CN111744545A - Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene liquid phase alkylation - Google Patents

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

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CN111744545A
CN111744545A CN201910245480.0A CN201910245480A CN111744545A CN 111744545 A CN111744545 A CN 111744545A CN 201910245480 A CN201910245480 A CN 201910245480A CN 111744545 A CN111744545 A CN 111744545A
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ethylbenzene
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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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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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Abstract

The present disclosure relates to a method for preparing a catalyst used in a method for preparing ethylbenzene by benzene-ethylene liquid phase alkylation, which comprises: mixing the inactivated liquid 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 the temperature of 100-150 ℃ for 4-72 hours, collecting a solid product, and drying and roasting the solid product; wherein the deactivated liquid phase method ethylbenzene catalyst contains beta 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 liquid phase alkylation
Technical Field
The present disclosure relates to a preparation method of catalyst used in a method for preparing ethylbenzene by benzene-ethylene liquid 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 liquid phase processes.
The new device mostly adopts a molecular sieve liquid phase method, wherein catalysts for realizing industrialization comprise MCM-22 and beta molecular sieves. The one-way operation period of the liquid phase method ethylbenzene catalyst taking the beta molecular sieve as an active component can reach 5 years, the catalyst can be operated for 5 years after being regenerated by burning carbon, but the activity of the catalyst after being regenerated by burning carbon again after being operated for 10 years is low, and the production requirement cannot 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 beta molecular sieve catalyst can only be treated as solid waste, and needs to be subjected to harmless treatment by invested capital and then 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 liquid phase method ethylbenzene catalyst as a raw material, can repair the framework defect of a beta 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 liquid phase alkylation of benzene-ethylene, the method comprising: mixing the inactivated liquid 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 the temperature of 100-150 ℃ for 4-72 hours, collecting a solid product, and drying and roasting the solid product; wherein the deactivated liquid phase method ethylbenzene catalyst contains beta molecular sieve.
Optionally, in the first mixture, SiO2The molar ratio of the deactivated liquid phase method ethylbenzene catalyst, the first organic template agent calculated by N and the 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 125-145 ℃, 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 liquid phase method ethylbenzene catalyst is (0.001-0.016): 1, preferably (0.0015-0.01): 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 activity of the deactivated liquid phase ethylbenzene catalyst is less than 70% of the activity of the fresh agent.
According to the technical scheme, the method adopts an inactivated liquid phase method ethylbenzene catalyst which takes the beta molecular sieve as an active component to carry out hydrothermal crystallization reaction, and the beta 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 can keep higher strength, can improve the 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 of preparing ethylbenzene by liquid phase alkylation of benzene-ethylene. 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 method for preparing ethylbenzene by benzene-ethylene liquid phase alkylation, which comprises: mixing the inactivated liquid 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 the temperature of 100-150 ℃ for 4-72 hours, collecting a solid product, and drying and roasting the solid product; wherein the deactivated liquid phase method ethylbenzene catalyst contains beta molecular sieve.
The method adopts an inactivated liquid phase method ethylbenzene catalyst which takes a beta molecular sieve as an active component to carry out hydrothermal crystallization reaction, the beta molecular sieve is recrystallized in the presence of an organic template agent, the framework defect of the molecular sieve can be repaired, the prepared catalyst not only can keep higher strength, but also can improve the crystallinity, the catalytic activity is equivalent to the level of a fresh agent, and the catalyst can be used as the catalyst again to be applied to the reaction of preparing ethylbenzene by liquid phase alkylation of styrene.
According to the present disclosure, the deactivated liquid phase ethylbenzene catalyst is a deactivated catalyst used in the liquid phase alkylation of benzene-ethylene to produce ethylbenzene. The specific composition of the deactivated liquid phase ethylbenzene catalyst is not particularly limited by the present disclosure, that is, the method of the present application is applicable to various deactivated catalysts using beta molecular sieve as an active component for preparing ethylbenzene by liquid phase alkylation of benzene-ethylene, for example, the deactivated liquid phase ethylbenzene catalyst may contain beta molecular sieve and alumina. The activity of the deactivated liquid phase ethylbenzene catalyst can be less than 70% of that of a fresh agent, namely the ethylene conversion rate when the deactivated liquid phase ethylbenzene 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 125-145 ℃, and the time is 12-48 h. The first mixture is placed in a closed reactor, and under a 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 beta molecular sieve is repaired. The hydrothermal crystallization reaction is carried out within the above preferred condition range, which is advantageous for further improving the crystallinity of the beta molecular sieve.
According to the disclosure, the first mixture is in SiO2The molar ratio of the deactivated liquid phase ethylbenzene catalyst, the first organic template agent in terms of N and water can be 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 in the preferable ratio range, which is favorable for improving the crystallinity of the β molecular sieve.
According to the present disclosure, the first organic templating agent can be a quaternary ammonium base, a quaternary ammonium salt, or a fatty amine, or a combination 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 a fatty amine represented by formula III.
Figure BDA0002010945260000051
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 BDA0002010945260000052
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, and may be 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 the aluminum source and the deactivated liquid phase method ethylbenzene catalyst are subjected to hydrothermal crystallization reaction, so that the silicon-aluminum ratio of the beta 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 deactivated liquid phase method ethylbenzene catalyst can be used in a molar ratio of (0.001-0.016): 1, preferably (0.0015-0.01): 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 is further illustrated by the following examples, but is not limited thereby.
In the following examples and comparative examples, the deactivated liquid phase ethylbenzene catalyst was derived from deactivated catalyst discharged from an industrial ethylbenzene plant, and contained beta molecular sieve and alumina, and the activity calculated according to the ethylene conversion was 68% of the fresh agent.
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 produced as a ratio to a reference value, i.e. the relative crystallinity value (r.c.%), in percent, as measured by XRD analysis method, based on 100% crystallinity of fresh catalyst AEB-6 of ethylbenzene used on a commercial plant.
Example 1
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetramethylammonium hydroxide solution and deionized water, and adding SiO into the obtained mixture2The molar ratio of the deactivated liquid 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 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 F-1, wherein the crystallinity of the catalyst F-1 is 88.7%.
Example 2
Mixing the deactivated liquid phase ethylbenzene catalyst, 27 wt% tetraethylammonium hydroxide solution and deionized water, and adding SiO to the mixture2The molar ratio of the deactivated ethylbenzene catalyst by the liquid phase method, the tetraethylammonium hydroxide and the water is 1: 0.06: 12.7. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 30h at 140 ℃ 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 F-2, wherein the crystallinity of the catalyst F-2 is 90.2%.
Example 3
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetrapropylammonium hydroxide solution and deionized water, and adding SiO into the obtained mixture2Measured deactivated liquid phase ethylbenzene catalyst, tetrapropyl hydrogen and oxygenThe molar ratio of ammonium hydroxide to water is 1: 0.1: 11. placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 145 ℃ 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 F-3, wherein the crystallinity of the catalyst F-3 is 87.6%.
Example 4
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetramethylammonium hydroxide solution and deionized water, and adding SiO into the obtained mixture2The molar ratio of the deactivated liquid 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 8h 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 F-4, wherein the crystallinity of the catalyst F-4 is 86.5%.
Example 5
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetramethylammonium hydroxide solution and deionized water, and adding SiO into the obtained mixture2The molar ratio of the deactivated liquid phase method ethylbenzene catalyst, the tetramethyl ammonium hydroxide and the water is 1: 0.15: 17.5. 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 F-5, wherein the crystallinity of the catalyst F-5 is 86.9%.
Example 6
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetramethylammonium hydroxide solution and deionized water, and adding SiO into the obtained mixture2The molar ratio of the deactivated liquid phase method ethylbenzene catalyst, the tetramethyl ammonium hydroxide and the water is 1: 0.02: 4. 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 F-6, wherein the crystallinity of the catalyst F-6 is 85.6%.
Example 7
Mixing the deactivated liquid phase ethylbenzene catalyst and 25 wt% tetramethyl ammonium hydroxideMixing the solution with deionized water, and adding SiO to the mixture2The molar ratio of the deactivated liquid phase method ethylbenzene catalyst, the tetramethyl ammonium hydroxide and the water is 1: 0.2: 25. 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 F-7, wherein the crystallinity of the catalyst F-7 is 86.8%.
Example 8
Pseudo-boehmite (Al)2O3Calculated) was mixed with 27 wt% tetraethylammonium hydroxide solution in a molar ratio of 0.01, treated at 120 ℃ for 4h in a closed reaction vessel with stirring, and then cooled to obtain a second mixture.
Mixing the deactivated liquid 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 ethylbenzene catalyst by the liquid phase method, the tetraethylammonium hydroxide and the water is 1: 0.03: 6.2, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated ethylbenzene catalyst in the liquid phase method was 0.008. 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 F-8, wherein the crystallinity of the catalyst F-8 is 89.7%.
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.
Mixing the deactivated liquid 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 liquid 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 liquid phase ethylbenzene catalyst was 0.006. Subjecting the mixture to a high pressure reactionIn a kettle, carrying out hydrothermal crystallization reaction for 30h at 140 ℃ under autogenous pressure, filtering and collecting a solid product, then drying for 12h at 120 ℃, roasting for 4h at 550 ℃ to prepare the catalyst F-9, wherein the X-ray diffraction pattern of the catalyst is shown in figure 1, and the crystallinity is 92.6%.
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 ethylbenzene catalyst by liquid phase method, 25 wt% tetrapropylammonium hydroxide solution, the second mixture and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated liquid phase method ethylbenzene catalyst, the tetrapropylammonium hydroxide and the water is 1: 0.1: 11, with Al2O3Calculated as aluminum hydroxide and SiO2The molar ratio of the deactivated ethylbenzene catalyst in the liquid phase method was 0.0015. Placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction for 48h at 145 ℃ 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 F-10, wherein the crystallinity of the catalyst F-10 is 89.3%.
Example 11
Pseudo-boehmite (Al)2O3Calculated) was mixed with 27 wt% tetraethylammonium hydroxide solution in a molar ratio of 0.008, treated at 120 ℃ for 4 hours with stirring in a closed reaction vessel, and then cooled to obtain a second mixture.
Mixing the deactivated liquid 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 ethylbenzene catalyst by the liquid phase method, the tetraethylammonium hydroxide and the water is 1: 0.03: 6.2, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated ethylbenzene catalyst in the liquid phase method was 0.0012. Placing the mixture in a high-pressure reaction kettle, performing hydrothermal crystallization reaction at 125 deg.C under autogenous pressure for 12h, filtering to collect solid product, and drying at 120 deg.CRoasting for 4h at 550 ℃ for 12h to prepare the catalyst F-11, wherein the crystallinity of the catalyst F-11 is 89.0%.
Example 12
Pseudo-boehmite (Al)2O3Calculated) was mixed with 27 wt% tetraethylammonium hydroxide solution in a molar ratio of 0.8, treated at 120 ℃ for 4h in a closed reaction vessel with stirring, and then cooled to give a second mixture.
Mixing the deactivated liquid phase ethylbenzene catalyst, 27 wt% tetraethylammonium hydroxide solution, the second mixture and deionized water to obtain a first mixture, wherein the first mixture is SiO2The molar ratio of the deactivated ethylbenzene catalyst by the liquid phase method, the tetraethylammonium hydroxide and the water is 1: 0.09: 6.2, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated ethylbenzene catalyst in the liquid phase method was 0.016. 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 F-12, wherein the crystallinity of the catalyst F-12 is 88.9%.
Example 13
Pseudo-boehmite (Al)2O3Calculated) was mixed with 27 wt% tetraethylammonium hydroxide solution in a molar ratio of 0.009, treated at 120 ℃ for 4h in a closed reaction vessel with stirring, and then cooled to give a second mixture.
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetrapropylammonium hydroxide solution, the second mixture and deionized water, and adding SiO into the mixture2The molar ratio of the deactivated ethylbenzene catalyst by the liquid phase method, the tetraethylammonium hydroxide and the water is 1: 0.15: 17.5, with Al2O3Pseudo-boehmite measured and SiO2The molar ratio of the deactivated ethylbenzene catalyst in the liquid phase method was 0.001. 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 F-13, wherein the crystallinity of the catalyst F-13 is 87.3%.
Comparative example 1
The deactivated ethylbenzene catalyst by the liquid phase method was calcined at 550 ℃ for 6 hours in an air atmosphere to obtain catalyst D-1 of the present comparative example, which had a crystallinity of 81.1%.
Comparative example 2
Mixing the deactivated ethylbenzene catalyst by liquid phase method, 25 wt% tetramethylammonium hydroxide solution and deionized water, and adding SiO into the obtained mixture2The molar ratio of the deactivated liquid 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 76.5%.
Test examples
The strength of the catalysts prepared in examples and comparative examples was measured on a DL III smart particle strength tester and the results are shown in table 1.
The liquid phase alkylation reaction was carried out using the catalysts prepared in examples and comparative examples under the conditions of starting materials of benzene and ethylene. The reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 3.6MPa, the molar ratio of benzene to ethylene is 12, and the volume space velocity of benzene is 3h-1The loading of the catalyst was 30mL, 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 Strength (N/mm) Ethylene conversion (%)
F-1 11.6 100
F-2 11.8 100
F-3 11.7 100
F-4 11.5 100
F-5 11.5 100
F-6 11.5 100
F-7 11.6 100
F-8 11.6 100
F-9 11.8 100
F-10 11.6 100
F-11 11.5 100
F-12 11.6 100
F-13 11.5 100
D-1 11.6 72
D-2 9.7 76
Fresh catalyst 11.2 100
As can be seen from table 1, the catalyst prepared by the method of the present disclosure can maintain high strength, and catalytic activity 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 liquid phase alkylation of benzene-ethylene is characterized by comprising the following steps: mixing the inactivated liquid 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 the temperature of 100-150 ℃ for 4-72 hours, collecting a solid product, and drying and roasting the solid product; wherein the deactivated liquid phase method ethylbenzene catalyst contains beta molecular sieve.
2. The method of claim 1, wherein the first mixture is in SiO2The molar ratio of the deactivated liquid phase method ethylbenzene catalyst, the first organic template agent calculated by N and the 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 125-145 ℃, 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 liquid phase method ethylbenzene catalyst is (0.001-0.016): 1, preferably (0.0015-0.01): 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 activity of the deactivated liquid phase ethylbenzene catalyst is less than 70% of that of the fresh agent.
CN201910245480.0A 2019-03-28 2019-03-28 Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene liquid phase alkylation Pending CN111744545A (en)

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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
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
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
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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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