CN114602538A - Molecular sieve catalyst, and preparation method and application thereof - Google Patents

Molecular sieve catalyst, and preparation method and application thereof Download PDF

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Publication number
CN114602538A
CN114602538A CN202011445550.6A CN202011445550A CN114602538A CN 114602538 A CN114602538 A CN 114602538A CN 202011445550 A CN202011445550 A CN 202011445550A CN 114602538 A CN114602538 A CN 114602538A
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molecular sieve
sample
sieve catalyst
catalyst
hierarchical pore
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黄声骏
虞永华
张大治
邹明明
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a molecular sieve catalyst, a preparation method and an application thereof, wherein the molecular sieve catalyst comprises a hierarchical pore molecular sieve; modification elements are modified on the hierarchical pore molecular sieve; the modifying element is at least one of alkaline earth metal elements, rare earth metal elements and nonmetal elements. The modified molecular sieve catalyst provided by the application has good catalytic performance for the reaction of preparing 6-aminocapronitrile by ammoniation of caprolactam, the conversion rate of caprolactam can reach more than 93%, and the conversion rate of 6-aminocapronitrile reaches 96%.

Description

Molecular sieve catalyst, and preparation method and application thereof
Technical Field
The application relates to a molecular sieve catalyst, a preparation method and application thereof, and belongs to the technical field of catalytic synthesis.
Background
6-aminocapronitrile is an important chemical intermediate and can be used for synthesizing 1, 6-hexamethylene diamine. The production of 6-aminocapronitrile is currently obtained for the most part by partial hydrogenation of 1, 6-adiponitrile. The reports on the preparation of 6-aminocapronitrile from caprolactam are relatively few, and the patents US2234566, FR1573490 and the like report methods for preparing 6-aminocapronitrile from caprolactam, but the reaction results are relatively poor.
Disclosure of Invention
According to one aspect of the application, a molecular sieve catalyst, a preparation method and an application thereof are provided, wherein a hierarchical pore molecular sieve modified by aid of auxiliary component elements is used in a reaction for preparing 6-aminocapronitrile by ammoniation of caprolactam, and shows good catalytic performance.
The molecular sieve catalyst comprises a hierarchical pore molecular sieve;
the hierarchical pore molecular sieve is modified with auxiliary component elements.
The auxiliary component element is at least one of alkaline earth metal elements, rare earth metal elements and nonmetal elements.
Optionally, the alkaline earth metal element is selected from at least one of Mg and Ca;
the rare earth metal element is selected from at least one of La and Ce;
the non-metallic element is at least one selected from P, F, B.
Optionally, in the molecular sieve catalyst, the content of the auxiliary component element is 0.5-10 wt%.
Optionally, the hierarchical pore molecular sieve is an MFI-type molecular sieve.
Optionally, the hierarchical pore molecular sieve is a hierarchical pore ZSM-5 molecular sieve.
Optionally, the silica-alumina ratio of the original molecular sieve of the multi-stage pore ZSM-5 molecular sieve is 20-50.
Preferably, the silica-alumina ratio of the original molecular sieve of the multi-stage pore ZSM-5 molecular sieve is 20-35.
In another aspect of the present application, a method for preparing the above molecular sieve catalyst is provided, which is characterized by at least comprising the following steps:
and (3) dipping the hierarchical pore molecular sieve in a solution I containing an auxiliary component element to obtain the molecular sieve catalyst.
Optionally, the additive component elements are derived from a modified element precursor;
in the solution I, the concentration of the modified element precursor is 0.5-10 wt% based on the mass of the auxiliary component elements;
preferably, the precursor of the elements of the auxiliary component is at least one selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, ammonium fluoride, boric acid, magnesium nitrate, magnesium carbonate, magnesium chloride, calcium nitrate, calcium phosphate, lanthanum nitrate, lanthanum chloride and cerium nitrate.
Specifically, the lower limit of the concentration of the precursor of the element of the auxiliary component can be independently selected from 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%; the upper concentration limit of the element precursor of the auxiliary component can be independently selected from 5 wt%, 6 wt%, 7 wt%, 8 wt% and 10 wt%.
Alternatively, the impregnation conditions are:
the solid-liquid ratio of the hierarchical pore molecular sieve to the solution I is 1: 5-1: 10 g/ml.
Preferably, the solid-to-liquid ratio of the hierarchical pore molecular sieve to solution I is 1:6 g/ml.
Specifically, the lower limit of the solid-to-liquid ratio of the hierarchical pore molecular sieve to the solution I can be independently selected from 1:5g/ml, 1:5.5g/ml, 1:6g/ml, 1:6.5g/ml and 1:7 g/ml; the upper limit of the solid-liquid ratio of the hierarchical pore molecular sieve to the solution I can be independently selected from 1:7.5g/ml, 1:8g/ml, 1:8.5g/ml, 1:9g/ml and 1:10 g/ml.
Alternatively, the impregnation is carried out at normal temperature.
Optionally, the method further comprises drying and calcining the molecular sieve catalyst;
the drying conditions are as follows: the drying temperature is lower than 100 ℃, preferably, the drying temperature is 60-90 ℃;
the roasting conditions are as follows: the roasting temperature is 500-600 ℃, and the roasting time is 2-4 h.
The drying time is not particularly limited in the present application, and those skilled in the art can set the drying time as needed as long as the moisture in the molecular sieve catalyst is sufficiently volatilized. The drying temperature should not be too high, above 100 ℃, which may cause the solute containing the elements of the adjuvant component to volatilize with the solvent.
Specifically, the lower limit of the drying temperature can be selected from 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, and 80 deg.C; the upper limit of the drying temperature can be independently selected from 85 deg.C, 87 deg.C, 90 deg.C, 95 deg.C, and 100 deg.C.
Specifically, the lower limit of the roasting temperature can be independently selected from 500 ℃, 510 ℃, 520 ℃, 530 ℃ and 550 ℃; the upper limit of the calcination temperature may be independently selected from 560 ℃, 570 ℃, 580 ℃, 590 ℃ and 600 ℃.
Specifically, the calcination time may be independently selected from 2h, 2.5h, 3h, 3.5h, 4h, or any value therebetween.
In one embodiment, the method for preparing the molecular sieve catalyst at least comprises the following steps:
carrying out alkali treatment and ammonium exchange on an original ZSM-5 molecular sieve to obtain a hierarchical pore ZSM-5 molecular sieve; adding the hierarchical porous ZSM-5 molecular sieve into a solution containing an auxiliary component precursor, and performing impregnation, drying and roasting to obtain the modified molecular sieve catalyst.
Alternatively, the alkali treatment comprises: and adding the ZSM-5 molecular sieve into an alkali solution for treatment, and washing, drying and roasting to obtain a sample I.
Optionally, the concentration of the alkali solution is 0.2-0.6 mol/L.
Alternatively, the concentration of the alkali solution has an upper limit selected from 0.6mol/L, 0.5mol/L, 0.4mol/L and a lower limit selected from 0.2mol/L, 0.3mol/L, 0.4 mol/L.
Preferably, the concentration of the alkali solution is 0.2 mol/L.
Alternatively, the alkaline solution is selected from NaOH solution, KOH solution, Na2CO3At least one of the solutions.
Preferably, the alkali solution is a NaOH solution.
Optionally, the conditions of the treatment include: stirring for 30min at 65-85 ℃.
Alternatively, the upper limit of the temperature of the treatment may be independently selected from 85 deg.C, 80 deg.C, 75 deg.C, and the lower limit may be independently selected from 65 deg.C, 70 deg.C, 75 deg.C.
Preferably, the temperature of the treatment is 65 ℃.
Alternatively, the ammonium exchange comprises: and adding the sample I into an ammonium salt solution for treatment, and washing, drying and roasting to obtain the multistage-pore ZSM-5 molecular sieve.
Optionally, the concentration of the ammonium salt solution is 0.5-1.5 mol/L.
Preferably, the concentration of the ammonium salt solution is 0.8 mol/L.
Alternatively, the ammonium salt solution comprises NH4NO3Solution, NH4At least one of a Cl solution.
Preferably, the ammonium salt solution is NH4NO3And (3) solution.
According to yet another aspect of the present application, there is provided a method for preparing 6-aminocapronitrile, the method comprising:
caprolactam is adopted as a raw material, and the reaction is carried out in the presence of a catalyst to obtain 6-aminocapronitrile;
the catalyst is selected from any molecular sieve catalyst and the molecular sieve catalyst prepared by any method.
Alternatively, the reaction conditions are:
the reaction temperature is 320-420 ℃, and the mass space velocity of caprolactam is 0.5-2 h-1。
Preferably, the reaction temperature is 320-350 ℃, and the mass space velocity of caprolactam is 1.5h-1。
Specifically, the lower limit of the reaction temperature can be independently selected from 320 ℃, 330 ℃, 340 ℃, 350 ℃ and 360 ℃; the upper limit of the reaction temperature can be independently selected from 370 deg.C, 380 deg.C, 390 deg.C, 400 deg.C, 420 deg.C.
Specifically, the lower mass space velocity limit of caprolactam can be independently selected from 0.5h-1、0.7h-1、0.9h-1、1h-1、1.2h-1(ii) a The upper limit of the mass space velocity of caprolactam can be independently selected from 1.4h-1、1.5h-1、1.7h-1、1.9h-1、2h-1。
Alternatively, the reaction pressure herein is atmospheric pressure.
Alternatively, the reaction is carried out in a fixed bed reactor.
In the present application, the "solid-to-liquid ratio" refers to the ratio of solid mass to liquid volume, for example, the solid-to-liquid ratio of the hierarchical pore ZSM-5 molecular sieve to the solution containing the active component precursor refers to the ratio of the mass to volume of the hierarchical pore ZSM-5 molecular sieve to the solution containing the active component precursor.
As used herein, "silicon to aluminum ratio" or "Si/Al" refers to the molar ratio of silicon atoms to aluminum atoms in a molecular sieve.
In this application, "as-received molecular sieve" refers to molecular sieve that has not been chemically treated, such as molecular sieve purchased directly, without chemical treatment such as alkali treatment, ammonium ion exchange, and the like.
In the present application, "normal temperature" means 20 to 35 ℃.
In the present application, "normal pressure" refers to the gas pressure generated in the atmosphere in ordinary life, and usually means about 0.1 Mpa.
The beneficial effects that this application can produce include:
1) the molecular sieve catalyst provided by the application has good catalytic performance for the reaction of preparing 6-aminocapronitrile by ammoniating caprolactam.
2) The preparation method of the molecular sieve catalyst provided by the application is simple and low in cost.
3) The method for preparing 6-aminocapronitrile by ammoniating caprolactam provided by the application has the advantages of high conversion rate and high selectivity, the conversion rate of caprolactam can reach more than 93%, and the conversion rate of 6-aminocapronitrile reaches 96%.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the feedstock and catalyst in the examples of this application were commercially available, wherein the ZSM-5 molecular sieve was obtained from Shanghai Shuxu molecular sieves Co., Ltd and the silica/alumina ratio was 30.9.
Example 1
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
Dissolving 0.43g of diammonium hydrogen phosphate in 30ml of deionized water, adding 5.00g of multi-stage pore ZSM-5 molecular sieve, magnetically stirring for 6 hours at 25 ℃, and then drying for 24 hours in an oven at 60 ℃. Finally, the dried sample is placed in a muffle furnaceRoasting at 550 ℃ for 3h in air atmosphere, and marking as sample No. 1, wherein the content of P is 2%. Taking 1.00g of sample No. 1 which is subjected to tabletting and sieving by a 20-40 mesh sieve, filling the sample No. 1 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And cooling and collecting the product, sampling for gas chromatographic analysis, wherein the conversion rate is 95.1 percent, and the selectivity is 96.1 percent.
Example 2
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
Dissolving 0.66g of diammonium hydrogen phosphate in 30ml of deionized water, adding 5.00g of multi-stage pore ZSM-5 molecular sieve, magnetically stirring for 6 hours at 25 ℃, and then drying for 24 hours in an oven at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 2, wherein the content of P is 3%. Taking 1.00g of sample No. 2 which is subjected to tabletting and sieving by a 20-40 mesh sieve, filling the sample No. 2 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 94.6 percent, and the selectivity is 95.8 percent.
Example 3
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
0.58g of phosphoric acid was dissolved inAdding 5.00g of multi-stage hole ZSM-5 molecular sieve into 30ml of deionized water, magnetically stirring for 6h at 25 ℃, and then drying for 24h in an oven at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 3, wherein the content of P is 3%. Taking 1.00g of sample No. 3 which is subjected to tabletting and sieving by a 20-40 mesh sieve, loading the sample No. 3 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding at a mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 94.4 percent, and the selectivity is 95.6 percent.
Example 4
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange are carried out at 85 ℃, 2 hours are carried out for each time, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, finally roasting is carried out for 3 hours at 550 ℃, and the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
0.98g of phosphoric acid is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at 25 ℃, and then the mixture is placed in an oven to be dried for 24h at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 4, wherein the content of P is 5%. Taking 1.00g of sample No. 4 which is subjected to tabletting and sieving by a 20-40 mesh sieve, filling the sample No. 4 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 93.5 percent, and the selectivity is 95.1 percent.
Example 5
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In solution, 3 times of ion exchange are carried out at 85 ℃ for 2h each time, and centrifugal washing is carried outDrying at 120 ℃ for 12h, and finally roasting at 550 ℃ for 3h to obtain the sample which is the multi-stage pore ZSM-5 molecular sieve.
0.30g of ammonium fluoride is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at the temperature of 25 ℃, and then the mixture is placed in an oven to be dried for 24h at the temperature of 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 5, wherein the content of F is 3%. Taking 1.00g of sample No. 5 which is subjected to tabletting and sieving by a 20-40 mesh sieve, filling the sample No. 5 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 94.0 percent, and the selectivity is 96.2 percent.
Example 6
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. Adding 8.00g of roasted sample into 160ml of 0.8mol/L NH4NO3 solution, carrying out ion exchange for 3 times at 85 ℃, carrying out ion exchange for 2 hours each time, drying at 120 ℃ for 12 hours after centrifugal washing, and finally roasting at 550 ℃ for 3 hours to obtain the sample which is the hierarchical porous ZSM-5 molecular sieve.
0.51g of ammonium fluoride is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at 25 ℃, and then the mixture is placed in an oven to be dried for 24h at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 6, wherein the content of F is 5%. Taking 1.00g of sample No. 6 which is subjected to tabletting and sieving by a 20-40 mesh sieve, loading the sample into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding at a mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 93.7 percent, and the selectivity is 95.6 percent.
Example 7
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the sample after calcination was takenAdding the product into 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
0.63g of magnesium nitrate is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at 25 ℃, and then the mixture is placed in an oven to be dried for 24h at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in the air atmosphere of a muffle furnace, and marking as a sample No. 7, wherein the content of Mg is 2%. Taking 1.00g of a sample No. 7 which is subjected to tabletting and sieving by a 20-40 mesh sieve, putting the sample into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃ for reaction, wherein the feeding mass space velocity is 1.5h < -1 >, cooling and collecting a product, sampling for gas chromatography analysis, and the conversion rate is 93.6 percent and the selectivity is 94.8 percent.
Example 8
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
1.28g of magnesium nitrate is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at 25 ℃, and then the mixture is placed in an oven to be dried for 24h at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in the air atmosphere of a muffle furnace, and marking as a sample No. 8, wherein the content of Mg is 4%. Taking 1.00g of sample No. 8 which is subjected to tabletting and sieving by a 20-40 mesh sieve, filling the sample No. 8 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 93.2 percent, and the selectivity is 94.6 percent.
Example 9
Weighing 10.00g of original ZSM-5 molecular sieve, adding into 300ml of 0.2mol/L NaOH solution, stirring at 65 ℃ for 30min, and centrifugally washingWashing to be neutral, drying the obtained sample in an oven at 120 ℃ for 12h, and roasting the dried sample in a muffle furnace at 550 ℃ for 3h in air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
0.48g of lanthanum nitrate is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at 25 ℃, and then the mixture is placed in an oven to be dried for 24h at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 9, wherein the La content is 3%. Taking 1.00g of sample No. 9 which is subjected to tabletting and sieving by a 20-40 mesh sieve, filling the sample No. 9 into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 92.1 percent, and the selectivity is 94.2 percent.
Example 10
Weighing 10.00g of original ZSM-5 molecular sieve, adding the original ZSM-5 molecular sieve into 300ml of 0.2mol/L NaOH solution, stirring for 30min at 65 ℃, centrifugally washing to be neutral, placing the obtained sample in a drying oven to dry for 12h at 120 ℃, and roasting the dried sample for 3h at 550 ℃ in a muffle furnace under air atmosphere. 8.00g of the calcined sample was added to 160ml of 0.8mol/L NH4NO3In the solution, 3 times of ion exchange is carried out at 85 ℃, each time of ion exchange is 2 hours, after centrifugal washing, drying is carried out for 12 hours at 120 ℃, and finally roasting is carried out for 3 hours at 550 ℃, so that the obtained sample is the multi-stage hole ZSM-5 molecular sieve.
0.82g of lanthanum nitrate is dissolved in 30ml of deionized water, 5.00g of multi-stage pore ZSM-5 molecular sieve is added, magnetic stirring is carried out for 6h at 25 ℃, and then the mixture is placed in an oven to be dried for 24h at 60 ℃. And finally, roasting the dried sample for 3 hours at 550 ℃ in a muffle furnace air atmosphere, and marking as a sample No. 10, wherein the La content is 5%. Taking 1.00g of a sample No. 10 which is subjected to tabletting and sieving by a 20-40 mesh sieve, putting the sample into a fixed bed reactor, pretreating for 60min at 450 ℃ under nitrogen, cooling to 320 ℃, reacting, and feeding with the mass space velocity of 1.5h-1And the product is cooled and collected, and a sample is taken for gas chromatographic analysis, so that the conversion rate is 91.8 percent, and the selectivity is 93.9 percent.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A molecular sieve catalyst, wherein the molecular sieve catalyst comprises a hierarchical pore molecular sieve;
auxiliary component elements are modified on the hierarchical pore molecular sieve;
the auxiliary component element is at least one selected from alkaline earth metal elements, rare earth metal elements and nonmetal elements.
2. The molecular sieve catalyst of claim 1,
the alkaline earth metal element is selected from at least one of Mg and Ca;
the rare earth metal element is selected from at least one of La and Ce;
the non-metallic element is at least one selected from P, F, B.
3. The molecular sieve catalyst according to claim 1, wherein the content of the auxiliary component element in the molecular sieve catalyst is 0.5-10 wt%;
preferably, the hierarchical pore molecular sieve is an MFI-type molecular sieve.
4. The molecular sieve catalyst of claim 1 or 3, wherein the hierarchical pore molecular sieve is a hierarchical pore ZSM-5 molecular sieve;
preferably, the silica-alumina ratio of the original molecular sieve of the multi-stage pore ZSM-5 molecular sieve is 20-50.
5. A process for the preparation of a molecular sieve catalyst according to any of claims 1 to 4, characterized in that the process comprises at least the following steps:
and (3) dipping the hierarchical pore molecular sieve in a solution I containing an auxiliary component element to obtain the molecular sieve catalyst.
6. The method of claim 5, wherein the adjunct component elements are derived from a modifying element precursor;
in the solution I, the concentration of an additive component element precursor is 0.5-10 wt% based on the mass of the additive component elements;
preferably, the precursor of the elements of the auxiliary component is at least one selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, ammonium fluoride, boric acid, magnesium nitrate, magnesium carbonate, magnesium chloride, calcium phosphate, calcium nitrate, lanthanum chloride and cerium nitrate.
7. The method of claim 5, wherein the impregnation conditions are:
the solid-to-liquid ratio of the hierarchical pore molecular sieve to the solution I is 1: 5-1: 10 g/ml.
8. The method of preparing a molecular sieve catalyst according to claim 5, further comprising drying, calcining, the molecular sieve catalyst;
the drying conditions are as follows: the drying temperature is lower than 100 ℃;
the roasting conditions are as follows: the roasting temperature is 500-600 ℃, and the roasting time is 2-4 h.
9. A process for the preparation of 6-aminocapronitrile, characterized in that it comprises:
caprolactam is adopted as a raw material, and the reaction is carried out in the presence of a catalyst to obtain 6-aminocapronitrile;
the catalyst is selected from the group consisting of the molecular sieve catalyst of any one of claims 1 to 4, the molecular sieve catalyst produced by the process of any one of claims 5 to 8.
10. The method of claim 9, wherein the reaction conditions are:
the reaction temperature is 320-420 ℃, and the mass space velocity of caprolactam is 0.5-2 h-1。
CN202011445550.6A 2020-12-08 2020-12-08 Molecular sieve catalyst, and preparation method and application thereof Pending CN114602538A (en)

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GB1121038A (en) * 1965-09-30 1968-07-24 Rhone Poulenc Sa Process for the manufacture of aminonitriles
US3555059A (en) * 1967-07-07 1971-01-12 Bayer Ag Process for the production of omega-aminoalkane nitriles
CH516527A (en) * 1967-07-07 1971-12-15 Bayer Ag Omega-aminoalkane nitriles
US6121481A (en) * 1996-08-03 2000-09-19 Basf Aktiengesellschaft Process for preparing 6-aminocapronitrile
CN103623860A (en) * 2013-12-20 2014-03-12 上海兖矿能源科技研发有限公司 Catalyst for light olefin oligomerization of Fischer-Tropsch synthesis product and preparation method and application thereof
CN110404582A (en) * 2019-08-21 2019-11-05 中触媒新材料股份有限公司 A kind of preparation method of the catalyst for caprolactam ammonification
CN111004148A (en) * 2019-12-30 2020-04-14 河南省化工研究所有限责任公司 Method for preparing 6-aminocapronitrile by gas phase method
CN111495419A (en) * 2019-01-31 2020-08-07 中国科学院宁波材料技术与工程研究所 Metal-loaded hierarchical-pore ZSM-5 molecular sieve, and preparation method and application thereof
CN111992241A (en) * 2020-09-27 2020-11-27 江苏扬农化工集团有限公司 Catalyst for synthesizing hexamethylene diamine key intermediate and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1121038A (en) * 1965-09-30 1968-07-24 Rhone Poulenc Sa Process for the manufacture of aminonitriles
US3555059A (en) * 1967-07-07 1971-01-12 Bayer Ag Process for the production of omega-aminoalkane nitriles
CH516527A (en) * 1967-07-07 1971-12-15 Bayer Ag Omega-aminoalkane nitriles
US6121481A (en) * 1996-08-03 2000-09-19 Basf Aktiengesellschaft Process for preparing 6-aminocapronitrile
CN103623860A (en) * 2013-12-20 2014-03-12 上海兖矿能源科技研发有限公司 Catalyst for light olefin oligomerization of Fischer-Tropsch synthesis product and preparation method and application thereof
CN111495419A (en) * 2019-01-31 2020-08-07 中国科学院宁波材料技术与工程研究所 Metal-loaded hierarchical-pore ZSM-5 molecular sieve, and preparation method and application thereof
CN110404582A (en) * 2019-08-21 2019-11-05 中触媒新材料股份有限公司 A kind of preparation method of the catalyst for caprolactam ammonification
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