CN107511171B - Preparation method of binderless Beta molecular sieve catalyst - Google Patents

Preparation method of binderless Beta molecular sieve catalyst Download PDF

Info

Publication number
CN107511171B
CN107511171B CN201610440702.0A CN201610440702A CN107511171B CN 107511171 B CN107511171 B CN 107511171B CN 201610440702 A CN201610440702 A CN 201610440702A CN 107511171 B CN107511171 B CN 107511171B
Authority
CN
China
Prior art keywords
molecular sieve
beta molecular
sieve catalyst
binder
catalyst precursor
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.)
Active
Application number
CN201610440702.0A
Other languages
Chinese (zh)
Other versions
CN107511171A (en
Inventor
杨为民
王振东
孙洪敏
张斌
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 CN201610440702.0A priority Critical patent/CN107511171B/en
Publication of CN107511171A publication Critical patent/CN107511171A/en
Application granted granted Critical
Publication of CN107511171B publication Critical patent/CN107511171B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J29/7007—Zeolite Beta
    • 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
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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

Abstract

The invention relates to a preparation method of a binderless Beta molecular sieve catalyst, which mainly solves the problems of complex preparation process, high binder content and poor catalytic performance of the binderless Beta molecular sieve catalyst in the prior art. The invention adopts the following steps: the technical scheme is that a Beta molecular sieve catalyst precursor is contacted with a solution which takes at least one compound chemically reacting with a binder in the Beta molecular sieve catalyst precursor as a solute, and then a solid product is separated, dried and roasted to obtain the Beta molecular sieve catalyst.

Description

Preparation method of binderless Beta molecular sieve catalyst
Technical Field
The invention relates to a preparation method of a binderless Beta molecular sieve catalyst.
Background
Beta molecular sieves were first successfully synthesized by Mobil corporation in 1967. The catalyst has a unique three-dimensional twelve-membered ring channel system, a linear channel with the pore diameter of 0.76 nanometers multiplied by 0.64 nanometers, and a bent channel with the pore diameter of 0.55 nanometers multiplied by 0.55 nanometers. The estimated structure of Beta molecular sieves is very complex and contains various crystal forms, such as a form (. about.BEA structure), B form and C form (BEC structure). Due to the strong acidity and the unique pore structure, the Beta molecular sieve has wide application in the petrochemical industry. Such as the adsorbent used for the separation of aromatic hydrocarbon, the catalyst used for the reaction processes of gasoline upgrading, hydroisomerization, hydrocracking, catalytic reforming dewaxing, benzene alkylation, transalkylation and the like. The catalyst prepared by using Beta molecular sieve 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 isopropylbenzene (cumene) by benzene and propylene liquid phase alkylation. In particular, in order to meet the requirements of industrial application, the molecular sieve and additives such as a binder are mixed and 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 Beta molecular sieve catalyst is much lower than the Beta molecular sieve before shaping.
In order to overcome the problems of binder-free Beta molecular sieve catalyst containing less active centers, document CN105439164A discloses a preparation method of a binder-free Beta molecular sieve catalyst, which converts the binder into Beta molecular sieve through secondary crystal transformation. However, the time required for crystal transformation is long (48-120 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.
In addition, the inventors of the present invention found that the catalyst strength significantly affects the catalytic performance. In the reaction of preparing alkylbenzene by benzene alkylation, the compressive strength of the catalyst is not as high as possible, 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 of complex preparation process, low molecular sieve content and poor catalytic performance of the binderless Beta molecular sieve catalyst in the prior art. The method for obtaining the binder-free catalyst by carrying out secondary crystallization on the binder-containing Beta molecular sieve catalyst has the problems of long crystallization time, incomplete crystallization and low catalytic performance in the reaction of preparing alkylbenzene by liquid phase alkylation of benzene and olefin, and provides a novel preparation method of the binder-free Beta molecular sieve catalyst. The method can dissolve the binder in a short time and completely remove the binder, and the compressive strength of the obtained catalyst meets the requirement of liquid-phase alkylation reaction of benzene and olefin on the catalyst, so that the method 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 preparation method of a binderless Beta molecular sieve catalyst comprises the following steps: the Beta molecular sieve catalyst precursor is contacted with a solution which takes at least one compound which has chemical reaction with a binder in the Beta molecular sieve catalyst precursor as a solute, and then a solid product is separated, dried and roasted to obtain the Beta molecular sieve catalyst.
According to the technical scheme, the Beta molecular sieve catalyst precursor is obtained by mixing, molding and drying the synthesized Beta molecular sieve and a binder. Preferably, the binder is selected from the group consisting of silica sol, fumed silica, water glass, and silica having the formula Y4-nSiXnThe silicon-containing compound (n is 1-4, Y is alkyl group such as methyl, ethyl, propyl, etc., X is hydrolysable group such as Cl, methoxy OMe, ethoxy OEt, trimethylsiloxy OSiMe3Etc.), at least one of alumina; the content of the Beta molecular sieve in the Beta molecular sieve catalyst precursor is 40-90 wt% based on the weight of the roasted Beta molecular sieve catalyst precursor. Wherein, the Beta molecular sieve content in the Beta molecular sieve catalyst precursor is preferably 60-85 wt%. The technical scheme is adopted to keep the compressive strength of the catalyst in an optimal range.
Wherein the "binder" is different from the "binder in the Beta molecular sieve procatalyst". The binder is added before the Beta molecular sieve catalyst precursor is formed and is mixed with the Beta molecular sieve in a synthetic state, such as silica sol, fumed silica and the like. The "binder in the Beta molecular sieve catalyst precursor" refers to the binder in the formed Beta molecular sieve catalyst precursor, and as in embodiment 1 of the present invention, the "binder (alkaline silica sol)" is added to the synthesized molecular sieve catalyst, mixed, formed, dried, and converted into the "binder in the Beta molecular sieve catalyst precursor (amorphous silica)".
The synthesized Beta molecular sieve in the technical scheme is the Beta 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 synthesized Beta molecular sieve can be obtained by crystallizing a mixture of the directing agent, the silicon compound, the aluminum compound, the base and water, and separating and drying the solid product. Wherein the molar ratio of the silicon compound, the aluminum compound, the alkali, the guiding agent and the water is as follows: 1 (0.001-0.07): (0.05-0.30): 0.02-2.0): 6-50, preferably 1 (0.01-0.067): 0.05-0.25): 0.05-0.30): 10-30. The hydrothermal crystallization conditions include: the crystallization temperature is 130-210 ℃, and preferably 150-180 ℃; the crystallization time is 10 hours to 5 days, preferably 1 to 3 days. 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; the guiding agent is at least one of tetraethylammonium hydroxide and tetraethylammonium bromide.
In the above technical solution, the molding 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 Beta 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.
In the technical scheme, the roasting adopts a conventional molecular sieve roasting method in the field, for example, roasting for 3-10 hours at 400-800 ℃ in an oxygen-containing atmosphere to obtain the Beta molecular sieve catalyst.
In the technical scheme, the method also comprises the following steps of contacting the obtained Beta molecular sieve catalyst in at least one solution or steam with the pH value not higher than 7, and then separating, drying and roasting the solid product. Preferably, the obtained Beta molecular sieve catalyst is contacted with at least one solution or steam with the pH value not higher than 7, and the specific implementation is that the Beta molecular sieve catalyst is contacted with at least one solution or steam with the pH value not higher than 7 for 1-5 times at 10-600 ℃, and each time lasts for 10 minutes to 3 hours; more preferably, the solution comprises an aqueous solution of an ammonium salt, such as ammonium nitrate, ammonium phosphate, ammonium oxalate, an aqueous solution of an acid, such as oxalic acid, phosphoric acid, an aqueous solution of an alkaline earth metal salt or a rare earth metal salt, such as lanthanum nitrate, and the steam comprises water vapor.
In the above technical solution, the solution in which the at least one compound chemically reacts with the binder in the Beta molecular sieve catalyst precursor is a solute comprises an aqueous acid solution or an aqueous alkali solution; preferably, the aqueous solution of a base selected from the group consisting of inorganic acids, organic acids, quaternary ammonium bases, and bases having an alkali metal element or an alkaline earth metal element as a cation; preferably, the inorganic acid includes nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, the organic acid includes formic acid, acetic acid, propionic acid, acrylic acid or oxalic acid, the quaternary ammonium base includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N-trimethyladamantyl ammonium hydroxide or dimethyldiethylammonium hydroxide, and the base having an alkali metal element or an alkaline earth metal element as a cation includes NaOH or KOH. By adopting the method, the catalyst containing the binder is contacted with the solution taking at least one compound which has chemical reaction with the binder in the Beta molecular sieve catalyst precursor as the solute, so that the binder component can be simply, efficiently and fully removed from the catalyst to prepare the binderless molecular sieve catalyst.
In the technical scheme, the mass fraction of the solute in the solution with the at least one compound which is chemically reacted with the binder in the Beta molecular sieve catalyst precursor as the solute is 0.001-5%; preferably 0.01% -3%; preferably 0.01% -1%; preferably 0.03% -0.9%; most preferably 0.05% to 0.7%. The mass fraction of the solute is controlled within the range, the etching of molecular sieve crystals is avoided while the binder is rapidly removed, the compressive strength of the catalyst is kept within the optimal range, and the optimal binder-free Beta molecular sieve catalyst is obtained.
In the technical scheme, the mass ratio of the solution in which at least one compound chemically reacts with the binder in the Beta molecular sieve catalyst precursor is a solute to the Beta molecular sieve catalyst precursor is 5-100: 1; preferably 10-50: 1; preferably 10-40: 1; preferably 10-30: 1. The mass ratio of the solution to the Beta molecular sieve catalyst precursor is controlled within the range, so that the etching of molecular sieve crystals is avoided while the binder is rapidly removed, the compressive strength of the catalyst is kept within an optimal range, and the optimal binder-free Beta molecular sieve catalyst is obtained.
In the technical scheme, the contact temperature is not higher than 240 ℃, and the contact time is 10 minutes to 2 days; preferably, the contact temperature is not higher than 190 ℃, and the contact time is 20 minutes to 12 hours; preferably, the contact temperature is 60-180 ℃, and the contact time is 30 minutes-6 hours; preferably, the contact temperature is 100-. The contact temperature and the contact time are controlled within the ranges, so that the etching of molecular sieve crystals is avoided while the binder is rapidly removed, the compressive strength of the catalyst is kept within an optimal range, and the optimal binder-free Beta molecular sieve catalyst is obtained.
In the technical scheme, the Beta molecular sieve catalyst precursor is contacted with a solution which takes at least one compound chemically reacting with a binder in the Beta molecular sieve catalyst precursor as a solute and organic amine; preferably, the organic amine includes at least one selected from the group consisting of ethylamine, propylamine, butylamine, hexamethyleneimine, piperidine, homopiperazine, ethylenediamine and hexamethylenediamine. Meanwhile, organic amine is added to protect the molecular sieve crystal from being etched by the solution and keep the integrity of the molecular sieve crystal.
The invention also provides the binderless Beta molecular sieve synthesized by the preparation method of the binderless Beta molecular sieve.
The binderless Beta molecular sieve has a binder content of less than 3 wt.%, preferably less than 2 wt.%, more preferably less than 1 wt.%.
The compression strength of the binderless Beta molecular sieve is 60-120N/cm, preferably 65-100N/cm, and more preferably 65-90N/cm.
The invention also provides an application of the binderless Beta molecular sieve catalyst synthesized by the binderless Beta molecular sieve preparation method in the reaction of preparing alkylbenzene by benzene alkylation.
The binderless Beta molecular sieve provided by the invention has good catalytic performance in the reactions of preparing ethylbenzene by alkylating benzene and ethylene in a liquid phase and preparing cumene by alkylating benzene and propylene, and can be used as an alkylation catalyst to be applied to the reactions of preparing ethylbenzene by alkylating benzene and ethylene in a liquid phase and preparing cumene by alkylating benzene and propylene.
For the reaction of benzene and ethylene to prepare ethylbenzene by liquid phase alkylation and benzene and propylene to prepare isopropylbenzene (cumene) by liquid phase alkylation, the catalyst is required to have certain compressive strength (more than 60N/cm) so as to avoid catalyst pulverization, thereby leading to catalyst loss and bed pressure drop increase. However, the higher the crushing strength of the catalyst, the better, and when the crushing strength of the catalyst exceeds 120N/cm, for example 130N/cm, the catalytic performance of the catalyst is significantly lower than that of a catalyst having a crushing strength lower than 120N/cm. Therefore, the compressive strength of the Beta molecular sieve catalyst for preparing ethylbenzene and cumene by the liquid phase alkylation reaction of benzene and ethylene and the liquid phase alkylation reaction of benzene and propylene is controlled to be 60-120N/cm, preferably 65-100N/cm, and more preferably 65-90N/cm.
In order to obtain the binderless Beta molecular sieve catalyst with the compressive strength, the invention adopts a method for post-treating the binder-containing molecular sieve catalyst to selectively remove the binder to prepare the binderless molecular sieve catalyst. The problems of incomplete crystal transformation, long time and complex operation of the Beta molecular sieve catalyst without the binder prepared by a secondary crystallization method in the prior art are solved. By adopting the technical scheme of the invention, the rapid removal of the binder can be realized within 12 hours, the compressive strength of the obtained catalyst is 60-120N/cm, the binder is completely removed, the content of the binder in the product is less than 3 wt%, and a better technical effect is obtained.
The binderless Beta molecular sieve disclosed by the invention is used for testing the contained phase and the content of each phase by XRD. And observing the removal condition of the binder and the morphology of the molecular sieve by a scanning electron microscope. The content of the binder in the catalyst prepared by carrying out post-treatment on the catalyst containing the binder is determined by XRD phase quantification and the content of the binder in a scanning electron microscope picture. The silicon-aluminum ratio of the molecular sieve is determined by a chemical analysis method. The compression strength of the molecular sieve is tested by adopting a compression testing machine on the calcined catalyst, and the testing 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.
Drawings
Fig. 1 is an XRD spectrum of the prepared binderless Beta molecular sieve [ example 1 ]. As can be seen from the spectrogram, the diffraction peak is consistent with the characteristic diffraction peak of the Beta molecular sieve.
Detailed Description
[ example 1 ]
a) Synthesis of Beta molecular sieves (as-synthesized Beta molecular sieves): the method is characterized in that alkaline silica sol, aluminum sulfate octadecahydrate, tetraethyl ammonium hydroxide (TEAOH) and water are used as synthesis raw materials, and the raw materials are prepared according to the following material ratio (molar ratio):
SiO2/Al2O3＝25
TEAOH/SiO2＝0.20
H2O/SiO2＝18
after being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 3 days at 150 ℃ under the condition of stirring. And after crystallization, filtering, washing and drying to obtain the Beta molecular sieve in a synthetic state. The weight loss rate of the synthesized Beta molecular sieve is tested to be 16.4 wt%.
b) Preparation of Beta molecular sieve catalyst precursor: 41.866 g of the synthetic Beta molecular sieve and alkaline silica Sol (SiO)240.0 wt.%), sesbania powder 0.5616 g and aqueous solution of nitric acid (5 wt.%) were mixed uniformly, and the precursor of the catalyst was prepared by extrusion molding, the precursor of the catalyst being a strip-shaped Beta molecular sieve having a Beta molecular sieve content of 70 wt.% and a clover cross-section.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with an aqueous solution of sodium hydroxide at 150 ℃ for 3 hours, wherein the mass ratio of the aqueous solution of sodium hydroxide to the Beta molecular sieve catalyst precursor is 30: and 1, the mass fraction of the sodium hydroxide aqueous solution is 0.4%, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in an air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD spectrum of the product is shown in figure 1. The content of the molecular sieve in the product reaches 99.1 weight percent, and the compressive strength is 76N/cm.
In this embodiment, alkaline silica sol is used as a binder, sodium hydroxide is used to remove the binder in the formed Beta molecular sieve catalyst, and the sodium hydroxide reacts with amorphous silica (the binder in the formed Beta molecular sieve catalyst) therein to convert the amorphous silica into sodium silicate dissolved in water, so that the binder in the Beta molecular sieve catalyst is efficiently and rapidly removed.
[ example 2 ]
As in example 1, except that in step b) 41.866 g of as-synthesized Beta molecular sieve, alkaline silica Sol (SiO)240.0 wt.%), sesbania powder 1.05 g and aqueous solution of nitric acid (5 wt.%) were mixed uniformly, and the precursor of the catalyst was prepared by extrusion molding, the Beta molecular sieve content of which was 50 wt.% and the cross-section of which was clover.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with an aqueous sodium hydroxide solution at 150 ℃ for 4 hours, wherein the mass ratio of the aqueous sodium hydroxide solution to the Beta molecular sieve catalyst precursor is 25: and 1, the mass fraction of the sodium hydroxide aqueous solution is 0.6%, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in an air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.2 weight percent, and the compressive strength is 68N/cm.
[ example 3 ]
As in example 1, except that in step b) 41.866 g of as-synthesized Beta molecular sieve, alkaline silica Sol (SiO)240.0 wt.%) 21.875 g, sesbania powder 0.9 g, and ammonium nitrate aqueous solution (3 wt.%) were mixed uniformly, and the precursor of the catalyst was prepared by extrusion molding, the precursor of the molecular sieve having a Beta molecular sieve content of 80 wt.% and a clover cross-section.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with an aqueous solution of sodium hydroxide at 120 ℃ for 3 hours, wherein the mass ratio of the aqueous solution of sodium hydroxide to the Beta molecular sieve catalyst precursor is 28: and 1, the mass fraction of the sodium hydroxide aqueous solution is 0.3%, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in an air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 99.5 weight percent, and the compressive strength is 81N/cm.
[ example 4 ]
As in example 1, except that in step b) 41.866 g of as-synthesized Beta molecular sieve, alkaline silica Sol (SiO)240.0 wt.%) 21.875 g, fumed Silica (SiO)295.0 weight percent) 27.632 g, sesbania powder 0.9 g and water are evenly mixed, and the precursor of the molecular sieve catalyst with the Beta molecular sieve content of 50 weight percent and the cross section of clover is prepared by extrusion molding.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with an aqueous solution of sodium hydroxide at 110 ℃ for 5 hours, wherein the mass ratio of the aqueous solution of sodium hydroxide to the Beta molecular sieve catalyst precursor is 45: and 1, the mass fraction of the sodium hydroxide aqueous solution is 0.4%, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in an air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 97.3 weight percent, and the compressive strength is 66N/cm.
[ example 5 ]
As in example 1, except that in step b) 41.866 g of as-synthesized Beta molecular sieve, alkaline silica Sol (SiO)240.0 wt.%) 15 g of fumed Silica (SiO)295.0 wt.%) 2.895 g, sesbania powder 0.9 g, and aqueous solution of nitric acid (3 wt.%) were mixed uniformly, and the precursor of the catalyst was prepared by extrusion molding, the precursor of the molecular sieve having a Beta molecular sieve content of 80 wt.% and a clover cross-section.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with a potassium hydroxide aqueous solution at 130 ℃ for 3 hours, wherein the mass ratio of the sodium hydroxide aqueous solution to the Beta molecular sieve catalyst precursor is 40: and 1, the mass fraction of the sodium hydroxide aqueous solution is 0.2%, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in an air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.7 weight percent, and the compressive strength is 77N/cm.
[ example 6 ]
Similarly [ example 1 ], except that 41.866 g of synthesized Beta molecular sieve and alkaline silica Sol (SiO)240.0 wt.%) 15 g of fumed Silica (SiO)295.0 wt.%) 2.895 g, sesbania powder 0.9 g, and aqueous solution of nitric acid (3 wt.%) were mixed uniformly, and the precursor of the catalyst was prepared by extrusion molding, the precursor of the molecular sieve having a Beta molecular sieve content of 80 wt.% and a clover cross-section.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with an aqueous solution of N, N, N-trimethyladamantyl ammonium hydroxide at 170 ℃ for 3 hours, wherein the mass ratio of the aqueous solution of sodium hydroxide to the Beta molecular sieve catalyst precursor is 35: the mass fraction of the 1, N, N, N-trimethyl adamantyl ammonium hydroxide aqueous solution is 1 percent, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in the air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.4 weight percent, and the compressive strength is 79N/cm.
[ example 7 ]
Similarly [ example 1 ], except that in the step b), 41.866 g of Beta molecular sieve in a synthetic state, 8.838 g of alumina (99.0 wt%), 0.9 g of sesbania powder and 3 wt% of nitric acid aqueous solution are uniformly mixed, and a strip-shaped molecular sieve catalyst precursor with the Beta molecular sieve content of 80 wt% and the clover cross section is prepared by strip extrusion molding.
c) Contacting the Beta molecular sieve catalyst precursor prepared in the step b) with an aqueous solution (hydrochloric acid) of hydrogen chloride at 130 ℃ for 5 hours, wherein the mass ratio of the hydrochloric acid to the Beta molecular sieve catalyst precursor is 30:1, the mass fraction of the hydrochloric acid is 1%, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in the air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.6 weight percent, and the compressive strength is 72N/cm.
[ example 8 ]
As in example 1, except that the precursor of the molecular sieve catalyst in the form of a strand having a Beta molecular sieve content of 90% by weight and a circular cross-section was prepared by extrusion molding in step b). The XRD spectrum of the final product binderless Beta molecular sieve catalyst is similar to that of figure 1. The content of the molecular sieve in the product reaches 97.5 weight percent, and the compressive strength is 75N/cm.
[ example 9 ]
As in example 1, except that the precursor of the molecular sieve catalyst in the form of a strand having a Beta molecular sieve content of 90% by weight and a circular cross-section was prepared by extrusion molding in step b).
The XRD spectrum of the product binderless Beta molecular sieve catalyst is similar to that in figure 1. The content of the molecular sieve in the product reaches 98.5 weight percent, and the compressive strength is 74N/cm.
[ example 10 ]
As in example 1, except that the precursor of the molecular sieve catalyst in the form of a strand having a Beta molecular sieve content of 90% by weight and a circular cross-section was prepared by extrusion molding in step b).
The XRD spectrum of the product binderless Beta molecular sieve catalyst is similar to that in figure 1. The content of the molecular sieve in the product reaches 98.5 weight percent, and the compressive strength is 71N/cm.
[ example 11 ]
As in example 7, except that the precursor of the molecular sieve catalyst in the form of a strand having a Beta molecular sieve content of 90% by weight and a circular cross-section was prepared by extrusion molding in step b).
c) The Beta molecular sieve catalyst precursor prepared in the step b) is contacted with phosphoric acid at 110 ℃ for 5 hours, and the mass ratio of the phosphoric acid to the Beta molecular sieve catalyst precursor is 30:1, the mass fraction of the phosphoric acid is 0.5 percent, and after the reaction is finished, the solid product is separated, dried and roasted for 5 hours at 550 ℃ in the air atmosphere to obtain the Beta molecular sieve catalyst.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.2 weight percent, and the compressive strength is 75N/cm.
[ example 12 ]
Like [ example 1 ], except for the step of synthesizing the Beta zeolite (as-synthesized Beta zeolite) in the step a), the material ratio (molar ratio) of the reaction mixture is as follows:
SiO2/Al2O3＝40
TEAOH/SiO2＝0.15
H2O/SiO2＝18；
b) a precursor of a molecular sieve in the form of a strand having a Beta molecular sieve content of 75% by weight and a circular cross-section was prepared by extrusion molding.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.1 weight percent, and the compressive strength is 67N/cm.
[ example 13 ]
Similarly to [ example 1 ], except for the step a) of synthesizing the Beta molecular sieve (as-synthesized Beta molecular sieve), the material ratio (molar ratio) of the reaction mixture is as follows:
SiO2/Al2O3＝50
TEAOHOH/SiO2＝0.16
TEABr/SiO2＝0.06
H2O/SiO2＝20；
b) a precursor of a molecular sieve in the form of a strand having a Beta molecular sieve content of 75% by weight and a circular cross-section was prepared by extrusion molding.
The XRD pattern of the product was similar to that of FIG. 1. The content of the molecular sieve in the product reaches 98.7 weight percent, and the compressive strength is 79N/cm.
[ COMPARATIVE EXAMPLE 1 ]
Similarly [ example 1 ], except that silica sol was used as the binder:
b) 48.1 g of synthetic Beta molecular sieve and alkaline silica Sol (SiO)240.0 wt%) 5.04 g and sesbania powder 0.5616 g, and the precursor is extruded to form the strip-shaped molecular sieve catalyst with the Beta 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 Beta molecular sieve catalyst had a crush strength of 32N/cm.
[ COMPARATIVE EXAMPLE 2 ]
The same as [ example 1 ] except that alumina was used as the binder:
b) 48.1 g of synthetic Beta molecular sieve 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 Beta 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 Beta molecular sieve catalyst had a compressive strength of 41N/cm.
[ COMPARATIVE EXAMPLE 3 ]
The binderless Beta molecular sieve catalyst was prepared according to the method of document CN 105439164A: the Beta molecular sieve in [ example 1 ] was mixed with silica Sol (SiO), silica white240.0 percent by weight), sodium aluminate and sodium silicate are mixed, molded and roasted to obtain the raw material with the proportion of 4.5Na2O：5Al2O3：100SiO2In TEAOH solution (TEA/SiO) with a Beta content of 50 wt. -%20.25, water/SiO2And 5), crystallizing at 160 ℃ for 96 hours, taking out, drying at 120 ℃ for 3 hours, roasting at 400 ℃ for 2 hours, and roasting at 550 ℃ for 3 hours to obtain the Beta 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 93.6 weight percent, and the compressive strength is 35N/cm.
[ example 14 ]
The Beta zeolite catalyst of [ example 1 ] was used in a continuous fixed bed liquid phase alkylation of benzene with ethylene. Before the reaction, the catalyst is converted to the hydrogen form by ammonium exchange. The alkylation reaction conditions are as follows: the temperature is 175 ℃, the pressure is 3.5MPa, the benzene/alkene feeding ratio is 2, and the ethylene mass space velocity is 6h-1After 5 hours of continuous reaction, the ethylene conversion was 70.6%.
[ COMPARATIVE EXAMPLE 4 ]
The catalyst obtained in [ comparative example 3 ] was used in a continuous fixed bed liquid phase alkylation of benzene with ethylene. Inverse directionThe catalyst is first converted to the hydrogen form by ammonium exchange before use. The alkylation reaction conditions are as follows: the temperature is 175 ℃, the pressure is 3.5MPa, the benzene/alkene feeding ratio is 2, and the ethylene mass space velocity is 6h-1After 5 hours of continuous reaction, the ethylene conversion was only 48.8%.

Claims (14)

1. A preparation method of a binderless Beta molecular sieve catalyst comprises the following steps:
contacting a Beta molecular sieve catalyst precursor with a solution which takes at least one compound in chemical reaction with a binder in the Beta molecular sieve catalyst precursor as a solute, so as to dissolve and remove the binder, and then separating, drying and roasting a solid product to obtain the Beta molecular sieve catalyst; the contact temperature is not higher than 240 ℃, and the contact time is 10 minutes to 6 hours; the mass fraction of solute in the solution taking at least one compound which chemically reacts with the binder in the Beta molecular sieve catalyst precursor as the solute is 0.01-3%; the mass ratio of the solution taking at least one compound which chemically reacts with the binder in the Beta molecular sieve catalyst precursor as a solute to the Beta molecular sieve catalyst precursor is 10-50: 1; the compressive strength of the binderless Beta molecular sieve catalyst is 60-90N/cm.
2. The method of claim 1, wherein the solution of the solute at least one compound that chemically reacts with the binder of the Beta molecular sieve catalyst precursor comprises an aqueous acid or an aqueous base.
3. The method of claim 1, wherein the Beta molecular sieve catalyst precursor has a Beta molecular sieve content of 40-90 wt% based on the weight of the calcined Beta molecular sieve catalyst precursor.
4. The method of claim 1, wherein the Beta molecular sieve catalyst precursor is contacted with a solution of solute comprising at least one compound that chemically reacts with the binder of the Beta molecular sieve catalyst precursor and an organic amine.
5. The method of claim 4, wherein said organic amine comprises at least one member selected from the group consisting of ethylamine, propylamine, butylamine, hexamethyleneimine, piperidine, homopiperazine, ethylenediamine, and hexamethylenediamine.
6. The method of claim 1, wherein the contact temperature is 100 ℃ to 170 ℃ and the contact time is 30 minutes to 4 hours; the solution taking at least one compound which chemically reacts with the binder in the Beta molecular sieve catalyst precursor as a solute comprises an aqueous solution of inorganic acid, organic acid, quaternary ammonium base, alkali taking alkali metal elements or alkaline earth metal elements as cations; the mass fraction of the solute in the solution taking at least one compound which chemically reacts with the binder in the Beta molecular sieve catalyst precursor as the solute is 0.05-1%; the mass ratio of the solution taking at least one compound which chemically reacts with the binder in the Beta molecular sieve catalyst precursor as a solute to the Beta molecular sieve catalyst precursor is 10-30: 1.
7. the method of claim 6, wherein said inorganic acid comprises nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, said organic acid comprises formic acid, acetic acid, propionic acid, acrylic acid or oxalic acid, said quaternary ammonium base comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, N, N, N-trimethyladamantyl ammonium hydroxide or dimethyldiethylammonium hydroxide, and said base having an alkali metal element or an alkaline earth metal element as a cation comprises NaOH or KOH.
8. The method of claim 1, wherein the Beta molecular sieve procatalyst is obtained by mixing the as-synthesized Beta molecular sieve with a binder, shaping, and drying.
9. The method of claim 1, wherein the binder comprises at least one member selected from the group consisting of silica sol, fumed silica, water glass, a silicon-containing compound having the formula Y, and alumina4-nSiXnWherein n is 1 to 4, Y is a hydrocarbon group, and X is a hydrolyzable group; based on the weight of the roasted Beta molecular sieve catalyst precursor, the content of the Beta molecular sieve in the Beta molecular sieve catalyst precursor is 60-85 wt%.
10. The method of preparing the binderless Beta molecular sieve catalyst of claim 1 further comprising the steps of: contacting the obtained Beta molecular sieve catalyst in at least one solution or steam with the pH value not higher than 7, and then separating, drying and roasting the solid product.
11. The method of claim 10, wherein said at least one solution having a pH of no greater than 7 comprises an aqueous solution of an ammonium salt, an aqueous solution of an acid, an aqueous solution of an alkaline earth metal salt or a rare earth metal salt, and said steam comprises steam.
12. The binderless Beta molecular sieve catalyst of any one of claims 1 to 11 synthesized by the process for preparing the binderless Beta molecular sieve catalyst.
13. The binderless Beta molecular sieve catalyst of claim 12 wherein the binderless Beta molecular sieve catalyst comprises less than 2 wt% binder.
14. The use of the binderless Beta molecular sieve catalyst synthesized by the method of any one of claims 1 to 11 in a fixed bed liquid phase alkylation reaction of benzene and olefin to produce alkylbenzene.
CN201610440702.0A 2016-06-18 2016-06-18 Preparation method of binderless Beta molecular sieve catalyst Active CN107511171B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610440702.0A CN107511171B (en) 2016-06-18 2016-06-18 Preparation method of binderless Beta molecular sieve catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610440702.0A CN107511171B (en) 2016-06-18 2016-06-18 Preparation method of binderless Beta molecular sieve catalyst

Publications (2)

Publication Number Publication Date
CN107511171A CN107511171A (en) 2017-12-26
CN107511171B true CN107511171B (en) 2020-10-30

Family

ID=60719997

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610440702.0A Active CN107511171B (en) 2016-06-18 2016-06-18 Preparation method of binderless Beta molecular sieve catalyst

Country Status (1)

Country Link
CN (1) CN107511171B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2770585C1 (en) * 2021-06-08 2022-04-18 Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") Method for obtaining isopropylbenzene by alkylation of benzene with propylene

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103121909A (en) * 2011-11-18 2013-05-29 中国石油化工股份有限公司 Method for producing ethylbenzene by performing vapor phase alkylation on ethanol and benzene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3101502A1 (en) * 1981-01-19 1982-08-26 Basf Ag, 6700 Ludwigshafen PHENYLPIPERAZINE DERIVATIVES OF HETARYLPHENOLS AND HETARYLANILINES, THEIR PRODUCTION AND THEIR CONTAINING THERAPEUTIC AGENTS

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103121909A (en) * 2011-11-18 2013-05-29 中国石油化工股份有限公司 Method for producing ethylbenzene by performing vapor phase alkylation on ethanol and benzene

Also Published As

Publication number Publication date
CN107511171A (en) 2017-12-26

Similar Documents

Publication Publication Date Title
CN107512729B (en) Preparation method of binder-free ZSM-5 molecular sieve
KR100606623B1 (en) Process for preparing bound zeolites
CN107512726B (en) Preparation method of binderless Beta molecular sieve
EP2920112A1 (en) Production and use of a zeolitic material in a process for the conversion of oxygenates to olefins
CN107511169B (en) ZSM-5 molecular sieve catalyst, preparation method and application
JP4630537B2 (en) Use of catalysts based on crystalline aluminosilicates
CN105565338B (en) A kind of preparation method of multi-stage porous EU-1 molecular sieves
CN107427820B (en) ZSM-5 catalyst
CN107512727B (en) Preparation method of binder-free MWW structure molecular sieve
CN107511171B (en) Preparation method of binderless Beta molecular sieve catalyst
CN107511165B (en) Preparation method of binder-free mercerized molecular sieve catalyst
CN107511168B (en) Preparation method of binder-free molecular sieve catalyst
CN107511175B (en) MWW structure molecular sieve catalyst, preparation method and application
EP2919906B1 (en) Process for the conversion of oxygenates to olefins
CN107511162B (en) Preparation method of binder-free Y molecular sieve catalyst
CN107511170B (en) Preparation method of binder-free ZSM-5 molecular sieve catalyst
CN106518600B (en) Method for preparing cyclohexylbenzene by liquid phase alkylation
CN109569701A (en) A kind of preparation method of ZSM-5/Silicalite-1 core shell molecular sieve
CN107511172B (en) Beta molecular sieve catalyst, preparation method and application
US9174204B2 (en) Catalyst based on zeolite for producing olefins and for oligomerizing olefins
JP5901817B2 (en) Heterojunction porous crystal for catalytic cracking and hydrocracking of heavy hydrocarbon oils
CN107511166B (en) Mercerized molecular sieve catalyst, preparation method and application
CN107511163B (en) Molecular sieve catalyst, preparation method and application
CN107020145A (en) A kind of mesoporous IM-5 molecular sieves and preparation method
CN107511174B (en) Preparation method of binder-free MWW structure molecular sieve catalyst

Legal Events

Date Code Title Description
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