CN114471701A - Regeneration method of deactivated binderless molecular sieve catalyst - Google Patents

Regeneration method of deactivated binderless molecular sieve catalyst Download PDF

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CN114471701A
CN114471701A CN202011158094.7A CN202011158094A CN114471701A CN 114471701 A CN114471701 A CN 114471701A CN 202011158094 A CN202011158094 A CN 202011158094A CN 114471701 A CN114471701 A CN 114471701A
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molecular sieve
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aluminum
sieve catalyst
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CN114471701B (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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    • 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
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    • 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
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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
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a regeneration method of a deactivated binderless molecular sieve catalyst. The method comprises the following steps: (1) contacting the inactivated binderless molecular sieve catalyst with an acid solution to obtain a semi-finished product A; (2) contacting the semi-finished product A, the silicon-aluminum sol and the reinforcing agent to obtain a semi-finished product B; (3) and treating the semi-finished product B to obtain the regenerated binderless 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 framework four-coordination aluminum active center, is particularly suitable for regenerating the benzene and ethylene alkylation catalyst, and the regenerated catalyst is used for the benzene and ethylene alkylation reaction, has high activity, good selectivity and low xylene content of the product.

Description

Regeneration method of deactivated binderless 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 gas phase alkylation of benzene and ethylene to prepare ethylbenzene is an acid catalytic reaction, the catalyst used in industry is generally a molecular sieve catalyst, especially a molecular sieve catalyst without a binder, and has an acidic catalytic active center, and the catalyst is gradually deactivated along with the reaction time, and the deactivation is mainly caused by the following points: carbon deposition generated in the reaction process can be deposited on the pore channels or the surface of the catalyst, so that the micropore pore channels of the catalyst are blocked, and an acid active center is covered, so that the catalytic performance of the catalyst is reduced; in addition, in the long-time operation process of the industrial ethylbenzene catalyst, the loss phenomenon of the acidic active center of the catalyst exists, and some framework aluminum is converted into non-framework aluminum, so that the catalytic capability is also reduced. When the performance of the catalyst is reduced to a certain degree, it is required to perform a regeneration treatment.
CN105597842B discloses a regeneration method of an ethylbenzene catalyst, the regeneration process is as follows: treating the inactivated ethylbenzene catalyst with 0.1-20.0 wt% of organic amine or organic ammonium solution for 2-20 hours, drying at 100-200 ℃ for 2-10 hours in a nitrogen atmosphere, and roasting at 800 ℃ for 2-10 hours in an air atmosphere, wherein the solid-liquid ratio of the inactivated 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 framework structure of the deactivated catalyst and increase part of mesoporous channels to recover the performance of the ethylbenzene catalyst, but the bulk density of the regenerated catalyst is reduced, and the damaged framework four-coordinate aluminum active center cannot be recovered due to deactivation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for regenerating a deactivated binderless molecular sieve catalyst. The catalyst regenerated by the regeneration method has high bulk density, can ensure the filling weight when being filled in a reactor, is not easy to break in the reaction process, has high occupation ratio of the four-coordinate aluminum active center of the framework, is particularly used for the reaction of preparing the ethylbenzene by the gas phase alkylation of the benzene and the ethylene after the inactivated catalyst for preparing the ethylbenzene by the gas phase alkylation of the benzene and the ethylene is regenerated, has high activity and good ethylbenzene selectivity, and obviously reduces the yield of the xylene.
The invention provides a regeneration method of a deactivated binderless molecular sieve catalyst, which comprises the following steps:
(1) contacting the deactivated molecular sieve catalyst without the adhesive with an acid solution to obtain a semi-finished product A;
(2) contacting the semi-finished product A, the silicon-aluminum sol and the 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 treating the semi-finished product B to obtain the regenerated binderless molecular sieve catalyst.
In the above technical scheme, the binderless molecular sieve catalyst can be a binderless molecular sieve catalyst used for preparing ethylbenzene by alkylating benzene and ethylene. The molecular sieve may be a silico-alumina molecular sieve, preferably a ZSM-5 molecular sieve.
In the above technical solution, preferably, the acid in 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 the step (1) is an aqueous solution, and the concentration is 0.1 wt% to 5.0 wt%.
In the above technical solution, preferably, the mass ratio of the deactivated binderless molecular sieve catalyst to the acid solution in step (1) is that the binderless molecular sieve catalyst: acid solution ═ (0.05-0.5): 1.
in the above technical solution, preferably, the step (1) of contacting the deactivated binderless molecular sieve catalyst with an acid solution to obtain the semi-finished product a comprises the following steps: stirring the inactivated adhesive-free molecular sieve catalyst and the acid solution in a closed space at the stirring temperature of 50-100 ℃ for 2-10 hours, and then washing and drying to obtain a semi-finished product A. Wherein the washing can be carried out by washing the acid solution in the catalyst with deionized water under the following drying conditions: drying at 100-170 deg.C for 6-12 hr.
In the above technical solution, preferably, the silica-alumina sol in step (2) is 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 as follows: aluminum source ═ (50-400): 1; water: silicon source ═ 5-10: 1. wherein the silicon source is SiO2Calculated, the aluminum source is Al2O3And (4) calculating.
In the above technical solution, 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 stirring temperature of 80-120 ℃ for 6-24 hours.
In the above technical solution, preferably, in the step (2), the semi-finished product a, the silica-alumina sol and the reinforcing agent are in a mass ratio of silica-alumina sol: semi-finished product a ═ (0.1-0.5): 1; reinforcing agent: semi-finished product a ═ (0.005-0.03): 1.
in the above technical solution, preferably, the step (2) of contacting the semi-finished product a, the silica-alumina sol and the reinforcing agent to obtain the semi-finished product B comprises the following steps: mixing and stirring the silicon-aluminum 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 the temperature of 120-170 ℃ for 12-72 hours.
In the above technical solution, preferably, the step (3) of processing the semi-finished product B to obtain the regenerated binderless molecular sieve catalyst comprises the following steps: 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 were as follows: the roasting temperature is 500-600 ℃, and the roasting time is 5-10 hours.
In another aspect, the 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 0.52-0.58 g/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 solution, preferably, the ratio of framework four-coordinate aluminum in the regenerated binderless ethylbenzene catalyst to total aluminum is 98-100%, preferably 99-100%. Preferably, the relative ratio of the proportion of tetra-coordinated aluminum of the regenerated catalyst framework to the proportion of tetra-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 above technical scheme, the operation conditions for the gas phase alkylation of benzene and ethylene are as follows: the reaction temperature is 330 ℃ and 400 ℃, the reaction pressure is 0.8-2.0MPa, and the mass space velocity of ethylene is 0.2-2.5h-1The benzene/ethylene molar ratio is 4-7.
The invention has the following beneficial effects:
1. the regeneration method of the deactivated binderless molecular sieve catalyst can ensure that the regenerated binderless molecular sieve catalyst has higher bulk density, the recovery rate of the framework four-coordinate 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 molecular sieve catalyst without the binder is particularly suitable for a benzene and ethylene gas-phase alkylation catalyst, the regenerated catalyst is used for the benzene and ethylene gas-phase alkylation reaction, the activity is high, the selectivity is good, the xylene content in a product alkylation liquid is obviously reduced and can reach below 600ppm, preferably below 550ppm, and the level of the fresh catalyst is recovered.
Drawings
FIG. 1 is an aluminum nuclear magnetic spectrum of a binderless ethylbenzene catalyst regenerated in example 1 of the present invention;
FIG. 2 is an aluminum nuclear magnetic spectrum of the binderless ethylbenzene catalyst regenerated in comparative example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
In the invention, the bulk density of the regenerated binderless molecular sieve catalyst is calculated by taking a 1000mL measuring cylinder as a container, adding 400g of the catalyst and then vibrating the container, and dividing the weight of the added catalyst by the actual volume to obtain the bulk density with the unit of g/mL after the volume scale mark is not reduced any more.
In the invention, the proportion of framework four-coordinate aluminum in total aluminum is obtained by aluminum nuclear magnetic test, and the test is carried out by adopting a nuclear magnetic resonance instrument manufactured by VARIAN company in America, the instrument model is VNMRS-400WB, the resonance frequency is 104.2MHz, the rotating speed is 10000rps, and the standard substance is KAl (SO)4)2·12H2And O. The signal peak at 58ppm in the spectrogram corresponds to the four-coordinate aluminum state of the framework, the signal peak at 0ppm corresponds to the six-coordinate state outside the framework, and the ratio of the area of the signal peak at 58ppm to the sum of the areas of the two signal peaks at 58ppm and 0ppm is the ratio of the four-coordinate aluminum of the framework to the total aluminum.
[ example 1 ]
This example was used to regenerate deactivated binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100 wt% ZSM-5 molecular sieve and has a mechanical strength of 75N/cm) by the following procedure: mixing 1 ton of deactivated ethylbenzene catalyst and 20 ton of 0.1 wt% hydrochloric acid aqueous solution, stirring in a closed space at 50 deg.C for 10 hr, washing with deionized water to remove hydrochloric acid solution in ethylbenzene catalyst, and drying at 100 deg.C for 12 hr to obtain semi-finished product A1. 600 kg of white carbon black, 133.2 kg of aluminum sulfate octadecahydrate and 900 kg of deionized water are uniformly mixed and stirred for 24 hours at 80 ℃ in a closed space to obtain the silicon-aluminum sol. 100 kg of silica-alumina sol and 5 kg of Arabic gum are mixed and stirred for 2 hours at 60 ℃, then 1 ton of semi-finished product A1 is added, and the mixture is stirred for 72 hours at 120 ℃ in a closed space to obtain a semi-finished product B1. And drying the semi-finished product B1 in an industrial oven at 100 ℃ for 12 hours, and then roasting in a roasting oven at 500 ℃ for 10 hours to obtain the regenerated ethylbenzene catalyst C1. The bulk density of C1 was tested to be 0.58 g/mL. The nuclear magnetic spectrum of C1 shows in FIG. 1, and only one signal peak appears at 58ppm, and the proportion of skeleton four-coordinate 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 four-coordination aluminum in the total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.50g/mL, and the proportion of framework tetra-coordinated aluminum in the total aluminum was 85%.
[ example 2 ]
This example was used to regenerate deactivated binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100 wt% ZSM-5 molecular sieve and has a mechanical strength of 70N/cm) by the following procedure: mixing 1 ton of deactivated ethylbenzene catalyst and 2 ton of sulfuric acid aqueous solution with the concentration of 5 wt%, stirring for 2 hours in a closed space at 100 ℃, washing out the sulfuric acid solution in the ethylbenzene catalyst by using deionized water after the stirring is finished, and drying for 6 hours at 170 ℃ 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 for 6 hours at 120 ℃ in a closed space to obtain the 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 the mixture is stirred for 12 hours at 170 ℃ in a closed space to obtain semi-finished product B2. And (3) drying the semi-finished product B2 in an industrial oven at 170 ℃ for 6 hours, and then roasting in a roasting furnace at 600 ℃ for 5 hours to obtain a regenerated ethylbenzene catalyst C2. The bulk density of C2 was tested to be 0.52 g/mL. The nuclear magnetic spectrum of the C2 aluminum also shows a signal peak at 58ppm, and the proportion of framework four-coordinate aluminum in the total aluminum is 100%. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.52g/mL, and the proportion of framework four-coordination aluminum in the total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.46g/mL and the proportion of framework tetra-coordinated aluminium in the total aluminium was 88%.
[ example 3 ]
This example was used to regenerate deactivated binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100 wt% ZSM-5 molecular sieve and has a mechanical strength of 72N/cm) by the following procedure: mixing 1 ton of deactivated ethylbenzene catalyst and 10 tons of oxalic acid aqueous solution with the concentration of 3 wt%, stirring for 5 hours in a closed space at 80 ℃, washing the oxalic acid solution in the ethylbenzene catalyst by deionized water after the stirring is finished, and drying for 8 hours at 140 ℃ 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 for 12 hours at 100 ℃ in a closed space to obtain the 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 semi-finished product B3. And (3) drying the semi-finished product B3 in an industrial oven at 140 ℃ for 9 hours, and then roasting in a roasting furnace at 560 ℃ for 7 hours to obtain a regenerated ethylbenzene catalyst C3. The bulk density of C3 was tested to be 0.56 g/mL. According to the areas of two signal peaks at 58ppm and 0ppm in the nuclear magnetic spectrum of the aluminum of C3, the proportion of skeleton four-coordinate aluminum in the total aluminum is calculated to be 99%. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.56g/mL, and the proportion of framework four-coordination aluminum in the total aluminum is 100%; the bulk density of the deactivated ethylbenzene catalyst was 0.48g/mL, and the proportion of framework tetra-coordinated aluminum in the total aluminum was 91%.
[ example 4 ]
This example was used to regenerate deactivated binderless molecular sieve catalyst (ethylbenzene catalyst, which consists of 100 wt% ZSM-5 molecular sieve and has a mechanical strength of 74N/cm) by the following procedure: mixing 1 ton of deactivated ethylbenzene catalyst and 20 ton of hydrochloric acid aqueous solution with the concentration of 0.1 wt%, stirring for 10 hours at 50 ℃ in a closed space, washing the hydrochloric acid solution in the ethylbenzene catalyst by deionized water after the stirring is finished, and drying for 12 hours at 100 ℃ to obtain a semi-finished product A4. 600 kg of white carbon black, 133.2 kg of aluminum sulfate octadecahydrate and 900 kg of deionized water are uniformly mixed and stirred for 24 hours at 80 ℃ in a closed space to obtain the silicon-aluminum sol. 100 kg of silica-alumina sol and 5 kg of sodium alginate are mixed and stirred for 2 hours at the temperature of 60 ℃, then 1 ton of semi-finished product A4 is added, and the mixture is stirred for 72 hours at the temperature of 120 ℃ in a closed space to obtain a semi-finished product B4. And (3) drying the semi-finished product B4 in an industrial oven at 100 ℃ for 12 hours, and then roasting in a roasting furnace at 500 ℃ for 10 hours to obtain a regenerated ethylbenzene catalyst C4. The bulk density of C4 was tested to be 0.55 g/mL. The aluminum nuclear magnetic spectrum of C4 shows a signal peak only at 58ppm, and the proportion of skeleton four-coordinate aluminum in the total aluminum is 100%. In addition, the bulk density of the fresh ethylbenzene catalyst is 0.55g/mL, and the proportion of framework four-coordination aluminum in the total aluminum is 100%; the deactivated ethylbenzene catalyst had a bulk density of 0.49g/mL and the proportion of framework tetra-coordinated aluminum in the total aluminum was 84%.
Comparative example 1
The deactivated binderless ethylbenzene catalyst was regenerated according to the method of patent CN105597842B, which comprises the following steps: after discharging the deactivated binderless molecular sieve catalyst (same deactivated ethylbenzene catalyst of example 1) from the reactor, treating the catalyst 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 drying the catalyst for 4 hours at 145 ℃ in a nitrogen atmosphere; finally, the catalyst is roasted for 5 hours at the high temperature of 550 ℃ in the air atmosphere to prepare the regenerated ethylbenzene catalyst D1. The bulk density of D1 was tested to be 0.46 g/mL. The aluminum nuclear magnetic spectrum of D1 is shown in FIG. 2, and the proportion of framework four-coordinate 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 (the deactivated ethylbenzene catalyst of example 1) was calcined at 600 deg.C in a calciner for 5 hours to provide regenerated ethylbenzene catalyst D2. The bulk density of D2 was tested to be 0.48 g/mL. According to the areas of two signal peaks at 58ppm and 0ppm in the aluminum nuclear magnetic spectrum, the proportion of D2 framework four-coordinate aluminum in the total aluminum is calculated to be 85%.
[ example 4 ]
The regenerated binderless ethylbenzene catalysts C1-C4 and D1-D2 of examples 1-4 and comparative examples 1-2 and the fresh catalysts of examples 1-3 are respectively applied to the gas phase alkylation reaction of benzene and ethylene at the reaction temperature of 370 ℃, the pressure of 1.6MPa and the ethylene mass space velocity of 0.6h-1The xylene content, the ethylene conversion and the ethyl selectivity of the hydrocarbon liquid were tested at a benzene to ethylene molar ratio of 5. The test results are shown in table 1 below.
TABLE 1 gas phase alkylation of benzene and ethylene results
Figure BDA0002743400870000061
The specific embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A process for regenerating a deactivated binderless molecular sieve catalyst comprising:
(1) contacting the inactivated binderless molecular sieve catalyst with an acid solution to obtain a semi-finished product A;
(2) contacting the semi-finished product A, the silicon-aluminum sol and the 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 treating the semi-finished product B to obtain the regenerated binderless molecular sieve catalyst.
2. Regeneration process according to claim 1, wherein the binderless molecular sieve catalyst is a binderless molecular sieve catalyst for the alkylation of benzene with ethylene to produce ethylbenzene, preferably wherein the molecular sieve is a ZSM-5 molecular sieve.
3. The regeneration 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; preferably, the acid solution is an aqueous solution with a concentration of 0.1 wt% to 5.0 wt%.
4. The regeneration method of claim 1, wherein the deactivated binderless molecular sieve catalyst and the acid solution of step (1) are present in a mass ratio of binderless molecular sieve catalyst: acid solution ═ (0.05-0.5): 1.
5. the regeneration method of claim 1, wherein the step (1) of contacting the deactivated binderless molecular sieve catalyst with the acid solution to obtain the semi-finished product A comprises: stirring the inactivated adhesive-free molecular sieve catalyst and the acid solution in a closed space at the stirring temperature of 50-100 ℃ for 2-10 hours, and then washing and drying to obtain a semi-finished product A; preferably, the drying conditions are as follows: drying at 100-170 deg.C for 6-12 hr.
6. The regeneration method of claim 1, wherein the silica-alumina sol in step (2) is obtained by contacting a silicon source, an aluminum source and water;
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;
preferably, the molar ratio of the silicon source to the aluminum source to the water is, respectively, silicon source: aluminum source ═ (50-400): 1; water: silicon source ═ 5-10: 1; wherein the silicon source is SiO2Calculated, the aluminum source is Al2O3Calculating;
preferably, the preparation method of the silicon-aluminum sol comprises the steps of stirring a silicon source, an aluminum source and water in a closed space, wherein the stirring temperature is 80-120 ℃, and the stirring time is 6-24 hours.
7. The regeneration method according to claim 1 or 6, wherein the mass ratio of the semi-finished product A, the silicon-aluminum sol and the reinforcing agent in the step (2) is as follows: semi-finished product a ═ (0.1-0.5): 1; reinforcing agent: semi-finished product a ═ (0.005-0.03): 1.
8. the regeneration method of claim 1, wherein the step (2) of contacting the semi-finished product A, the silica-alumina sol and the reinforcing agent to obtain the semi-finished product B comprises the following steps: mixing and stirring the silicon-aluminum 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 the temperature of 120-170 ℃ for 12-72 hours.
9. The regeneration method of claim 1, wherein the step (3) of treating the semi-finished product B to obtain the regenerated binderless molecular sieve catalyst comprises the following steps: drying and roasting the semi-finished product B to obtain a regenerated binder-free molecular sieve catalyst; preferably, the drying conditions are as follows: the drying temperature is 100-170 ℃, and the drying time is 6-12 hours; the roasting conditions were as follows: the roasting temperature is 500-600 ℃, and the roasting time is 5-10 hours.
10. A regenerated binderless molecular sieve catalyst prepared by the regeneration process of any one of claims 1 to 9.
11. A process for the vapor phase alkylation of benzene and ethylene using the regenerated binderless molecular sieve catalyst of claim 10.
12. The process as claimed in claim 11, wherein the benzene and ethylene are vapor phase alkylated under the following operating conditions at a reaction temperature of 330 ℃ and a reaction pressure of 0.8 to 2.0MPa and a mass space velocity of ethylene of 0.2 to 2.5h-1The benzene/ethylene molar ratio is 4-7.
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