochloric acid or sulfuric acid solution, and the aluminum source is at least one of aluminum nitrate or aluminum sulfate.
In order to solve the third technical problem, the invention provides an application of the H-type MCM-22 molecular sieve in benzene alkylation reaction.
Further, the reaction conditions for the benzene alkylation reaction include: the reaction temperature is 160-240 ℃, the pressure is 2.8-4.0 MPa, the benzene/ethylene molar ratio is 2-30, and the total mass airspeed of the materials is 5-80 hours-1。
Compared with the prior art, the invention has the following advantages:
1. the H-type MCM-22 molecular sieve provided by the invention has the external surface area of 270-500 m2H-type MCM-22 molecular sieve with lamella thickness not more than 20 nm. In addition, the aluminum mole fraction in the H-type MCM-22 molecular sieve can be flexibly regulated and controlled, and the maximum aluminum mole fraction can reach 10%. The H-type MCM-22 molecular sieve solves the problems of low external surface area, thick lamella and low aluminum mole fraction of the H-type MCM-22 molecular sieve in the prior art.
2. The method for preparing the H-type MCM-22 molecular sieve provided by the invention comprises the steps of firstly preparing the B-MWW molecular sieve which does not contain alkali metal or alkaline earth metal and has the lamella thickness not more than 20nm, and then carrying out boron removal and aluminum supplement treatment on the molecular sieve, so that the condition that the Na-type MCM-22 molecular sieve can obtain the H-type MCM-22 molecular sieve only by carrying out ammonium exchange for many times is avoided, and a large amount of Al is introduced into a molecular sieve framework while the structure and the appearance of the molecular sieve are protected from being influenced, and the H-type MCM-22 molecular sieve with high acid center content is obtained.
3. The H-type MCM-22 molecular sieve provided by the invention has the advantages of large acid center number, high external surface area, thin lamella and the like, so that the H-type MCM-22 molecular sieve has good application in benzene alkylation reaction and shows excellent catalytic performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of the H-type MCM-22 molecular sieve synthesized in example 1;
FIG. 2 is an X-ray diffraction pattern of the H-type MCM-22 molecular sieve synthesized in comparative example 1;
FIG. 3 is an X-ray diffraction pattern of the H-type MCM-22 molecular sieve synthesized in comparative example 2;
FIG. 4 is a transmission electron micrograph of the synthesized H-type MCM-22 molecular sieve [ example 1 ];
FIG. 5 is a transmission electron micrograph of the H-type MCM-22 molecular sieve synthesized in comparative example 1;
FIG. 6 is a transmission electron micrograph of the H-type MCM-22 molecular sieve synthesized in comparative example 2.
In the X-ray diffraction diagrams of fig. 1,2 and 3, diffraction peaks appear at 7.2 °, 8.0 °, 9.6 °, 12.7 °, 14.4 °, 15.8 °, 20.0 °, 22.7 °, 25.1 °, 26.1 ° and 26.9 ° of 2 θ, which match with the characteristic diffraction peaks of the MCM-22 molecular sieve, indicating that both are MCM-22 molecular sieves, but there is a certain overlap between the two diffraction peaks at 8.0 ° and 9.6 ° in fig. 1, indicating that the stacking between layers in the H-type MCM-22 molecular sieve provided by the present invention is not too large, the outer surface area thereof should be higher, and the ordered layer thickness thereof is thinner, compared with comparative examples 1 and 2. From the results of FIGS. 4, 5 and 6, it can be further confirmed that the thickness of the H-type MCM-22 molecular sieve in example 1 is 2.5-7.5 nm as seen in FIG. 4, while the thickness of the H-type MCM-22 molecular sieve in comparative examples 1 and 2 is more than 30nm as seen in FIGS. 5 and 6.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
In the present invention, percentages and percentages are by mass unless otherwise specifically indicated.
Throughout the specification and claims, unless explicitly described otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated step or element but not the exclusion of any other step or element.
In the present invention, including the following examples and comparative examples, the structure, external surface area, thickness, aluminum content and boron content of the H-type MCM-22 molecular sieve were determined by X-ray diffraction, nitrogen desorption, transmission electron microscopy, elemental analysis test, respectively.
The X-ray diffraction test method of the molecular sieve product comprises the following steps: analyzing the phase of the sample by using a Nippon Rigaku Ultima IV type X-ray powder diffractometer, and taking Cu Ka line as a radiation source
Figure BDA0002179646930000051
A nickel optical filter, wherein the 2 theta scanning range is 2-50 degrees, the operating voltage is 40KV, the current is 40mA, and the scanning speed is 10 degrees/min; the nitrogen adsorption and desorption test method comprises the following steps: measuring a nitrogen adsorption-desorption isotherm of the sample by adopting a Japanese BEL-MAX specific surface and aperture analyzer, thereby obtaining the external surface area of the sample, measuring the temperature at 77K, and carrying out vacuum pretreatment on the sample at 573K for 6 hours before the test; the transmission electron microscope test method comprises the following steps: determining the thickness of the sample by adopting a JEOL JEM-2100F electron microscope, wherein the accelerating voltage is 200 kV; the element analysis test method comprises the following steps: the boron content and the aluminum content of the sample were analyzed by a Varian-2000 analyzer, and the sample was dissolved with a hydrofluoric acid solution before the test.
[ example 1 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing, drying for 16 hours at 80 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ in air atmosphere for 10 hours to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in figures 1 and 4, respectively, and has an external surface area of 500m2The thickness of the lamella is 2.5-7.5 nm, the mole fraction of aluminum is 10%, and the mole fraction of boron is 0.2%.
[ example 2 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: hexamethyleneimine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, hexamethyleneimine, boric acid, 60 g of gas phase method silicon dioxide and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing, drying for 16 hours at 80 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ in air atmosphere for 10 hours to obtain the H-type MCM-22 molecular sieve product. X-ray diffraction pattern and transmission electron microscope pattern of the molecular sieveSimilar to FIGS. 1 and 4, respectively, the outer surface area is 362m2The thickness of the lamella is 10-15 nm, the mole fraction of aluminum is 5%, and the mole fraction of boron is 0.8%.
[ example 3 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: hexamethyleneimine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, hexamethyleneimine, boric acid, 60 g of gas phase method silicon dioxide and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization for 6.5 days at 50rpm and 170 ℃, centrifuging, washing, drying for 16 hours at 80 ℃, and roasting for 10 hours at 550 ℃ in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing, drying for 16 hours at 80 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ in air atmosphere for 10 hours to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, respectively, and has an external surface area of 284m2The thickness of the lamella is 15-20 nm, the mole fraction of aluminum is 2.3%, and the mole fraction of boron is 1.2%.
[ example 4 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 7 days, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing, drying for 16 hours at 80 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50 are mixedAnd (3) mixing, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ in air atmosphere for 10 hours to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, respectively, and has an outer surface area of 412m2The thickness of the lamella is 5-15 nm, the mole fraction of aluminum is 7%, and the mole fraction of boron is 0.5%.
[ example 5 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 4 days, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing, drying for 16 hours at 80 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ in air atmosphere for 10 hours to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, respectively, and has an outer surface area of 306m2The thickness of the lamella is 10-20 nm, the mole fraction of aluminum is 3.5%, and the mole fraction of boron is 1.0%.
[ example 6 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 150 ℃ for 7 days, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating at 120 ℃ for 24 hours,centrifuging, washing and drying at 100 ℃ for 8 hours to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, and has an outer surface area of 486m2The thickness of the lamella is 2.5-10 nm, the mole fraction of aluminum is 9.6%, and the mole fraction of boron is 0.3%.
[ example 7 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, performing dynamic hydrothermal crystallization at 50rpm and 130 ℃ for 10 days, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing and drying for 8 hours at 100 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, respectively, and has an outer surface area of 453m2The thickness of the lamella is 5-10 nm, the mole fraction of aluminum is 8.5%, and the mole fraction of boron is 0.4%.
[ example 8 ]
First, the molar ratio of SiO is used2: dimethyl dichlorosilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20 mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyldichlorosilane uniformly to obtain glue, dynamic hydrothermal crystallizing at 50rpm and 170 deg.C for 5.5 days, centrifuging, washing, drying at 100 deg.C for 8 hr, and cooling to 550 deg.CRoasting for 10 hours in an air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing and drying for 8 hours at 100 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in figures 1 and 4, and has an outer surface area of 461m2The thickness of the lamella is 5-10 nm, the mole fraction of aluminum is 8.6%, and the mole fraction of boron is 0.4%.
[ example 9 ]
First, the molar ratio of SiO is used2: dimethyl dichlorosilane: b is2O3: piperidine: h2O is 1: 0.02: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of gas phase method silicon dioxide and dimethyldichlorosilane to form glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing and drying for 8 hours at 100 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in figures 1 and 4, respectively, and has an outer surface area of 340m2The thickness of the lamella is 10-20 nm, the mole fraction of aluminum is 4.6%, and the mole fraction of boron is 0.9%.
[ example 10 ]
First, the molar ratio of SiO is used2: dimethyl dichlorosilane: b is2O3: piperidine: h2O is 1: 0.06: 0.6: 1.5: 20 corresponding amounts of water, piperidine, boric acid, 60 g of gas phase process twoSilicon oxide and dimethyldichlorosilane are uniformly mixed to form glue, dynamic hydrothermal crystallization is carried out for 8 days at 50rpm and 170 ℃, centrifugation, washing and drying are carried out for 8 hours at 100 ℃, and roasting is carried out for 10 hours at 550 ℃ in air atmosphere, thus obtaining the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing and drying for 8 hours at 100 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 100 ℃ for 8 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in figures 1 and 4, and has an outer surface area of 473m2The thickness of the lamella is 2.5-10 nm, the mole fraction of aluminum is 8.9%, and the mole fraction of boron is 0.3%.
[ example 11 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 0.5mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating at 100 ℃ for 36 hours, centrifuging, washing, drying at 90 ℃ for 12 hours to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 50, treating at 120 ℃ for 36 hours, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in figures 1 and 4, and its outer surface area is 491m2The thickness of the lamella is 2.5-7.5 nm, the mole fraction of aluminum is 8.7%, and the mole fraction of boron is 0.4%.
[ example 12 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L sulfuric acid solution according to the mass ratio of 1: 30, treating for 6 hours at 100 ℃, centrifuging, washing, drying for 12 hours at 90 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5: 30, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 530 ℃ for 8 hours in an oxygen atmosphere to obtain the H-type MCM-22 molecular sieve product. The X-ray diffraction pattern and transmission electron micrograph of the molecular sieve are similar to those of figures 1 and 4 respectively, and the external surface area is 485m2The thickness of the lamella is 2.5-10 nm, the mole fraction of aluminum is 7.1%, and the mole fraction of boron is 0.6%.
[ example 13 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 0.5mol/L nitric acid solution according to the mass ratio of 1: 80, treating for 48 hours at 80 ℃, centrifuging, washing, drying for 12 hours at 90 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum sulfate and deionized water according to the mass ratio of 1: 0.5: 30, treating at 120 ℃ for 36 hours, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 530 ℃ for 8 hours in an oxygen atmosphere to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, respectively, and has an outer surface area of 478m2G, lamella thickness of 2.5 &10nm, 5.2 percent of aluminum mole fraction and 0.8 percent of boron mole fraction.
[ example 14 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 6mol/L nitric acid solution according to the mass ratio of 1: 40, treating for 12 hours at 150 ℃, centrifuging, washing, drying for 12 hours at 90 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum sulfate and deionized water according to the mass ratio of 1: 0.5: 40, treating for 18 hours at 60 ℃, centrifuging, washing, drying for 12 hours at 90 ℃, and roasting for 6 hours at 600 ℃ in air atmosphere to obtain the H-type MCM-22 molecular sieve product. The X-ray diffraction pattern and transmission electron micrograph of the molecular sieve are similar to those of FIGS. 1 and 4 respectively, and the external surface area is 492m2The thickness of the lamella is 2.5-7.5 nm, the mole fraction of aluminum is 4.6%, and the mole fraction of boron is 0.2%.
[ example 15 ]
First, the molar ratio of SiO is used2: dimethyl diethoxysilane: b is2O3: piperidine: h2O is 1: 0.035: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid, 60 g of fumed silica and dimethyl diethoxysilane into glue, carrying out dynamic hydrothermal crystallization at 50rpm and 170 ℃ for 5.5 days, centrifuging, washing, drying at 90 ℃ for 12 hours, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 6mol/L nitric acid solution according to the mass ratio of 1: 40, treating for 12 hours at 150 ℃, centrifuging, washing, drying for 12 hours at 90 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum sulfate and deionized water according to the mass ratio of 1: 0.5: 40, treating at 60 deg.C for 10 hr, centrifuging, washing, drying at 90 deg.C for 12 hr, and calcining at 600 deg.C in air atmosphere for 6 hrAnd obtaining the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph similar to those of FIG. 1 and FIG. 4, respectively, and has an external surface area of 490m2The thickness of the lamella is 2.5-7.5 nm, the mole fraction of aluminum is 2.8%, and the mole fraction of boron is 0.2%.
[ example 16 ]
Mixing the H-type MCM-22 molecular sieve prepared in the example 1 and the binder alumina according to the mass ratio of 2: 1, fully mixing in a kneader, and slowly adding dilute nitric acid to form a colloidal precursor with moderate dryness and humidity. And extruding and molding the precursor, drying, roasting at 550 ℃ for 6 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve catalyst, and using the H-type MCM-22 molecular sieve catalyst for the reaction of benzene and ethylene alkylation for preparing ethylbenzene. Reaction conditions are as follows: temperature 180 ℃, pressure 3.8MPa, benzene/ethylene molar ratio 3: 1, total mass airspeed of material 28.1 hours-1. The ethylene conversion rate was 99.4%, the ethylation selectivity was 99.6%, and the ethylbenzene selectivity was 91.0%, with the specific results shown in table 1.
[ examples 17 to 20 ]
The H-type MCM-22 molecular sieve prepared in the examples 2, 4, 7 and 9 is used for preparing H-type MCM-22 molecular sieve catalyst, the method is the same as the example 16, the reaction conditions are the same, and the reaction results are shown in the table:
examples Conversion of ethylene Selectivity of ethylation Ethylbenzene selectivity
Example 16 (based on example 1) 99.4％ 99.6％ 91.0％
Example 17 (based on example 2) 47.3％ 99.4％ 90.8％
Example 18 (based on example 4) 71.5％ 99.5％ 90.9％
Example 19 (based on example 7) 86.2％ 99.6％ 90.8％
Example 20 (based on example 9) 42.8％ 99.4％ 90.7％
[ COMPARATIVE EXAMPLE 1 ]
First, the molar ratio of SiO is used2：B2O3: piperidine: h2O is 1: 0.6: 1.5: 20, uniformly mixing corresponding amount of water, piperidine, boric acid and 60 g of gas phase method silicon dioxide to form glue, carrying out dynamic hydrothermal crystallization for 5.5 days at 50rpm and 170 ℃, centrifuging, washing, drying for 16 hours at 80 ℃, and roasting for 10 hours at 550 ℃ in air atmosphere to obtain the B-MWW molecular sieve. And then mixing the B-MWW molecular sieve with 2mol/L hydrochloric acid solution according to the mass ratio of 1: 50, treating for 24 hours at 120 ℃, centrifuging, washing, drying for 16 hours at 80 ℃ to obtain the boron-removed B-MWW molecular sieve, and mixing the boron-removed B-MWW molecular sieve with aluminum nitrate and deionized water according to the mass ratio of 1: 0.5:50, treating at 120 ℃ for 24 hours, centrifuging, washing, drying at 80 ℃ for 16 hours, and roasting at 550 ℃ in air atmosphere for 10 hours to obtain the H-type MCM-22 molecular sieve product. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in FIGS. 2 and 5, and outer surface area of 122m2The thickness of the lamella is 30-50 nm, the mole fraction of aluminum is 1.8%, and the mole fraction of boron is 1.5%.
[ COMPARATIVE EXAMPLE 2 ]
Reference US4954325 by molar ratio SiO2：Al2O3：Na2O: hexamethyleneimine: h2O is 1: 0.033: 0.06: 0.5: 26, uniformly mixing corresponding amounts of water, hexamethyleneimine, sodium metaaluminate, sodium hydroxide and 60 g of fumed silica to form glue, carrying out dynamic hydrothermal crystallization at 50rpm and 150 ℃ for 5 days, centrifuging, washing, drying, and roasting at 550 ℃ for 10 hours in air atmosphere to obtain the Na MCM-22 molecular sieve. Mixing the prepared Na type MCM-22 molecular sieve with 10 wt% ammonium nitrate solution according to the mass ratio of 1: 30, performing ammonium ion exchange at 90 ℃ for 1 hour each time for 3 times, then drying, and roasting at 550 ℃ for 6 hours in an air atmosphere to obtain the H-type MCM-22 molecular sieve. The molecular sieve has X-ray diffraction pattern and transmission electron micrograph shown in figures 3 and 6, respectively, and has an outer surface area of 113m2The thickness of the lamella exceeds 30nm, the mole fraction of aluminum is 6.4 percent, and the mole fraction of boron is 0 percent.
[ COMPARATIVE EXAMPLE 3 ]
Mixing the H-type MCM-22 molecular sieve prepared in the comparative example 1 and the alumina serving as a binder according to the mass ratio of 2: 1, fully mixing in a kneader, and slowly adding dilute nitric acid to form a colloidal precursor with moderate dryness and humidity. And extruding and molding the precursor, drying, roasting at 550 ℃ for 6 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve catalyst, and using the H-type MCM-22 molecular sieve catalyst for the reaction of benzene and ethylene alkylation for preparing ethylbenzene. Reaction conditions are as follows: temperature 180 ℃, pressure 3.8MPa, benzene/ethylene molar ratio 3: 1, total mass airspeed of material 28.1 hours-1. The conversion rate of ethylene is 23.6%, the selectivity of ethylation is 99.2%, and the selectivity of ethylbenzene is 90.5%.
[ COMPARATIVE EXAMPLE 4 ]
The H-type MCM-22 molecule prepared in comparative example 2The mass ratio of the sieve to the binder alumina is 2: 1, fully mixing in a kneader, and slowly adding dilute nitric acid to form a colloidal precursor with moderate dryness and humidity. And extruding and molding the precursor, drying, roasting at 550 ℃ for 6 hours in air atmosphere to obtain the H-type MCM-22 molecular sieve catalyst, and using the H-type MCM-22 molecular sieve catalyst for the reaction of benzene and ethylene alkylation for preparing ethylbenzene. Reaction conditions are as follows: temperature 180 ℃, pressure 3.8MPa, benzene/ethylene molar ratio 3: 1, total mass airspeed of material 28.1 hours-1. The conversion rate of ethylene is 34.6%, the selectivity of ethylation is 99.4%, and the selectivity of ethylbenzene is 90.8%.

Claims (10)

1. An H-type MCM-22 molecular sieve, the X-ray diffraction pattern of which shows diffraction peaks at 2 theta of 7.2 +/-0.09 °, 8.0 +/-0.10 °, 9.6 +/-0.07 °, 12.7 +/-0.10 °, 14.4 +/-0.07 °, 15.8 +/-0.08 °, 20.0 +/-0.11 °, 22.7 +/-0.15 °, 25.1 +/-0.15 °, 26.1 +/-0.12 ° and 26.9 +/-0.13 °; the external surface area is 270-500 m2A/g, preferably 300 to 500m2(ii)/g; the thickness of the lamella is 2.5 to 20nm, preferably 2.5 to 10 nm.
2. The H-type MCM-22 molecular sieve of claim 1, wherein the molar fraction of aluminum in the H-type MCM-22 molecular sieve is 0.1-10%, preferably 1-10%; the boron mole fraction is 0.1-10%, preferably 0.1-3%.
3. The MCM-22 molecular sieve form H of claim 1 characterized by an overlap of X-ray diffraction patterns at 8.0 ± 0.10 °, 9.6 ± 0.07 ° 2 Θ.
4. A process for the preparation of an H-type MCM-22 molecular sieve as claimed in any of claims 1-3, comprising the steps of:
(1) contacting water, organic amine, a boron source, a silicon source and organic silicon to form gel, and performing hydrothermal crystallization treatment to obtain the B-MWW molecular sieve;
(2) carrying out boron removal treatment on the B-MWW molecular sieve obtained in the step (1);
(3) and (3) carrying out aluminum supplement treatment on the product obtained in the step (2) to obtain the H-type MCM-22 molecular sieve.
5. The process for preparing H-type MCM-22 molecular sieve of claim 4, wherein in step (1), the silicon source is SiO in mole ratio2Counting: organosilicon: source of boron as B2O3Counting: organic amine: h2O is 1: w: x: y: and z, uniformly mixing water, organic amine, a boron source, a silicon source and organic silicon into glue, and carrying out hydrothermal crystallization to obtain the B-MWW molecular sieve, wherein w is 0.01-0.15, x is 0.2-3, y is 0.2-3, z is 10-50, preferably w is 0.02-0.1, x is 0.5-2, y is 0.5-2, and z is 20-40.
6. The method for preparing H-type MCM-22 molecular sieve according to claim 4 or 5, wherein the hydrothermal crystallization conditions in step (1) are as follows: the rotating speed is 1-100 rpm, the crystallization temperature is 110-190 ℃, the crystallization time is 1-10 days, and the following steps are preferably performed: the rotating speed is 10-50 rpm, the crystallization temperature is 130-170 ℃, and the crystallization time is 3-8 days.
7. The method for preparing the H-type MCM-22 molecular sieve of claim 4, wherein the step (2) is specifically: mixing the B-MWW molecular sieve obtained in the step (1) with n mol/L acid solution according to the mass ratio of 1: m, mixing, and carrying out boron removal treatment to obtain a boron-removed B-MWW molecular sieve; wherein n is 0.01-10, m is 10-80, preferably n is 0.1-6, and m is 10-50.
8. The method for preparing the H-type MCM-22 molecular sieve of claim 4, wherein the step (3) is specifically: and (3) mixing the boron-removed B-MWW molecular sieve obtained in the step (2) with an aluminum source and water according to the mass ratio of 1: a: b, mixing, and performing aluminum supplement treatment to obtain the H-type MCM-22 molecular sieve; wherein a is 0.05-1, b is 10-80, preferably a is 0.1-0.5, and b is 10-50.
9. The process for the preparation of the H-type MCM-22 molecular sieve of claim 4, characterized in that the deboronation conditions in step (2) are: treating at 30-150 ℃ for 1-48 hours, preferably: treating for 6-36 hours at 50-120 ℃; the aluminum supplementing condition in the step (3) is as follows: treating at 30-150 ℃ for 1-48 hours, preferably: treating at 50-120 ℃ for 6-36 hours.
10. Use of the H-form MCM-22 molecular sieve of any of claims 1-3 in benzene alkylation reactions.
CN201910791355.XA 2019-08-26 2019-08-26 H-type MCM-22 molecular sieve and preparation method and application thereof Active CN112429745B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910791355.XA CN112429745B (en) 2019-08-26 2019-08-26 H-type MCM-22 molecular sieve and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910791355.XA CN112429745B (en) 2019-08-26 2019-08-26 H-type MCM-22 molecular sieve and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112429745A true CN112429745A (en) 2021-03-02
CN112429745B CN112429745B (en) 2023-04-07

Family

ID=74690226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910791355.XA Active CN112429745B (en) 2019-08-26 2019-08-26 H-type MCM-22 molecular sieve and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112429745B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1616350A (en) * 2003-11-10 2005-05-18 中国科学院大连化学物理研究所 Method for refilling aluminium to synthesinze high silicon MWW molecular sieve
CN1654331A (en) * 2004-02-10 2005-08-17 中国科学院大连化学物理研究所 Method for preparing MWW molecular screen material with variable silicon-aluminium proportion
CN102689909A (en) * 2012-05-28 2012-09-26 中国科学院山西煤炭化学研究所 Titanium-rich lamellar Ti-Si molecular sieve and compound method thereof
CN103803577A (en) * 2012-11-08 2014-05-21 中国石油化工股份有限公司 Small-crystal ultra-thin MCM-22 molecular sieve and preparation method thereof
CN106517232A (en) * 2015-09-15 2017-03-22 中国石油化工股份有限公司 H-MCM-22 molecular sieve synthesis method and synthesized molecular sieve

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1616350A (en) * 2003-11-10 2005-05-18 中国科学院大连化学物理研究所 Method for refilling aluminium to synthesinze high silicon MWW molecular sieve
CN1654331A (en) * 2004-02-10 2005-08-17 中国科学院大连化学物理研究所 Method for preparing MWW molecular screen material with variable silicon-aluminium proportion
CN102689909A (en) * 2012-05-28 2012-09-26 中国科学院山西煤炭化学研究所 Titanium-rich lamellar Ti-Si molecular sieve and compound method thereof
CN103803577A (en) * 2012-11-08 2014-05-21 中国石油化工股份有限公司 Small-crystal ultra-thin MCM-22 molecular sieve and preparation method thereof
CN106517232A (en) * 2015-09-15 2017-03-22 中国石油化工股份有限公司 H-MCM-22 molecular sieve synthesis method and synthesized molecular sieve

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TOSHIYUKI YOKOI ET AL.: "Synthesis and structural characterization of", 《THE ROYAL SOCIETY OF CHEMISTRY》 *
张斌: "苯和乙烯液相烷基化催化材料的制备、表征及催化性能的研究", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技I辑》 *

Also Published As

Publication number Publication date
CN112429745B (en) 2023-04-07

Similar Documents

Publication Publication Date Title
EP3165280B1 (en) Scm-11 molecular sieve, a process for producing same and use thereof
CN104511271B (en) A kind of molecular sieve, its manufacture method and its application
CN108726535B (en) Preparation method of phosphorus modified ZSM-5 molecular sieve with hierarchical pores
CN109678171B (en) Ti-MWW molecular sieve with high external surface area and high framework titanium content, and preparation method and catalytic application thereof
CN104211080B (en) A kind of preparation method of Fe isomorphous substitution ZSM-22 molecular sieve
TW202216598A (en) Silicon-aluminum molecular sieve catalyst, and preparation and application thereof
CN112536066B (en) Preparation method of mesoporous Fe-Beta molecular sieve catalyst containing core-shell structure
CN112429745B (en) H-type MCM-22 molecular sieve and preparation method and application thereof
CN108217677B (en) Cobalt-containing Beta molecular sieve and preparation method thereof
CN107151022B (en) Mesoporous P-IM-5 molecular sieve, and preparation method and application thereof
CN104760971A (en) Beta molecular sieve alkali-free metal ion synthesis method
CN112585090A (en) Method for producing Cu-P co-supported zeolite, catalyst precursor composition and treatment solution that can be used for same, and method for producing layered catalyst
CN107344108A (en) A kind of catalyst for improving hydrocracking tail oil viscosity index (VI) and preparation method thereof
CN108793187B (en) Preparation method of high-dispersion zeolite
CN107262148B (en) Strip-shaped crystal grain titanium-silicon molecular sieve and synthesis method and application thereof
CN111689505A (en) Preparation method of ZSM-5 molecular sieve with mesoporous-microporous hierarchical structure
CN105712374A (en) Preparation method of hollow USY molecular sieve
CN115196650B (en) Metal modified mesoporous ZSM-5 molecular sieve and preparation method thereof
CN113318781B (en) Light gasoline cracking yield-increasing propylene catalyst containing spherical chlorite mesoporous composite material, and preparation method and application thereof
CN106517232B (en) The synthetic method of H-MCM-22 molecular sieve and its molecular sieve of synthesis
CN113880111A (en) Ti-MWW molecular sieve and preparation method and application thereof
CN113559920A (en) ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof
CN108996517B (en) Hierarchical-pore wide-silica-alumina-ratio EU-1 molecular sieve and preparation method thereof
CN115010146A (en) Hierarchical pore ZSM-5 nano aggregate molecular sieve and preparation method thereof
Xu et al. Synthesis of hierarchically porous zeolite Ti-MWW with different hard templates and their application in allyl alcohol conversion

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant