CN114471701B - Regeneration method of deactivated non-binder molecular sieve catalyst - Google Patents

Regeneration method of deactivated non-binder molecular sieve catalyst Download PDF

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CN114471701B
CN114471701B CN202011158094.7A CN202011158094A CN114471701B CN 114471701 B CN114471701 B CN 114471701B CN 202011158094 A CN202011158094 A CN 202011158094A CN 114471701 B CN114471701 B CN 114471701B
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molecular sieve
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finished product
catalyst
sieve catalyst
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CN114471701A (en
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杨为民
王达锐
孙洪敏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—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
    • 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
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • 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
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
    • 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
    • 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
    • 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

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Abstract

The invention discloses a regeneration method of an inactivated binderless molecular sieve catalyst. The method comprises the following steps: (1) Contacting the deactivated non-binder molecular sieve catalyst with an acid solution to obtain a semi-finished product A; (2) Contacting the semi-finished product A, silica-alumina sol and reinforcing agent to obtain a semi-finished product B; (3) And (3) treating the semi-finished product B to obtain the regenerated binder-free molecular sieve catalyst. The regeneration method of the invention can lead the regenerated catalyst to have higher bulk density and high recovery rate of the skeleton four-coordination aluminum active center, is particularly suitable for the regeneration of the benzene and ethylene alkylation catalyst, and the regenerated catalyst is used in the benzene and ethylene alkylation reaction, has high activity, good selectivity and low xylene content of the product.

Description

Regeneration method of deactivated non-binder molecular sieve catalyst
Technical Field
The invention belongs to the technical field of catalytic chemistry and chemical engineering, and particularly relates to a regeneration method of an inactivated binderless molecular sieve catalyst.
Background
The ethylbenzene is prepared by gas phase alkylation of benzene and ethylene, and the catalyst used in industry is generally a molecular sieve catalyst, especially a binderless molecular sieve catalyst, which has an acidic catalytic active center, and the catalyst is gradually deactivated along with the progress of reaction time, wherein the deactivation causes mainly include the following points: carbon deposition generated in the reaction process can be deposited on pore channels or surfaces of the catalyst, so that microporous pore channels of the catalyst are blocked, and acidic active centers are covered, so that the catalytic performance of the catalyst is reduced; in addition, in the industrial ethylbenzene catalyst, the loss phenomenon exists in the acid active center of the catalyst in the long-time operation process, and some framework aluminum is converted into non-framework aluminum, so that the catalytic capability is reduced. When the performance of the catalyst is reduced to a certain extent, it is necessary to perform a regeneration treatment.
CN105597842B discloses a method for regenerating ethylbenzene catalyst, the regeneration process is: treating the deactivated ethylbenzene catalyst with 0.1-20.0wt% organic amine or organic ammonium solution for 2-20 hours, drying at 100-200 ℃ for 2-10 hours under nitrogen atmosphere, and roasting at 400-800 ℃ for 2-10 hours under air atmosphere, wherein the solid-to-liquid ratio of the deactivated catalyst to the organic amine or organic ammonium solution is (5-50): 1, the treatment temperature is 50-120 ℃. The regeneration method can only maintain the skeleton structure of the deactivated catalyst and increase part of mesoporous pore canal to recover the performance of the ethylbenzene catalyst, but the bulk density of the regenerated catalyst is reduced, and the damaged skeleton four-coordination aluminum active center cannot be recovered due to the deactivation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a regeneration method of an inactivated binderless molecular sieve catalyst. The catalyst regenerated by the regeneration method has high bulk density, can ensure the loading weight when being loaded in a reactor, is not easy to break in the reaction process, has high active center ratio of skeleton four-coordinate aluminum, is particularly used in the reaction of preparing ethylbenzene by gas phase alkylation of benzene and ethylene after being regenerated, has high activity and good ethylbenzene selectivity, and obviously reduces the xylene yield.
The invention provides a regeneration method of an inactivated binderless molecular sieve catalyst, which comprises the following steps:
(1) Contacting the deactivated non-binder molecular sieve catalyst with an acid solution to obtain a semi-finished product A;
(2) Contacting the semi-finished product A, silica-alumina sol and reinforcing agent to obtain a semi-finished product B; the reinforcing agent is one or more of acacia, pectin, carrageenan and sodium alginate;
(3) And (3) treating the semi-finished product B to obtain the regenerated binder-free molecular sieve catalyst.
In the above technical scheme, the binderless molecular sieve catalyst may be a binderless molecular sieve catalyst for preparing ethylbenzene by alkylation of benzene and ethylene. The molecular sieve can be a silicon-aluminum molecular sieve, preferably a ZSM-5 molecular sieve.
In the above technical solution, preferably, the acid in the step (1) is one or more of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid and citric acid.
In the above technical solution, preferably, the acid solution in step (1) is an aqueous solution, and the concentration is 0.1wt% to 5.0wt%.
In the above technical solution, preferably, the mass ratio of the deactivated binderless molecular sieve catalyst and the acid solution in the step (1) is: acid solution= (0.05-0.5): 1.
in the above technical solution, preferably, the process of contacting the deactivated binder-free molecular sieve catalyst with the acid solution in the step (1) to obtain the semi-finished product a is: stirring the deactivated non-adhesive molecular sieve catalyst and the acid solution in a closed space at 50-100 ℃ for 2-10 hours, and then washing and drying to obtain a semi-finished product A. Wherein the washing can remove the acid solution in the catalyst by deionized water, and the drying conditions are as follows: drying at 100-170deg.C for 6-12 hr.
In the above technical solution, preferably, the silica-alumina sol in the step (2) is a silica-alumina sol obtained by contacting a silicon source, an aluminum source and water (preferably deionized water).
In the above technical solution, preferably, the silicon source is one or more of silica sol, white carbon black and silicon powder; the aluminum source is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum isopropoxide.
In the above technical solution, preferably, the molar ratios of the silicon source, the aluminum source and the water are respectively: aluminum source= (50-400): 1, a step of; water: silicon source= (5-10): 1. wherein the silicon source is SiO 2 Calculated, aluminum source is Al 2 O 3 And (5) calculating.
In the above technical scheme, preferably, the preparation method of the silica-alumina sol comprises stirring a silicon source, an aluminum source and water in a closed space at a temperature of 80-120 ℃ for 6-24 hours.
In the above technical solution, preferably, the mass ratio of the semi-finished product a, the silica-alumina sol and the reinforcing agent in the step (2) is that the silica-alumina sol: semi-finished product a= (0.1-0.5): 1, a step of; reinforcing agent: semi-finished product a= (0.005-0.03): 1.
in the above technical solution, preferably, the contacting the semi-finished product a, the silica alumina sol and the reinforcing agent in the step (2) to obtain the semi-finished product B includes: mixing and stirring the silica-alumina sol and the reinforcing agent at 40-60 ℃ for 2-5 hours, then adding the semi-finished product A, and heating in a closed space at 120-170 ℃ for 12-72 hours.
In the above technical solution, preferably, the process of treating the semi-finished product B in the step (3) to obtain the regenerated binder-free molecular sieve catalyst is: and drying and roasting the semi-finished product B to obtain the regenerated binder-free molecular sieve catalyst. Wherein, the drying conditions are as follows: the drying temperature is 100-170 ℃ and the drying time is 6-12 hours; the roasting conditions are as follows: the roasting temperature is 500-600 ℃, and the roasting time is 5-10 hours.
In another aspect, the present invention provides a regenerated binderless molecular sieve catalyst, wherein the catalyst is prepared by the above regeneration method.
In the technical scheme, the bulk density of the regenerated binderless molecular sieve catalyst is 0.5-0.6g/mL, preferably 0.52-0.58g/mL. Preferably, the relative ratio of the bulk density of the regenerated catalyst to the bulk density of the fresh catalyst is from 0.98 to 1.0.
In the above technical scheme, preferably, the proportion of framework tetra-coordinated aluminum in the regenerated binderless ethylbenzene catalyst is 98-100%, preferably 99-100% of total aluminum. Preferably, the relative ratio of the proportion of the four-coordinated aluminum of the regenerated catalyst framework to the proportion of the four-coordinated aluminum of the fresh catalyst framework to the total aluminum is 0.98-1.0.
In a third aspect, the invention provides a process for the vapor phase alkylation of benzene and ethylene using a regenerated binderless molecular sieve catalyst.
In the technical scheme, the operation conditions of the gas-phase alkylation of benzene and ethylene are as follows: the reaction temperature is 330-400 ℃, the reaction pressure is 0.8-2.0MPa, and the ethylene mass airspeed is 0.2-2.5h -1 The benzene/ethylene molar ratio is 4-7.
The invention has the following beneficial effects:
1. the regeneration method of the deactivated non-binder molecular sieve catalyst can ensure that the regenerated non-binder molecular sieve catalyst has higher bulk density, the recovery rate of the skeleton four-coordination aluminum active center is high, and the mechanical strength and the catalytic performance of the catalyst are recovered to the level of a fresh catalyst.
2. The method for regenerating the deactivated non-binder molecular sieve catalyst is particularly suitable for the gas phase alkylation catalyst of benzene and ethylene, the regenerated catalyst is used in the gas phase alkylation reaction of benzene and ethylene, the activity is high, the selectivity is good, the xylene content in the product hydrocarbonated liquid is obviously reduced, the xylene content can reach below 600ppm, preferably below 550ppm, and the catalyst is recovered to the level of a fresh catalyst.
Drawings
FIG. 1 is an aluminum nuclear magnetic spectrum of a regenerated binderless ethylbenzene catalyst of example 1 of the present invention;
FIG. 2 is an aluminum nuclear magnetic resonance spectrum of the binderless ethylbenzene catalyst regenerated in comparative example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by the embodiments.
In the invention, the bulk density of the regenerated non-binder molecular sieve catalyst takes a 1000mL measuring cylinder as a container, the container is vibrated after 400g of catalyst is added, and after the volume scale mark is not reduced any more, the bulk density is calculated by dividing the weight of the added catalyst by the actual volume, and the unit is g/mL.
In the invention, the proportion of skeleton tetra-coordinated aluminum to total aluminum is obtained by aluminum nuclear magnetic resonance test, and is tested by nuclear magnetic resonance apparatus manufactured by VARIAN company in the United states, wherein the apparatus model is VNMS-400 WB, the resonance frequency is 104.2MHz, the rotating speed is 10000rps, and the standard substance is KAl (SO 4 ) 2 ·12H 2 O. The signal peak at 58ppm corresponds to the framework four-coordination aluminum state, the signal peak at 0ppm corresponds to the framework six-coordination state, and the ratio of the area of the signal peak at 58ppm to the sum of the areas of the two signal peaks at 0ppm is the ratio of the framework four-coordination aluminum to the total aluminum.
[ example 1 ]
This example was used for regeneration of an inactive binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100wt% ZSM-5 molecular sieve with a mechanical strength of 75N/cm) as follows: 1 ton of deactivated ethylbenzene catalyst and 20 tons of hydrochloric acid aqueous solution with the concentration of 0.1wt% are mixed, stirred in a closed space at 50 ℃ for 10 hours, after the completion, the hydrochloric acid solution in the ethylbenzene catalyst is washed by deionized water, and dried at 100 ℃ for 12 hours to obtain a semi-finished product A1. 600 kg of white carbon black, 133.2 kg of aluminum sulfate octadecanoate and 900 kg of deionized water are uniformly mixed, and stirred for 24 hours at 80 ℃ in a closed space to obtain silica-alumina sol. 100 kg of silica-alumina sol and 5 kg of acacia gum are mixed and stirred for 2 hours at 60 ℃, then 1 ton of semi-finished product A1 is added, and stirring is carried out for 72 hours at 120 ℃ in a closed space, so as to obtain a semi-finished product B1. The semi-finished product B1 is dried in an industrial oven at 100 ℃ for 12 hours, and then is roasted in a roasting furnace at 500 ℃ for 10 hours, so as to obtain the regenerated ethylbenzene catalyst C1. The bulk density of C1 was tested to be 0.58g/mL. As shown in FIG. 1, only one signal peak appears at 58ppm, and the proportion of framework tetra-coordinated aluminum in the total aluminum is 100%. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.59g/mL, and the proportion of framework tetra-coordinated aluminum to total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.50g/mL and the proportion of framework tetra-coordinated aluminum to total aluminum was 85%.
[ example 2 ]
This example was used for regeneration of an inactive binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100wt% ZSM-5 molecular sieve with a mechanical strength of 70N/cm) as follows: 1 ton of deactivated ethylbenzene catalyst and 2 tons of sulfuric acid aqueous solution with the concentration of 5wt% are mixed, stirred in a closed space at the temperature of 100 ℃ for 2 hours, after the completion, the sulfuric acid solution in the ethylbenzene catalyst is washed by deionized water, and the mixture is dried at the temperature of 170 ℃ for 6 hours to obtain a semi-finished product A2. 600 kg of white carbon black, 18.76 kg of aluminum nitrate nonahydrate and 1800 kg of deionized water are uniformly mixed, and stirred in a closed space at 120 ℃ for 6 hours to obtain silica-alumina sol. 500 kg of silica-alumina sol and 30 kg of carrageenan are mixed and stirred for 2 hours at 60 ℃, then 1 ton of semi-finished product A2 is added, and stirring is carried out for 12 hours at 170 ℃ in a closed space, thus obtaining semi-finished product B2. And drying the semi-finished product B2 in an industrial oven at 170 ℃ for 6 hours, and roasting in a roasting furnace at 600 ℃ for 5 hours to obtain the regenerated ethylbenzene catalyst C2. The bulk density of C2 was tested to be 0.52g/mL. The C2 aluminum nuclear magnetic spectrum also only shows a signal peak at 58ppm, and the proportion of the framework tetra-coordinated aluminum to the total aluminum is 100 percent. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.52g/mL, and the proportion of framework tetra-coordinated aluminum to total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.46g/mL and the proportion of framework tetra-coordinated aluminum to total aluminum was 88%.
[ example 3 ]
This example was used for regeneration of an inactive binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100wt% ZSM-5 molecular sieve with a mechanical strength of 72N/cm) as follows: 1 ton of deactivated ethylbenzene catalyst and 10 tons of oxalic acid aqueous solution with the concentration of 3wt% are mixed, stirred in a closed space at 80 ℃ for 5 hours, after the completion, the oxalic acid solution in the ethylbenzene catalyst is washed by deionized water, and dried at 140 ℃ for 8 hours to obtain a semi-finished product A3. 600 kg of silicon powder, 18.76 kg of aluminum nitrate nonahydrate and 1000 kg of deionized water are uniformly mixed, and stirred in a closed space at 100 ℃ for 12 hours to obtain silica-alumina sol. 300 kg of silica-alumina sol and 10 kg of pectin are mixed and stirred for 2 hours at 60 ℃, then 1 ton of semi-finished product A3 is added, and the mixture is stirred for 26 hours at 140 ℃ in a closed space to obtain a semi-finished product B3. And drying the semi-finished product B3 in an industrial oven at 140 ℃ for 9 hours, and roasting in a roasting furnace at 560 ℃ for 7 hours to obtain the regenerated ethylbenzene catalyst C3. The bulk density of C3 was tested to be 0.56g/mL. And calculating the proportion of skeleton tetra-coordinated aluminum to total aluminum to be 99 percent according to the areas of two signal peaks at 58ppm and 0ppm in the C3 aluminum nuclear magnetic spectrum. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.56g/mL, and the proportion of framework tetra-coordinated aluminum to total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.48g/mL and the proportion of framework tetra-coordinated aluminum to total aluminum was 91%.
[ example 4 ]
This example was used for regeneration of an inactive binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100wt% ZSM-5 molecular sieve with a mechanical strength of 74N/cm) as follows: 1 ton of deactivated ethylbenzene catalyst and 20 tons of hydrochloric acid aqueous solution with the concentration of 0.1 weight percent are mixed, stirred for 10 hours at 50 ℃ in a closed space, after the completion, the hydrochloric acid solution in the ethylbenzene catalyst is washed by deionized water, and the semi-finished product A4 is obtained after drying for 12 hours at 100 ℃. 600 kg of white carbon black, 133.2 kg of aluminum sulfate octadecanoate and 900 kg of deionized water are uniformly mixed, and stirred for 24 hours at 80 ℃ in a closed space to obtain silica-alumina sol. 100 kg of silica-alumina sol and 5 kg of sodium alginate are mixed and stirred for 2 hours at 60 ℃, then 1 ton of semi-finished product A4 is added, and stirring is carried out for 72 hours at 120 ℃ in a closed space, thus obtaining semi-finished product B4. And drying the semi-finished product B4 in an industrial oven at 100 ℃ for 12 hours, and roasting in a roasting furnace at 500 ℃ for 10 hours to obtain the regenerated ethylbenzene catalyst C4. The bulk density of C4 was tested to be 0.55g/mL. The C4 aluminum nuclear magnetic spectrum only shows a signal peak at 58ppm, and the proportion of the framework tetra-coordinated aluminum to the total aluminum is 100 percent. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.55g/mL, and the proportion of framework tetra-coordinated aluminum to total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.49g/mL and the proportion of framework tetra-coordinated aluminum to total aluminum was 84%.
Comparative example 1
The deactivated binderless ethylbenzene catalyst was regenerated by the method described in patent CN105597842B, which is described in detail as follows: after discharging the deactivated binderless molecular sieve catalyst in the reactor (same as the deactivated ethylbenzene catalyst of example 1), the catalyst was treated with 1.5 wt.% tetrabutylammonium hydroxide solution for 5 hours, wherein the solid-to-liquid ratio of the deactivated catalyst to the tetrabutylammonium hydroxide solution was 15: 1. the treatment temperature is 85 ℃; then the catalyst is dried for 4 hours at 145 ℃ under nitrogen atmosphere; finally, roasting the catalyst at 550 ℃ for 5 hours in an air atmosphere to obtain the regenerated ethylbenzene catalyst D1. The bulk density of D1 was tested to be 0.46g/mL. The aluminum nuclear magnetic spectrum of D1 is shown in figure 2, and the proportion of the framework four-coordination aluminum in the total aluminum is calculated to be 82% according to the areas of two signal peaks at 58ppm and 0ppm in the aluminum nuclear magnetic spectrum of D1.
Comparative example 2
The deactivated binderless molecular sieve catalyst (same deactivated ethylbenzene catalyst as in example 1) was calcined in a calciner at 600 deg.c for 5 hours to give regenerated ethylbenzene catalyst D2. The bulk density of D2 was tested to be 0.48g/mL. According to the areas of two signal peaks at 58ppm and 0ppm in the aluminum nuclear magnetic spectrum, the proportion of D2 framework tetra-coordinated aluminum to total aluminum is calculated to be 85 percent.
[ example 4 ]
The regenerated binderless ethylbenzene catalysts C1-C4 and D1-D2 of examples 1-4 and comparative examples 1-2, and the fresh catalyst of examples 1-3 were applied to a benzene and ethylene vapor phase alkylation reaction, respectively, at a reaction temperature of 370℃under a pressure of 1.6MPa and an ethylene mass space velocity of 0.6h -1 The xylene content, ethylene conversion and ethyl selectivity of the hydrocarbonated liquid were tested at a benzene to ethylene molar ratio of 5. The test results are shown in Table 1 below.
TABLE 1 results of gas phase alkylation of benzene with ethylene
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (16)

1. A method of regenerating an inactivated binderless molecular sieve catalyst comprising:
(1) Contacting the deactivated non-binder molecular sieve catalyst with an acid solution to obtain a semi-finished product A;
(2) Contacting the semi-finished product A, silica-alumina sol and reinforcing agent to obtain a semi-finished product B; the reinforcing agent is one or more of acacia, pectin, carrageenan and sodium alginate;
(3) Treating the semi-finished product B to obtain a regenerated binder-free molecular sieve catalyst;
the process of contacting the deactivated non-binder molecular sieve catalyst with the acid solution in step (1) to obtain the semi-finished product A comprises the following steps: stirring the deactivated non-binder molecular sieve catalyst and the acid solution in a closed space at 50-100 ℃ for 2-10 hours, and then washing and drying to obtain a semi-finished product A;
the process of contacting the semi-finished product A, the silica-alumina sol and the reinforcing agent to obtain the semi-finished product B in the step (2) is as follows: mixing and stirring the silica-alumina sol and the reinforcing agent at 40-60 ℃ for 2-5 hours, then adding the semi-finished product A, and heating in a closed space at 120-170 ℃ for 12-72 hours;
the process of treating the semi-finished product B to obtain the regenerated binder-free molecular sieve catalyst in the step (3) is as follows: and drying and roasting the semi-finished product B to obtain the regenerated binder-free molecular sieve catalyst.
2. The regeneration process of claim 1, wherein the binderless molecular sieve catalyst is a binderless molecular sieve catalyst for the alkylation of benzene with ethylene to produce ethylbenzene.
3. The method of claim 2, wherein the molecular sieve is a ZSM-5 molecular sieve.
4. The method of claim 1, wherein the acid in step (1) is one or more of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, and citric acid.
5. The method according to claim 4, wherein the acid solution is an aqueous solution having a concentration of 0.1wt% to 5.0wt%.
6. The regeneration process according to claim 1, wherein the mass ratio of the deactivated binderless molecular sieve catalyst to the acid solution in step (1) is: acid solution= (0.05-0.5): 1.
7. the regeneration method according to claim 1, wherein in step (1), the drying conditions are as follows: drying at 100-170deg.C for 6-12 hr.
8. The method according to claim 1, wherein the silica-alumina sol in the step (2) is a silica-alumina sol obtained by contacting a silicon source, an aluminum source and water.
9. The method according to claim 8, wherein the silicon source in the step (2) is one or more of silica sol, white carbon black and silicon powder; the aluminum source is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum isopropoxide.
10. The regeneration method according to claim 8, wherein in the step (2), the molar ratios of the silicon source, the aluminum source and the water are respectively: aluminum source= (50-400): 1, a step of; water: silicon source= (5-10): 1, a step of; wherein the silicon source is SiO 2 Calculated, aluminum source is Al 2 O 3 And (5) calculating.
11. The method according to claim 8, wherein the silica-alumina sol is prepared by stirring a silicon source, an aluminum source and water in a closed space at a temperature of 80 to 120 ℃ for 6 to 24 hours.
12. The regeneration method according to claim 1, wherein the mass ratio of the semi-finished product a, the silica alumina sol and the reinforcing agent in the step (2) is that the silica alumina sol: semi-finished product a= (0.1-0.5): 1, a step of; reinforcing agent: semi-finished product a= (0.005-0.03): 1.
13. the regeneration method according to claim 1, wherein in the step (3), the drying conditions are as follows: the drying temperature is 100-170 ℃ and the drying time is 6-12 hours; the roasting conditions are as follows: the roasting temperature is 500-600 ℃, and the roasting time is 5-10 hours.
14. A regenerated binderless molecular sieve catalyst prepared by the regeneration process of any one of claims 1 to 13.
15. A process for the vapor phase alkylation of benzene and ethylene using the regenerated binderless molecular sieve catalyst of claim 14.
16. The process according to claim 15, wherein the benzene and ethylene gas phase alkylation is carried out at a reaction temperature of 330 to 400 ℃, a reaction pressure of 0.8 to 2.0MPa and an ethylene mass space velocity of 0.2 to 2.5h -1 The benzene/ethylene molar ratio is 4-7.
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