CN111744539A - Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation - Google Patents

Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation Download PDF

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CN111744539A
CN111744539A CN201910244609.6A CN201910244609A CN111744539A CN 111744539 A CN111744539 A CN 111744539A CN 201910244609 A CN201910244609 A CN 201910244609A CN 111744539 A CN111744539 A CN 111744539A
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catalyst
mixture
ethylbenzene
deactivated
gas phase
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孙敏
余少兵
贾晓梅
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The present disclosure relates to a method for preparing a catalyst used in a method for preparing ethylbenzene by benzene-ethylene gas phase alkylation, which comprises: mixing the inactivated gas phase method ethylbenzene catalyst, a first organic template agent and optional water to obtain a first mixture, carrying out hydrothermal crystallization reaction on the first mixture in a closed reactor at 120-180 ℃ for 2-72 h, collecting a solid product, and drying and roasting; wherein the deactivated vapor phase ethylbenzene catalyst contains a ZSM-5 molecular sieve. The method can recycle the deactivated ethylbenzene catalyst used as solid waste, and the catalytic activity of the prepared catalyst is equivalent to the level of a fresh agent.

Description

Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation
Technical Field
The present disclosure relates to a preparation method of catalyst used in a method for preparing ethylbenzene by benzene-ethylene gas phase alkylation.
Background
Ethylbenzene is an important organic chemical raw material, and is mainly used for producing styrene monomers so as to synthesize various high polymer materials such as engineering plastics, synthetic resins, synthetic rubbers and the like. With the steady increase of the economy of China, the demand of ethylbenzene is very vigorous. In 2018, the ethylbenzene demand in China is about 1000 ten thousand tons, the self-supporting rate is about 80%, and the annual growth rate of the ethylbenzene demand in nearly 5 years is 15%.
At present, ethylbenzene is mainly synthesized by an alkylation reaction of pure ethylene and benzene. The technology has a long development history, has a mature technology at home and abroad, and the production process mainly comprises the traditional AlCl3Processes, molecular sieve gas phase processes and molecular sieve gas phase processes.
The existing device mostly adopts a molecular sieve gas phase method and a molecular sieve liquid phase method, wherein a molecular sieve gas phase method catalyst for realizing industrialization adopts a ZSM-5 molecular sieve. The one-way operation period of the gas phase method ethylbenzene catalyst taking the ZSM-5 molecular sieve as the active component can reach 1-2 years, the catalyst can operate for 1-2 years after the charking regeneration, but the activity of the catalyst after the charking regeneration is low again, and the production requirement can not be met. The reasons of low activity or inactivation are that apart from carbon deposition of the catalyst, the skeleton of the molecular sieve is partially dealuminated, the skeleton of the molecular sieve is partially collapsed, and the crystallinity of the molecular sieve is reduced, so that the method of carbon burning regeneration cannot compensate the defect of the skeleton of the molecular sieve. The inactivated ZSM-5 molecular sieve catalyst can only be treated as solid waste, needs to be subjected to harmless treatment by invested capital and then is buried, which causes waste and certain environmental pollution.
At present, no report exists that the ethylbenzene catalyst which is used as solid waste is treated and then used as the ethylbenzene catalyst again. The prior regeneration technology is mainly a method for regenerating calcined carbon, such as the method for regenerating calcined carbon disclosed in CN1051902, and the literature that the research on the regeneration of a synthesized ethylbenzene molecular sieve catalyst (Vol.21No.1, the institute of clothing, Beijing, Nature science) is a method for regenerating calcined carbon by in vitro calcination. The roasting regeneration method cannot make up for the problems of partial dealumination of the framework of the molecular sieve, partial collapse of the framework of the molecular sieve and reduction of the crystallinity of the molecular sieve.
Disclosure of Invention
The method takes the inactivated gas phase method ethylbenzene catalyst as a raw material, can repair the framework defect of a ZSM-5 molecular sieve in the inactivated catalyst, and has the catalytic activity equivalent to the level of a fresh agent.
In order to achieve the above objects, the present disclosure provides a method for preparing a catalyst used in a process for preparing ethylbenzene by vapor phase alkylation of benzene-ethylene, the method comprising: mixing the inactivated gas phase method ethylbenzene catalyst, a first organic template agent and optional water to obtain a first mixture, carrying out hydrothermal crystallization reaction on the first mixture in a closed reactor at 120-180 ℃ for 2-72 h, collecting a solid product, and drying and roasting; wherein the deactivated vapor phase ethylbenzene catalyst contains a ZSM-5 molecular sieve.
Optionally, in the first mixture, SiO2The molar ratio of the deactivated vapor phase ethylbenzene catalyst, the first organic template in terms of N and water is 1: (0.02-0.2): (4-50), preferably 1: (0.03-0.15): (5-20), more preferably 1: (0.03-0.1): (6-14).
Optionally, the conditions of the hydrothermal crystallization reaction are as follows: the temperature is 125-170 ℃ and the time is 12-48 h.
Optionally, the first organic templating agent is a quaternary ammonium base, a quaternary ammonium salt, or a fatty amine, or a combination of two or three thereof; preferably, the first organic templating agent is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylamine, propylamine, or butylamine, or a combination of two or three thereof.
Optionally, the method further comprises: mixing an aluminum source and a second organic template agent, processing for 1-8 h at 60-150 ℃ in a closed reactor to obtain a second mixture, and mixing the second mixture with the first mixture to perform the hydrothermal crystallization reaction.
Alternatively, with Al2O3The molar ratio of the aluminum source to the second organic template calculated by N is (0.008-1): 1, preferably (0.01-0.5): 1.
alternatively, with Al2O3Calculated by the aluminum source and SiO2The molar ratio of the deactivated gas phase method ethylbenzene catalyst is (0.0002-0.008): 1, preferably (0.0008-0.006): 1.
optionally, the aluminum source is alumina, aluminum hydroxide or pseudo-boehmite, or a combination of two or three thereof; and/or the presence of a gas in the gas,
the second organic template agent is quaternary ammonium hydroxide and/or fatty amine; preferably, the second organic templating agent is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylamine, propylamine, or butylamine, or a combination of two or three thereof.
Optionally, the drying conditions include: the temperature is 80-120 ℃, and the time is 12-36 h; the roasting conditions comprise: the temperature is 450-550 ℃, and the time is 4-6 h.
Optionally, the deactivated vapor phase ethylbenzene catalyst has an activity of less than 75% of the freshness agent.
According to the technical scheme, the method adopts an inactivated liquid phase method ethylbenzene catalyst which takes a ZSM-5 molecular sieve as an active component as a raw material to carry out hydrothermal crystallization reaction, and the ZSM-5 molecular sieve can be subjected to recrystallization in the presence of an organic template agent, so that the framework defect of the molecular sieve is repaired. The catalyst prepared by the method disclosed by the invention has improved crystallinity, has the catalytic activity equivalent to the level of a fresh agent, and can be used as the catalyst again to be applied to the reaction for preparing ethylbenzene by benzene-ethylene gas phase alkylation. In addition, the method effectively retreats the deactivated catalyst which is used as solid waste, solves the problems of resource waste and environmental pollution, and has higher economic and environmental protection benefits.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is an X-ray diffraction pattern of the catalyst prepared in example 9.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method for preparing a catalyst used in a process for preparing ethylbenzene by benzene-ethylene vapor phase alkylation, the method comprising: mixing the inactivated gas phase method ethylbenzene catalyst, a first organic template agent and optional water to obtain a first mixture, carrying out hydrothermal crystallization reaction on the first mixture in a closed reactor at 120-180 ℃ for 2-72 h, collecting a solid product, and drying and roasting; wherein the deactivated vapor phase ethylbenzene catalyst contains a ZSM-5 molecular sieve.
The method adopts an inactivated gas phase ethylbenzene catalyst taking a ZSM-5 molecular sieve as an active component to carry out hydrothermal crystallization reaction, the ZSM-5 molecular sieve is subjected to recrystallization in the presence of an organic template agent, the framework defect of the molecular sieve can be repaired, the prepared catalyst does not have improved crystallinity, the catalytic activity is equivalent to the level of a fresh agent, and the catalyst can be used as a catalyst again to be applied to the reaction of preparing ethylbenzene by benzene-ethylene gas phase alkylation.
According to the present disclosure, the deactivated vapor phase ethylbenzene catalyst is a deactivated catalyst used in the vapor phase alkylation of benzene-ethylene to ethylbenzene. The specific composition of the deactivated vapor phase ethylbenzene catalyst is not particularly limited by the present disclosure, i.e., the method of the present application is applicable to various deactivated vapor phase ethylbenzene catalysts using ZSM-5 molecular sieve as an active component in the vapor phase alkylation of benzene-ethylene to prepare ethylbenzene, for example, the deactivated vapor phase ethylbenzene catalyst may contain ZSM-5 molecular sieve and alumina. The activity of the deactivated gas phase ethylbenzene catalyst can be less than 75% of that of a fresh agent, namely the ethylene conversion rate when the catalyst is used for preparing ethylbenzene by benzene-ethylene liquid phase alkylation, and the calculation method can be as follows: (moles of ethylene in the reaction raw material-moles of ethylene in the reaction product)/moles of ethylene in the reaction raw material X100%.
According to the present disclosure, the conditions of the hydrothermal crystallization reaction may preferably be: the temperature is 125-170 ℃ and the time is 12-48 h. The first mixture is placed in a closed reactor, and under the special temperature condition and the autogenous pressure of the closed reactor, the first mixture undergoes a hydrothermal crystallization reaction, so that the framework defect of the ZSM-5 molecular sieve is repaired. The hydrothermal crystallization reaction is carried out within the preferable condition range, which is beneficial to further improving the crystallinity of the ZSM-5 molecular sieve.
According to the disclosure, the first mixture is in SiO2The deactivated vapor phase ethylbenzene catalyst, the first organic template in terms of N, and water may be present in a molar ratio of 1: (0.02-0.2): (4-50), preferably 1: (0.03-0.15): (5-20), more preferably 1: (0.03-0.1): (6-14). The hydrothermal crystallization reaction is carried out within the preferable proportioning range, which is beneficial to improving the crystallinity of the ZSM-5 molecular sieve. Wherein "optional water" in the raw materials means that the water may be selectively added as long as the composition of the first mixture is within the above-mentioned compounding ratio range, for example, when the first organic template is in the form of an aqueous solution of an organic template having a certain concentration and the amount of water therein may satisfy the above-mentioned compounding ratio range, additional water may not be added.
According to the present disclosure, the first organic templating agent can be a quaternary ammonium base, quaternary ammonium salt, or esterFatty amines, or combinations of two or three thereof. Wherein the quaternary ammonium base can be organic quaternary ammonium base, the quaternary ammonium salt can be organic quaternary ammonium salt, and the aliphatic amine can be NH3Wherein at least one hydrogen is substituted with an aliphatic hydrocarbon group (e.g., an alkyl group).
Specifically, the first organic template may be at least one selected from the group consisting of a quaternary ammonium base represented by formula I, a quaternary ammonium salt represented by formula II, and an aliphatic amine represented by formula III.
Figure BDA0002010704080000051
In the formula I, R1、R2、R3And R4Alkyl groups each of C1-C4, including C1-C4 straight chain alkyl groups and C3-C4 branched chain alkyl groups, for example: r1、R2、R3And R4Each may independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
Figure BDA0002010704080000052
In the formula II, R5、R6、R7And R8Alkyl groups each of C1-C4, including C1-C4 straight chain alkyl groups and C3-C4 branched chain alkyl groups, for example: r5、R6、R7And R8Each may be independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl; x represents a halogen anion or an acid radical ion, such as F-, Cl-, Br-, I-or HSO4-。
R9(NH2)n(formula III)
In the formula III, n is an integer of 1 or 2. When n is 1, R9Is C1-C6 alkyl, including C1-C6 straight chain alkyl and C3-C6 branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl.When n is 2, R9Is C1-C6 alkylene, including C1-C6 linear alkylene and C3-C6 branched alkylene, such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, or n-hexylene.
Preferably, the first organic templating agent is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylamine, propylamine, or butylamine, or a combination of two or three thereof.
According to the present disclosure, the method may further comprise: mixing an aluminum source and a second organic template agent, processing for 1-8 h at 60-150 ℃ in a closed reactor to obtain a second mixture, and mixing the second mixture with the first mixture to perform the hydrothermal crystallization reaction. The aluminum source and the organic template agent are treated firstly and then are subjected to hydrothermal crystallization reaction with the inactivated gas phase method ethylbenzene catalyst, so that the silicon-aluminum ratio of the ZSM-5 molecular sieve can be adjusted to a certain degree, and the improvement of the crystallinity of the molecular sieve is facilitated.
In accordance with the present disclosure, the aluminum source can be used in relatively small amounts, for example, as Al2O3Calculated by the aluminum source and SiO2The molar ratio of the deactivated gas phase method ethylbenzene catalyst can be (0.0002-0.008): 1, preferably (0.0008-0.006): 1.
further, with Al2O3The molar ratio of the aluminum source to the second organic template in terms of N may be (0.008-1): 1, preferably (0.01-0.5): 1.
according to the present disclosure, the aluminum source is a material capable of providing aluminum, and may be, for example, alumina, aluminum hydroxide, or pseudoboehmite, or a combination of two or three thereof.
According to the present disclosure, the second organic templating agent can be a quaternary ammonium base and/or a fatty amine. The second organic template may be the same as the first organic template (i.e., the quaternary ammonium hydroxide and the fatty amine described above, which are not described herein again), or may be different, preferably the same organic template. Preferably, the second organic templating agent is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylamine, propylamine, or butylamine, or a combination of two or three thereof.
According to the present disclosure, the conditions of the drying may include: the temperature is 80-120 ℃, and the time is 12-36 h; the conditions for the firing may include: the temperature is 450-550 ℃, and the time is 4-6 h.
The present disclosure will be further illustrated by the following examples, but is not limited thereto.
In the following examples and comparative examples, the deactivated vapor phase ethylbenzene catalyst was derived from a deactivated catalyst removed from an ethylbenzene plant, which contained a ZSM-5 molecular sieve having an activity of 72% of the fresh agent, calculated as ethylene conversion.
In the examples, the X-ray diffraction (XRD) phase diagram of the sample was measured on a Japanese model D/MAX-IIIA X-ray diffractometer. Crystallinity means the crystallinity of the product prepared as a ratio to a reference value, i.e. the relative crystallinity value (r.c.%), in percent, based on 100% crystallinity of fresh catalyst AEB of ethylbenzene used on an ethylbenzene plant, as measured by XRD analysis.
Example 1
Mixing deactivated gas phase ethylbenzene catalyst, 25 wt% tetramethyl ammonium hydroxide solution and deionized water to obtain a mixture, and mixing with SiO2The molar ratio of the deactivated gas phase method ethylbenzene catalyst, the tetramethyl ammonium hydroxide and the water is 1: 0.03: 6.2. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 125 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-1, wherein the crystallinity of the catalyst QX-1 is 87.7%.
Example 2
Mixing the deactivated gas phase ethylbenzene catalyst, 27 wt% tetraethylammonium hydroxide solution and deionized water, and adding SiO to the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetraethylammonium hydroxide and water is 1: 0.06: 12.7. placing the mixture in a high-pressure reaction kettle, performing hydrothermal crystallization reaction for 16h at the autogenous pressure of 150 ℃, filtering and collecting a solid productThen drying at 120 ℃ for 12h, and roasting at 550 ℃ for 4h to prepare the catalyst QX-2 with the crystallinity of 88.3%.
Example 3
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.1: 11. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 12h at 170 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-3, wherein the crystallinity of the catalyst QX-3 is 87.9%.
Example 4
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.03: 6.2. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 55h at the autogenous pressure of 120 ℃, filtering and collecting a solid product, then drying for 12h at the temperature of 120 ℃, and roasting for 4h at the temperature of 550 ℃ to prepare the catalyst QX-4, wherein the crystallinity of the catalyst QX-4 is 86.3%.
Example 5
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.15: 20. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 12h at the autogenous pressure of 125 ℃, filtering and collecting a solid product, then drying for 12h at the temperature of 120 ℃, and roasting for 4h at the temperature of 550 ℃ to prepare the catalyst QX-5, wherein the crystallinity of the catalyst QX-5 is 87%.
Example 6
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% propyl ammonium hydroxide solution and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.02: 4. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 125 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-6, wherein the crystallinity of the catalyst QX-6 is 86.7%.
Example 7
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.2: 45. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 12h at the autogenous pressure of 125 ℃, filtering and collecting a solid product, then drying for 12h at the temperature of 120 ℃, and roasting for 4h at the temperature of 550 ℃ to prepare the catalyst QX-7, wherein the crystallinity of the catalyst QX-7 is 85.9%.
Example 8
Pseudo-boehmite (Al)2O3Calculated) was mixed with 25 wt% tetrapropylammonium hydroxide solution in a molar ratio of 0.01, treated at 120 ℃ for 4 hours in a closed reaction vessel with stirring, and then cooled to obtain a second mixture.
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% tetramethylammonium hydroxide solution, the second mixture and deionized water to obtain a first mixture, wherein SiO is used2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.03: 6.2, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated vapor phase ethylbenzene catalyst was calculated to be 0.0008. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 125 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-8, wherein the crystallinity of the catalyst QX-8 is 88.7%.
Example 9
Mixing alumina and 25 wt% tetramethyl ammonium hydroxide solution at a molar ratio of 0.08, treating at 100 deg.C for 8 hr in a sealed reaction kettle under stirring, and cooling to obtain a second mixture.
To be deactivatedMixing the vapor phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution, the second mixture and deionized water, and adding SiO to the mixture2The molar ratio of the deactivated gas phase method ethylbenzene catalyst, the tetramethyl ammonium hydroxide and the water is 1: 0.06: 12.7 aluminum oxide with SiO2The molar ratio of the deactivated vapor phase ethylbenzene catalyst was calculated to be 0.002. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 24h at the autogenous pressure of 150 ℃, filtering and collecting a solid product, then drying for 12h at the temperature of 120 ℃, roasting for 4h at the temperature of 550 ℃, and preparing the catalyst QX-9, wherein the X-ray diffraction pattern of the catalyst QX-9 is shown in figure 1, and the crystallinity is 89.2%.
Example 10
Aluminum hydroxide (as Al)2O3Calculated) was mixed with 27 wt% tetraethylammonium hydroxide solution in a molar ratio of 0.5, treated in a closed reaction vessel with stirring at 150 ℃ for 1h, and then cooled to give a second mixture.
Mixing the deactivated vapor phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution, the second mixture and deionized water, and adding SiO to the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetraethylammonium hydroxide and water is 1: 0.1: 11, with Al2O3Calculated as aluminum hydroxide and SiO2The molar ratio of deactivated vapor phase ethylbenzene catalyst was calculated to be 0.006. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 12h at 170 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-10, wherein the crystallinity of the catalyst QX-10 is 88.4%.
Example 11
Pseudo-boehmite (Al)2O3Calculated) was mixed with 25 wt% tetrapropylammonium hydroxide solution in a molar ratio of 0.008, treated at 120 ℃ for 4 hours in a closed reaction vessel with stirring, and then cooled to obtain a second mixture.
Mixing the deactivated gas phase ethylbenzene catalyst, 25 wt% ethylamine solution, the second mixture and deionized water to obtain a first mixture, wherein SiO is used2The molar ratio of the deactivated gas phase ethylbenzene catalyst, ethylamine and water is 1: 0.03: 6.2, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of deactivated vapor phase ethylbenzene catalyst was calculated to be 0.0005. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 125 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-11, wherein the crystallinity of the catalyst QX-11 is 88.0%.
Example 12
Pseudo-boehmite (Al)2O3Calculated) was mixed with 25 wt% tetrapropylammonium hydroxide solution in a molar ratio of 0.8, treated at 120 ℃ for 4 hours in a closed reaction vessel with stirring, and then cooled to obtain a second mixture.
Mixing the deactivated vapor phase ethylbenzene catalyst, 25 wt% tetrapropylammonium hydroxide solution, the second mixture and deionized water to obtain a first mixture, wherein SiO is used2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.03: 6.2, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated vapor phase ethylbenzene catalyst was 0.008. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 125 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-12, wherein the crystallinity of the catalyst QX-12 is 87.9%.
Example 13
Pseudo-boehmite (Al)2O3Calculated) was mixed with 25 wt% tetrapropylammonium hydroxide solution in a molar ratio of 0.008, treated at 120 ℃ for 4 hours in a closed reaction vessel with stirring, and then cooled to obtain a second mixture.
Mixing the deactivated gas phase ethylbenzene catalyst, 27 wt% tetraethylammonium hydroxide solution, the second mixture and deionized water, and adding SiO to the mixture2The molar ratio of the deactivated gas phase ethylbenzene catalyst, tetrapropylammonium hydroxide and water is 1: 0.15: 17.5, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated vapor phase ethylbenzene catalyst was 0.0002. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 125 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, and roasting for 4h at 550 ℃ to prepare the catalyst QX-13, wherein the crystallinity of the catalyst QX-13 is 87.4%.
Comparative example 1
The deactivated vapor-phase ethylbenzene catalyst was calcined at 550 ℃ for 6 hours in an air atmosphere to obtain catalyst D-1 of the present comparative example, whose crystallinity was 78.5%.
Comparative example 2
Mixing deactivated gas phase ethylbenzene catalyst, 25 wt% tetramethyl ammonium hydroxide solution and deionized water to obtain a mixture, and mixing with SiO2The molar ratio of the deactivated gas phase method ethylbenzene catalyst, the tetramethyl ammonium hydroxide and the water is 1: 0.03: 6.2. the mixture was placed in a three-necked flask and treated at 85 ℃ for 5 hours, and the solid product was collected by filtration, dried at 120 ℃ for 12 hours and calcined at 550 ℃ for 4 hours to obtain catalyst D-2 of this comparative example, which had a crystallinity of 75.3%.
Test examples
The catalysts prepared in examples and comparative examples were used to carry out a vapor phase alkylation reaction using benzene and ethylene as raw materials. The reaction conditions are as follows: the reaction temperature is 360 ℃, the reaction pressure is 1.1MPa, the molar ratio of benzene to ethylene is 6, and the weight space velocity of ethylene is 0.5h-1The loading of the catalyst was 4g, the ethylene conversion was calculated according to the following formula, and the reaction results are shown in Table 1.
Ethylene conversion (%) — the number of moles of ethylene in the reaction raw material-the number of moles of ethylene in the reaction product)/the number of moles of ethylene in the reaction raw material × 100%.
TABLE 1
Catalyst and process for preparing same Ethylene conversion (%)
QX-1 99.6
QX-2 99.7
QX-3 99.6
QX-4 99.3
QX-5 99.4
QX-6 99.3
QX-7 99.3
QX-8 99.7
QX-9 99.9
QX-10 99.8
QX-11 99.6
QX-12 99.5
QX-13 99.4
D-1 81
D-2 88
Fresh catalyst 99.9
As can be seen from table 1, the catalytic activity of the catalyst prepared using the process of the present disclosure is comparable to the level of the fresh agent.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. A method for preparing a catalyst used in a process for preparing ethylbenzene by benzene-ethylene gas phase alkylation, which is characterized by comprising the following steps: mixing the inactivated gas phase method ethylbenzene catalyst, a first organic template agent and optional water to obtain a first mixture, carrying out hydrothermal crystallization reaction on the first mixture in a closed reactor at 120-180 ℃ for 2-72 h, collecting a solid product, and drying and roasting; wherein the deactivated vapor phase ethylbenzene catalyst contains a ZSM-5 molecular sieve.
2. The method of claim 1, wherein the first mixture is in SiO2The molar ratio of the deactivated vapor phase ethylbenzene catalyst, the first organic template in terms of N and water is 1: (0.02-0.2): (4-50), preferably 1: (0.03-0.15): (5-20), more preferably 1: (0.03-0.1): (6-14).
3. The method of claim 1, wherein the conditions of the hydrothermal crystallization reaction are: the temperature is 125-170 ℃ and the time is 12-48 h.
4. The method of claim 1, wherein the first organic templating agent is a quaternary ammonium base, a quaternary ammonium salt, or a fatty amine, or a combination of two or three thereof; preferably, the first organic templating agent is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylamine, propylamine, or butylamine, or a combination of two or three thereof.
5. The method of claim 1, wherein the method further comprises: mixing an aluminum source and a second organic template agent, processing for 1-8 h at 60-150 ℃ in a closed reactor to obtain a second mixture, and mixing the second mixture with the first mixture to perform the hydrothermal crystallization reaction.
6. The method of claim 5, wherein Al is used2O3The molar ratio of the aluminum source to the second organic template calculated by N is (0.008-1): 1, preferably (0.01-0.5): 1.
7. the method of claim 5, wherein Al is used2O3Calculated by the aluminum source and SiO2The molar ratio of the deactivated gas phase method ethylbenzene catalyst is (0.0002-0.008): 1, preferably (0.0008 c-0.006)：1。
8. The process of claim 5 wherein the aluminum source is alumina, aluminum hydroxide or pseudoboehmite, or a combination of two or three thereof; and/or the presence of a gas in the gas,
the second organic template agent is quaternary ammonium hydroxide and/or fatty amine; preferably, the second organic templating agent is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ethylamine, propylamine, or butylamine, or a combination of two or three thereof.
9. A method according to any one of claims 1 to 8, wherein the drying conditions include: the temperature is 80-120 ℃, and the time is 12-36 h; the roasting conditions comprise: the temperature is 450-550 ℃, and the time is 4-6 h.
10. A process as claimed in any one of claims 1 to 8, wherein the deactivated vapour phase ethylbenzene catalyst has an activity of less than 75% of that of the fresh agent.
CN201910244609.6A 2019-03-28 2019-03-28 Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation Pending CN111744539A (en)

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CN102824923A (en) * 2011-06-17 2012-12-19 中国石油天然气股份有限公司 Catalyst for liquid phase synthesis of ethylbenzene, preparation method and application thereof
CN106938849A (en) * 2016-12-13 2017-07-11 江苏天诺新材料科技股份有限公司 The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst
CN107876082A (en) * 2017-11-01 2018-04-06 中国石油大学(华东) A kind of molecular sieves of alkali modification ZSM 5 and its preparation method and application
CN109225320A (en) * 2018-11-05 2019-01-18 宁夏大学 A kind of MFI structure deposed molecular sieve crystallization regeneration method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030050521A1 (en) * 2001-07-11 2003-03-13 Dandekar Ajit B. Reactivation of aromatics alkylation catalysts
CN102309982A (en) * 2010-06-30 2012-01-11 中国石油化工股份有限公司 Steam regeneration method of deactivated titanium-silicon molecular sieve
CN102824923A (en) * 2011-06-17 2012-12-19 中国石油天然气股份有限公司 Catalyst for liquid phase synthesis of ethylbenzene, preparation method and application thereof
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