CN117401694A - HZSM-23@Al-SBA-15 composite molecular sieve and preparation method and application thereof - Google Patents

HZSM-23@Al-SBA-15 composite molecular sieve and preparation method and application thereof Download PDF

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CN117401694A
CN117401694A CN202210777977.9A CN202210777977A CN117401694A CN 117401694 A CN117401694 A CN 117401694A CN 202210777977 A CN202210777977 A CN 202210777977A CN 117401694 A CN117401694 A CN 117401694A
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molecular sieve
hzsm
hours
sba
composite molecular
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陈玉晶
樊宏飞
于政敏
孙晓艳
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7046—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
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    • C01P2006/14—Pore volume

Abstract

The invention discloses an HZSM-23@Al-SBA-15 composite molecular sieve and a preparation method and application thereof. The composite molecular sieve takes an HZSM-23 molecular sieve as a core and an Al-SBA-15 molecular sieve as a shell, and the core crystallinity of the HZSM-23@Al-SBA-15 composite molecular sieve is 95-110%, preferably 97-108%. The preparation method of the composite molecular sieve comprises the preparation of HZSM-23 molecular sieve cores. The HZSM-23@Al-SBA-15 composite molecular sieve synthesized by the method has high crystallinity and good hydrothermal stability.

Description

HZSM-23@Al-SBA-15 composite molecular sieve and preparation method and application thereof
Technical Field
The invention relates to an HZSM-23@Al-SBA-15 composite molecular sieve and a preparation method and application thereof, in particular to an HZSM-23@Al-SBA-15 core-shell composite molecular sieve and a preparation method and application thereof.
Background
The ZSM-23 molecular sieve is a molecular sieve material with high silicon-aluminum ratio, and has a one-dimensional teardrop-shaped pore canal with a ten-membered ring structure. By virtue of the unique pore channel structure, the ZSM-23 molecular sieve is widely applied in the fields of separation adsorption and catalysis, and plays an irreplaceable role. However, the ZSM-23 molecular sieve prepared conventionally has higher strong acid content, and side reaction hydrocracking is easy to occur in hydroisomerization reaction. Therefore, in order to further expand the application range, it is necessary to increase the weak acid content in the ZSM-23 molecular sieve and introduce a mesoporous or macroporous structure into the microporous ZSM-23 molecular sieve.
In patent CN107235497, starch is added to regulate the synthesis path of ZSM-23 molecular sieve, and the subsequent calcination is carried out to obtain the ZSM-23 molecular sieve with mesoporous-microporous hierarchical composite structure. The method has simple process and lower cost, but the mesoporous structure is obtained by removing the pore-expanding agent, so that the crystallinity is low and the hydrothermal stability is poor.
CN105540607 discloses a preparation method of a multistage pore composite molecular sieve ZSM-22/ZSM-23, but both the ZSM-22 and the ZSM-23 molecular sieves are microporous structures, so that the mesoporous structures involved in the method are mainly stacking holes, and the regularity and stability are poor.
CN106513035 discloses a preparation method of a composite molecular sieve with a ZSM-23 molecular sieve as a core and SBA-15 as a shell. Because shell SBA-15 is synthesized under the strong acid condition, the crystallinity of ZSM-23 molecular sieve cores is further influenced, and the stability is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an HZSM-23@Al-SBA-15 composite molecular sieve as well as a preparation method and application thereof. The HZSM-23@Al-SBA-15 composite molecular sieve synthesized by the method has high crystallinity and good hydrothermal stability.
The first aspect of the invention provides a HZSM-23@Al-SBA-15 composite molecular sieve, wherein the composite molecular sieve takes the HZSM-23 molecular sieve as a core and takes the Al-SBA-15 molecular sieve as a shell, the core crystallinity of the HZSM-23@Al-SBA-15 composite molecular sieve is 95-110%, preferably 97-108%, and the core crystallinity of the composite molecular sieve is 96-108%, preferably 98-105% after being subjected to steam water heat treatment at 600 ℃ for 2 hours.
The mass ratio of the core shell to the shell in the composite molecular sieve is 1:1-1:9, preferably 1:2-1:4; the total acid amount of the composite molecular sieve is 0.07-0.35 mmol/g, preferably 0.09-0.32 mmol/g; wherein the acid content is 60-95%, preferably 65-90% at below 350 ℃; the Al-SBA-15 molecular sieve is characterized in that the mass content of Al calculated by alumina is 2.45-10.05%, preferably 2.83-8.50% based on the weight of the Al-SBA-15 molecular sieve.
The specific surface area of the composite molecular sieve is 310-470 m 2 Per gram, the pore volume is 0.31-0.68 cm 3 Preferably, the specific surface area of the composite molecular sieve is 330-460 m 2 Per gram, the pore volume is 0.32-0.65 cm 3 /g。
SiO of the composite molecular sieve of the invention 2 /Al 2 O 3 The molar ratio is 40 to 120, preferably 50 to 110.
The second aspect of the invention provides a preparation method of an HZSM-23@Al-SBA-15 composite molecular sieve, which comprises the following steps:
(1) Preparing a nuclear molecular sieve HZSM-23 molecular sieve:
(1) preparing a mixed solution A containing a first template agent and amorphous silica-alumina and/or an amorphous silica-alumina precursor;
(2) adding an alkali source and a silicon source into the mixed solution in the step (1);
(3) crystallizing, washing, drying, roasting and exchanging ammonium of the material obtained in the step (2) to obtain the HZSM-23 molecular sieve;
(2) Preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) Adding a silicon source into an acid solution, stirring for a period of time, and standing and aging to obtain a silicon source hydrolysate;
(2) and (3) uniformly mixing the hydrolysate obtained in the step (2) and the step (1) with the HZSM-23 molecular sieve obtained in the step (1) and the step (3), a second template agent and aluminum isopropoxide to obtain a mixed slurry B, and washing, drying and roasting after crystallization to obtain the HZSM-23@Al-SBA-15 composite molecular sieve.
In the step (1) (1) of the method, the first template agent is one or more of isopropylamine, pyrrolidine, N-dimethylformamide and dimethylamine.
In the method step (1) (1), silicon (in terms of silicon oxide) in the mixed solution A is as follows: the molar ratio of aluminum (calculated as aluminum oxide) is 1 (0.10-0.85), preferably 1 (0.20-0.79), and more preferably 1 (0.24-0.78); the aluminum (in terms of alumina): the molar ratio of the template agent is 1 (10-100), preferably 1 (15-85), and more preferably 1 (20-65).
In the method step (1) (1), preparing an amorphous silicon aluminum precursor by a carbonization method, and then adding a first template agent into the amorphous silicon aluminum precursor to obtain the mixed solution.
In the method step (1) (1), the mixed solution A is stirred for 0.2 to 2 hours at the temperature of 10 to 35 ℃.
In the steps (1) and (2) of the method, based on aluminum (calculated as aluminum oxide) in the mixed solution A of the step (1) and (1), the mixed solution A is prepared according to SiO 2 :Al 2 O 3 :R 2 O (alkali source, wherein R is alkali metal, such as sodium, potassium) H 2 O=1 (0.0025-0.025): 0.015-0.08): 30-80, template agent (SDA)/SiO 2 Total feed mole ratio of =0.10-1.8, preferably SiO 2 /Al 2 O 3 50-200, H 2 O/SiO 2 30-60, R 2 O/SiO 2 And (3) adding an alkali source and a supplementary silicon source into the materials in the step (1) (1) at a ratio of 0.025-0.06.
In the step (1) and the step (2), the silicon source is one or more of fumed silica, silica sol and water glass, and the alkali source is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
In the method steps (1) and (3), the crystallization conditions are as follows: crystallizing at 150-200deg.C for 8-72 hr; the drying temperature is 80-120 ℃ and the drying time is 4-8 hours; the roasting temperature is 530-570 ℃ and the roasting time is 3-6 hours.
In the above method steps (1) and (3), the ammonium exchange is carried out by a conventional method, such as one or more ammonium exchanges, na in ZSM-23 molecular sieve after ammonium exchange 2 The O content is lower than 0.2%; then washing, drying and roasting can be carried out,wherein the drying temperature is 80-120 ℃ and the drying time is 4-8 hours; the roasting temperature is 530-570 ℃ and the roasting time is 3-6 hours.
In the preparation method of the nuclear molecular sieve HZSM-23, all aluminum sources required by synthesis are added in the preparation process of the amorphous silica-alumina precursor, so that the generation of a primary structural unit of the molecular sieve is promoted; when the template agent is added into the amorphous silicon aluminum precursor, the template agent is preferentially chelated with Al species and then is adsorbed on the surface of a formed primary structural unit, so that the pre-assembly of the molecular sieve structure is realized, and a large number of crystal nuclei are generated; meanwhile, the binding site of Al atoms can be better controlled, the later crystallization is facilitated, the acid content below 350 ℃ is increased, after the supplementary silicon source is added to form final gel, a large number of crystal nuclei are rapidly grown into the ZSM-23 molecular sieve with high crystallinity through static crystallization.
In the method step (2) (1), the silicon source is one or two of ethyl orthosilicate and methyl orthosilicate. The acid is one or more of hydrochloric acid, nitric acid and sulfuric acid. The pH of the acid solution is 1.0-4.0.
In the method step (2) (1), the stirring time is 4-10 hours, and the temperature is 20-45 ℃; and standing and aging for 8-48 hours.
In the method step (2) (2), the second template agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123); preferably, aluminum isopropoxide and the template agent P123 are respectively dissolved in an acid solution and then mixed with other raw materials. The acid is one or more of hydrochloric acid, nitric acid and sulfuric acid. The molar concentration of hydrogen ions in the acid solution is 0.1-0.7 mol/L, preferably 0.2-0.6 mol/L.
In the method steps (2) and (2), adding P123 and HZSM-23 in a mass ratio of 0.15-0.55, preferably 0.18-0.50; the mass ratio of the added silicon source to HZSM-23 is 1-4, preferably 1.2-3; the mass ratio of the added deionized water to HZSM-23 is 18-50, preferably 20-40; siO in silicon source 2 With Al in aluminum isopropoxide 2 O 3 The molar ratio is 15 to 120, preferably 20 to 100.
In the method steps (2) and (2), the mixed solution B is continuously stirred for 6-8 hours at 15-30 ℃ before crystallization.
In the method steps (2) and (2), the crystallization temperature of the mixed solution B is 80-120 ℃ and the crystallization time is 16-40 hours.
In the step (2) and (2) of the method, the drying temperature is 80-120 ℃ and the time is 4-8 hours; the roasting temperature is 530-570 ℃ and the roasting time is 3-6 hours.
The HZSM-23@Al-SBA-15 composite molecular sieve is suitable for hydroisomerization reaction of raw materials rich in naphthenes, wherein the content of the naphthenes is 30-60%; the reaction temperature is 250-350 ℃ and the liquid space velocity is 0.5-1.5 h -1 The hydrogen-oil ratio is 600-1000, and the reaction hydrogen pressure is 3.5-5.0 Mpa.
Compared with the prior art, the HZSM-23@Al-SBA-15 composite molecular sieve and the preparation method and application thereof have the following advantages:
(1) The inventor surprisingly found that the HZSM-23 molecular sieve prepared by the method of the invention is taken as the core of the composite molecular sieve, and the synthesized core of the HZSM-23@Al-SBA-15 composite molecular sieve still maintains higher crystallinity in the process of synthesizing the shell Al-SBA-15 molecular sieve under the strong acid condition, thus greatly improving the hydrothermal stability of the HZSM-23@Al-SBA-15 composite molecular sieve;
(2) In the HZSM-23@Al-SBA-15 composite molecular sieve, the acid content is higher below 350 ℃, so that the isomerization reaction of a primary cracking product of the Al-SBA-15 molecular sieve is facilitated, and the secondary cracking and carbon deposition are effectively reduced.
Drawings
FIG. 1 is a wide-angle XRD spectrum of the synthesized product of example 1 of the present invention, namely, the XRD spectrum of a nuclear HZSM-23 molecular sieve.
FIG. 2 is a small angle XRD spectrum of the synthesized product of example 1 of the present invention, i.e., XRD spectrum of shell Al-SBA-15 molecular sieve.
Detailed Description
The preparation process of the non-limiting amorphous silicon aluminum precursor in the embodiment of the invention comprises the following steps: preparing an aluminum source (preferably sodium aluminate) solution and a silicon-containing compound solution respectively; mixing the aluminum source solution with part of the silicon compound solution, and introducing CO 2 The gas is glued, when the CO is introduced 2 When the volume of the gas is 50-100% of the total volume of the gas,preferably 70-90%, adding the rest silicon compound solution, and introducing the rest CO 2 And (3) preparing the amorphous silicon aluminum precursor by gas and optionally aging.
In the preparation process of the amorphous silicon aluminum precursor, the residual silicon compound-containing solution accounts for 5-85wt% of the total added silicon compound-containing solution calculated as silicon dioxide, and is preferably 30-70wt%.
In the preparation process of the amorphous silicon aluminum precursor, the reaction temperature of the gel forming is 10-40 ℃, preferably 15-35 ℃, and the pH value after the gel forming is controlled to be 9-12.
In the preparation process of the amorphous silicon aluminum precursor, the silicon-containing compound solution is water glass and/or sodium silicate solution.
In the preparation process of the amorphous silicon aluminum precursor, A1 is adopted 2 O 3 The concentration of the aluminum source solution is 15-60gAl by mass 2 O 3 L, siO 2 The concentration of the silicon-containing compound solution is 40-260gSiO by mass 2 L, said CO 2 The concentration of the gas is 30-60v%.
In the preparation process of the amorphous silicon aluminum precursor, the aging time is 5-60 minutes, and the aging temperature is 10-40 ℃.
In the present invention, the relative crystallinity was measured by XRD, and the crystallinity of the HZSM-23 molecular sieve prepared in step (1) of example 1 was 100% based on the result. In the XRD spectrum of the composite molecular sieve, the crystallinity is calculated according to the peak of the HZSM-23 molecular sieve.
The specific surface area and pore volume were measured by ASAP 2405 physical adsorption using low temperature liquid nitrogen physical adsorption method from Micromeritics company of America.
Total acid amount and acid content below 350 ℃ from NH 3 Programmed temperature desorption (NH) 3 TPD), wherein the total acid amount is the acid amount corresponding to the desorption temperature of 120-500 ℃.
In order to better illustrate the present invention, the following is further described with reference to examples and comparative examples. However, the scope of the present invention is not limited to these examples, and the following examples and comparative examples are given in mass% unless otherwise specified.
Example 1
(1) Preparation of nuclear molecular sieve HZSM-23
The concentration of the mixture is 40gAl 2 O 3 Collecting SiO-containing working solution of sodium aluminate 2 28 Sodium silicate solution of weight percent, and then diluted to a concentration of 100gSiO 2 L sodium silicate working solution. Placing 150 mL sodium aluminate working solution into a gelling tank, adding 50mL sodium silicate working solution, controlling the reaction temperature to 20 ℃, and introducing CO with the concentration of 50v percent 2 Stopping introducing CO when pH value reaches 10.0 2 Then 90mL of sodium silicate working solution is added, and the residual CO is introduced 2 And (3) stabilizing the gas, and aging at 25 ℃ for 30 minutes to obtain the amorphous silicon aluminum precursor. According to SiO 2 :Al 2 O 3 :Na 2 O:H 2 O=1:0.02:0.04:45、IPA/SiO 2 Adding isopropylamine into the obtained amorphous silicon aluminum precursor according to the total feeding molar ratio of IPA (template isopropylamine) of 0.7, and stirring for 0.8 hours at 15 ℃ to obtain a mixed solution containing the amorphous silicon aluminum precursor and the template; and then adding a mixture consisting of sodium hydroxide, silica sol and water into the mixture, and uniformly stirring to obtain the silica-alumina gel. Pouring the gel into a stainless steel reaction kettle, and carrying out static crystallization for 20 hours at 160 ℃. After crystallization, filtering, washing to neutrality, and drying at 120 deg.c to obtain molecular sieve product NaZSM-23-1. A certain amount of NaZSM-23-1 molecular sieve sample is weighed and placed in an ammonium nitrate solution with the concentration of 2 mol/L, the liquid-solid ratio is 10, and the mixture is filtered and washed after being continuously stirred for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain HZSM-23-1, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
(2) Preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) 15.0. 15.0 g ethyl orthosilicate is added to 50.0 g of HCl solution with pH=2.0, and the mixture is stirred at 40 ℃ for 4 hours and then left to stand for 36 hours, thus obtaining a silicon source hydrolysate.
(2) 3.0g of P123 are dissolved in 250mL of 0.30mol/L hydrochloric acid solution; adding 2.55g of aluminum isopropoxide, 10 g of HZSM-23-1 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 4 hours at room temperature; transferring the obtained mixed solution into a hydrothermal reaction kettle, crystallizing for 24 hours at 100 ℃, filtering, washing to neutrality, and drying at 100 ℃, wherein the specific properties of the molecular sieve product Z-1 are shown in table 1; fig. 1 is a wide-angle XRD spectrum of a core-shell type composite molecular sieve, and fig. 2 is a small-angle XRD spectrum of a core-shell type composite molecular sieve.
Example 2
(1) Preparation of nuclear molecular sieve HZSM-23
The concentration of the mixture is 40gAl 2 O 3 Collecting SiO-containing working solution of sodium aluminate 2 28wt% sodium silicate solution, and diluted to a concentration of 150gSiO 2 L sodium silicate working solution. 200mL of sodium aluminate working solution is taken and placed in a gel forming tank, 40mL of sodium silicate working solution is added, the reaction temperature is controlled at 25 ℃, and CO with the concentration of 50v% is introduced 2 Stopping introducing CO when pH value reaches 10.5 2 Then 40mL of sodium silicate working solution is added, and the residual CO is introduced 2 And (3) stabilizing the gas, and aging for 20 minutes at 20 ℃ to obtain the amorphous silicon aluminum precursor. According to SiO 2 :Al 2 O 3 :Na 2 O:H 2 O=1:0.005:0.04:60、IPA/SiO 2 Adding isopropylamine into the obtained amorphous silicon aluminum precursor according to the total feeding molar ratio of 0.15, and stirring for 1 hour at 20 ℃ to obtain a mixed solution containing the amorphous silicon aluminum precursor and a template agent; and then adding a mixture consisting of sodium hydroxide, silica sol and water into the mixture, and uniformly stirring to obtain the silica-alumina gel. Pouring the gel into a stainless steel reaction kettle, and carrying out static crystallization for 18 hours at 180 ℃. After crystallization, filtering, washing to neutrality, and drying at 120 ℃ to obtain a molecular sieve product NaZSM-23-2; a certain amount of NaZSM-23-2 molecular sieve sample is weighed and placed in an ammonium nitrate solution with the concentration of 2 mol/L, the liquid-solid ratio is 10, and the mixture is filtered and washed after being continuously stirred for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, and placing the sample in an oven at 80-100 ℃ to dry for 8 hours and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain HZSM-23-2, the relative crystallinity of which is measured; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
(2) Preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) 15.0. 15.0 g ethyl orthosilicate is added to 50.0 g of HCl solution with pH=2.0, and the mixture is stirred for 10 hours at 20 ℃ and then left to stand for 24 hours, so that a silicon source hydrolysate is obtained.
(2) 3.5 g of P123 are dissolved in 250mL of 0.40 mol/L hydrochloric acid solution; adding 2.55g of aluminum isopropoxide, 17 g of HZSM-23-2 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 4 hours at room temperature; transferring the obtained mixed solution into a hydrothermal reaction kettle, crystallizing for 24 hours at 100 ℃, filtering, washing to neutrality, and drying at 100 ℃, wherein the specific properties of the molecular sieve product Z-2 are shown in table 1; . Its wide angle XRD pattern is similar to figure 1 and its small angle XRD pattern is similar to figure 2.
Example 3
(1) Preparation of nuclear molecular sieve HZSM-23
The concentration of the mixture is 50gAl 2 O 3 Collecting SiO-containing working solution of sodium aluminate 2 28wt% sodium silicate solution, and diluted to a concentration of 100gSiO 2 L sodium silicate working solution. 200mL of sodium aluminate working solution is taken and placed in a gel forming tank, then 60mL of sodium silicate working solution is added, the reaction temperature is controlled at 30 ℃, and CO with the concentration of 50v% is introduced 2 Stopping introducing CO when pH value reaches 10.0 2 Then 40mL of sodium silicate working solution is added, and the residual CO is introduced 2 And (3) stabilizing the gas, and aging for 15 minutes at 35 ℃ to obtain the amorphous silicon aluminum precursor. According to SiO 2 :Al 2 O 3 :Na 2 O:H 2 O=1:0.01:0.04:30、IPA/SiO 2 Adding isopropylamine into the obtained amorphous silicon aluminum precursor in a total feeding molar ratio of 0.4, and stirring for 0.5 hours at 25 ℃ to obtain a mixed solution containing the amorphous silicon aluminum precursor and a template agent; and then adding a mixture consisting of sodium hydroxide, silica sol and water into the mixture, and uniformly stirring to obtain the silica-alumina gel. Pouring the gel into a stainless steel reaction kettle, and carrying out static crystallization for 18 hours at 180 ℃. After crystallization is finished, filtering and washingDrying at 120 ℃ after the reaction is neutral to obtain a molecular sieve product NaZSM-23-3; a certain amount of NaZSM-23-3 molecular sieve sample is weighed and placed in an ammonium nitrate solution with the concentration of 2 mol/L, the liquid-solid ratio is 10, and the mixture is filtered and washed after being continuously stirred for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain HZSM-23-3, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
(2) Preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) 15.0. 15.0 g ethyl orthosilicate is added to 50.0 g of HCl solution with pH=3.0, and the mixture is stirred at 30 ℃ for 8 hours and then left to stand for 36 hours, thus obtaining a silicon source hydrolysate.
(2) 3.93 g P123 are dissolved in 250mL of 0.50mol/L hydrochloric acid solution; adding 3.41g of aluminum isopropoxide, 10 g of HZSM-23-3 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 4 hours at room temperature; the obtained mixture was transferred to a hydrothermal reaction vessel, crystallized at 100℃for 24 hours, filtered, washed to neutrality, and dried at 100℃to give a molecular sieve product Z-3, the specific properties of which are shown in Table 1. Its wide angle XRD pattern is similar to figure 1 and its small angle XRD pattern is similar to figure 2.
Example 4
(1) Preparation of nuclear molecular sieve HZSM-23
The concentration of the mixture is 20 gAl 2 O 3 Collecting SiO-containing working solution of sodium aluminate 2 28 A sodium silicate solution of wt% was diluted again to a concentration of 150g SiO 2 L sodium silicate working solution. Placing 300 mL sodium aluminate working solution into a gel forming tank, adding 20mL sodium silicate working solution, controlling the reaction temperature to be 30 ℃, and introducing CO with the concentration of 50v% 2 Stopping introducing CO when pH value reaches 11.0 2 Then 20mL of sodium silicate working solution is added, and the residual CO is introduced 2 And (3) stabilizing the gas, and aging at 20 ℃ for 30 minutes to obtain the amorphous silicon aluminum precursor. According to SiO 2 :Al 2 O 3 :Na 2 O:H 2 O=1:0.01:0.04:45、IPA/SiO 2 Total feed mole ratio of =0.3, obtained aboveAdding isopropylamine into the amorphous silicon-aluminum precursor, and stirring for 1 hour at 15 ℃ to obtain a mixed solution containing the amorphous silicon-aluminum precursor and a template agent; and then adding a mixture consisting of sodium hydroxide, silica sol and water into the mixture, and uniformly stirring to obtain the silica-alumina gel. Pouring the gel into a stainless steel reaction kettle, and carrying out static crystallization for 18 hours at 180 ℃. After crystallization, filtering, washing to neutrality, and drying at 120 ℃ to obtain a molecular sieve product NaZSM-23-4; a certain amount of NaZSM-23-4 molecular sieve sample is weighed and placed in an ammonium nitrate solution with the concentration of 2 mol/L, the liquid-solid ratio is 10, and the mixture is filtered and washed after being continuously stirred for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain HZSM-23-4, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
(2) Preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) 15.0. 15.0 g ethyl orthosilicate is added to 80.0 g of HCl solution with pH=1.0, and the mixture is stirred for 6 hours at 35 ℃ and then left to stand for 24 hours, so that a silicon source hydrolysate is obtained.
(2) 3.0g P123 are dissolved in 200mL of 0.50mol/L hydrochloric acid solution; adding 1.75 g g of aluminum isopropoxide, 10 g of HZSM-23-3 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 4 hours at room temperature; transferring the obtained mixed solution into a hydrothermal reaction kettle, crystallizing for 24 hours at 100 ℃, filtering, washing to neutrality, and drying at 100 ℃ to obtain a molecular sieve product Z-4, wherein the specific properties are shown in table 1; its wide angle XRD pattern is similar to figure 1 and its small angle XRD pattern is similar to figure 2.
Example 5
(1) Preparation of nuclear molecular sieve HZSM-23
The concentration of the mixture is 40gAl 2 O 3 Collecting SiO-containing working solution of sodium aluminate 2 28 A sodium silicate solution of wt% was diluted again to a concentration of 50g SiO 2 L sodium silicate working solution. Placing 150 mL sodium aluminate working solution into a gel forming tank, adding 140 mL sodium silicate working solution, controlling the reaction temperature to 25 ℃, and introducing the concentration to be50v% CO 2 Stopping introducing CO when pH value reaches 10.0 2 Adding 140 mL sodium silicate working solution, and introducing residual CO 2 And (3) stabilizing the gas, and aging for 20 minutes at 25 ℃ to obtain the amorphous silicon aluminum precursor. According to SiO 2 :Al 2 O 3 :Na 2 O:H 2 O=1:0.01:0.04:45、IPA/SiO 2 Adding isopropylamine into the obtained amorphous silicon aluminum precursor according to the total feeding molar ratio of 0.4, and stirring for 1 hour at 15 ℃ to obtain a mixed solution containing the amorphous silicon aluminum precursor and a template agent; and then adding a mixture consisting of sodium hydroxide, fumed silica and water into the mixture, and uniformly stirring the mixture to obtain the silica-alumina gel. Pouring the gel into a stainless steel reaction kettle, and carrying out static crystallization for 18 hours at 180 ℃. After crystallization, filtering, washing to neutrality, and drying at 120 ℃ to obtain a molecular sieve product NaZSM-23-5; a certain amount of NaZSM-23-5 molecular sieve sample is weighed and placed in an ammonium nitrate solution with the concentration of 2 mol/L, the liquid-solid ratio is 10, and the mixture is filtered and washed after being continuously stirred for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain HZSM-23-5, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
(2) Preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) The silicon source hydrolysate was obtained by adding 23.31. 23.31 g tetraethoxysilane to 100.0 g of an HCl solution having ph=2.0, stirring at 40 ℃ for 4 hours, and then standing for 24 hours.
(2) 4.2 g of P123 are dissolved in 300 mL of 0.30mol/L hydrochloric acid solution; adding 0.92 g aluminum isopropoxide, 10 g HZSM-23-3 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 6 hours at room temperature; transferring the obtained mixed solution into a hydrothermal reaction kettle, crystallizing for 24 hours at 100 ℃, filtering, washing to neutrality, and drying at 100 ℃ to obtain a molecular sieve product Z-5, wherein the specific properties are shown in table 1; its wide angle XRD pattern is similar to figure 1 and its small angle XRD pattern is similar to figure 2.
Comparative example 1: (refer to CN 106513035A)
Will be 1.38 gAl 2 SO 4 1.36 g NaOH was dissolved in 12.8. 12.8 g deionized water, and after stirring thoroughly with 7.28. 7.28 g g pyrrolidine, 48.29 g silica sol (40 wt% SiO) was added 2 ) Stirring until gel is formed, wherein the feeding mole ratio is SiO 2 :0.0125Al 2 O 3 :0.05Na 2 O0.32 pyrrolidine 10H 2 O; transferring the formed gel into a high-pressure reaction kettle, heating and stirring, crystallizing at 180 ℃ for 72 hours, washing, filtering, and drying at 120 ℃ to obtain a molecular sieve product DNa-ZSM-23-1; weighing a certain amount of DNa-ZSM-23-1 molecular sieve sample, placing the sample in an ammonium nitrate solution with the concentration of 2 mol/L, wherein the liquid-solid ratio is 10, and filtering and washing after continuously stirring for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain DHZSM-23-1, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
6 g of P123 was weighed out and dissolved in 144 g deionized water, and 6.24 g silica sol (40 wt% SiO) was added in sequence 2 ) Mixing 0.31 g g aluminum sulfate and 10 g DHZSM-23-1 molecular sieve powder uniformly, adding a certain amount of HCl to regulate the pH value of the solution to 2-4, continuously stirring for 2 hours, transferring the obtained mixed slurry into a hydrothermal reaction kettle, and crystallizing at 100 ℃ for 24 hours; the reaction product is filtered, washed to be neutral and dried at 100 ℃ to obtain a molecular sieve product DZ-1, and the specific properties are shown in table 1.
Comparative example 2:
(refer to CN102992346A for preparing the Nuclear ZSM-23 molecular sieves)
0.092 g aluminum sulfate was dissolved in 8.12 gH 2 In O, 0.38 g of NaOH was added thereto, and after dissolution, 2.53. 2.53 g silica sol (40 wt% SiO) 2 ) Stirring was continued until the solution became homogeneous, and 10% ZSM-23 molecular sieve was added as seed crystals (seed amount to account for SiO charged 2 Calculated as mass percent). The reaction raw materials (SiO ratio) 2 :0.008319Al 2 O 3 :0.27Na 2 O:35H 2 O) is transferred into a hydrothermal reaction kettle and dynamically crystallized at 160 DEG CAfter 10 hours, the product is filtered, dried to obtain a molecular sieve product DNa-ZSM-23-2; weighing a certain amount of DNa-ZSM-23-2 molecular sieve sample, placing the sample in an ammonium nitrate solution with the concentration of 2 mol/L, wherein the liquid-solid ratio is 10, and filtering and washing after continuously stirring for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain DHZSM-23-2, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
15.0. 15.0 g ethyl orthosilicate is added to 50.0 g of HCl solution with pH=2.0, and the mixture is stirred at room temperature for 4 hours and then left to stand for 36 hours, thereby obtaining a silicon source hydrolysate.
3.0gP123 was dissolved in 250mL of 0.30mol/L hydrochloric acid solution; adding 2.55g aluminum isopropoxide, 10 g DHZSM-23-3 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 4 hours at room temperature; transferring the obtained mixed solution into a hydrothermal reaction kettle, crystallizing at 100 ℃ for 24 hours, filtering, washing to neutrality, and drying at 100 ℃ to obtain a molecular sieve product DZ-3, wherein the specific properties are shown in table 1.
Comparative example 3:
mixing water glass, aluminum sulfate, isopropyl amine (IPA), sodium hydroxide and water to obtain SiO in the silicon source 2 Al in aluminium source 2 O 3 :NaOH:IPA:H 2 The gel with O=1:0.01:0.08:1.0:50 is heated for 72 hours at 180 ℃, washed, filtered and dried at 120 ℃ to obtain a molecular sieve product DNa-ZSM-23-2; weighing a certain amount of DNa-ZSM-23-2 molecular sieve sample, placing the sample in an ammonium nitrate solution with the concentration of 2 mol/L, wherein the liquid-solid ratio is 10, and filtering and washing after continuously stirring for 1 hour in a water bath with the temperature of 80-90 ℃. Repeating the operation process twice, placing the sample in an oven at 80-100 ℃ for drying for 8 hours, and roasting for 3 hours in an air atmosphere at 550 ℃ to obtain DHZSM-23-3, and measuring the relative crystallinity; after 2 hours of heat treatment with 600 ℃ water vapor, the hydrothermal stability was measured, and the specific properties are shown in table 1.
15.0. 15.0 g ethyl orthosilicate is added to 50.0 g of HCl solution with pH=2.0, and the mixture is stirred at room temperature for 4 hours and then left to stand for 36 hours, thereby obtaining a silicon source hydrolysate.
3.0gP123 was dissolved in 250mL of 0.30mol/L hydrochloric acid solution; adding 2.55g aluminum isopropoxide, 10 g DHZSM-23-3 and the silicon source hydrolysate obtained in the step (2) and (1) successively, and stirring for 4 hours at room temperature; transferring the obtained mixed solution into a hydrothermal reaction kettle, crystallizing at 100 ℃ for 24 hours, filtering, washing to neutrality, and drying at 100 ℃ to obtain a molecular sieve product DZ-3, wherein the specific properties are shown in table 1.
The ZSM-23 molecular sieve samples were evaluated for performance on a fixed bed microreactor. The hydrogenation reaction of ethylcyclohexane is taken as a model reaction, the reaction raw materials are 90wt percent decalin and 10wt percent ethylcyclohexane, the reaction temperature is 300 ℃, and the liquid space velocity is 1.0 h -1 The hydrogen-oil ratio is 800, and the reaction hydrogen pressure is 4.0 Mpa. The samples of comparative example 1, comparative example 2 and example 1 and example 5 are taken as carriers, and the noble metal Pt is loaded to prepare the catalyst, and the catalytic results are as follows:
example 1:
ethyl cyclohexane conversion: 91%; c (C) 8 H 18 Yield: 74%; c (C) 8 H 18 Degree of isomerization: 98 percent; c (C) 8 H 18 Ratio of multi-branched to mono-branched components in the isomerised product: 2.2.
example 5:
ethyl cyclohexane conversion: 92%; c (C) 8 H 18 Yield: 72%; c (C) 8 H 18 Degree of isomerization: 97%; c (C) 8 H 18 Ratio of multi-branched to mono-branched components in the isomerised product: 2.4.
comparative example 1:
ethyl cyclohexane conversion: 81% of a glass fiber; c (C) 8 H 18 Yield: 51%; c (C) 8 H 18 Degree of isomerization: 66%; c (C) 8 H 18 Ratio of multi-branched to mono-branched components in the isomerised product: 0.7.
comparative example 2:
ethyl cyclohexane conversion: 78%; c (C) 8 H 18 Yield: 46%; c (C) 8 H 18 Degree of isomerization: 71%; c (C) 8 H 18 Ratio of multi-branched to mono-branched components in the isomerised product:1.0。
TABLE 1

Claims (23)

1. The HZSM-23@Al-SBA-15 composite molecular sieve is characterized in that: the composite molecular sieve takes an HZSM-23 molecular sieve as a core and an Al-SBA-15 molecular sieve as a shell, the core crystallinity of the HZSM-23@Al-SBA-15 composite molecular sieve is 95-110%, preferably 97-108%, and after being subjected to steam heat treatment at 600 ℃ for 2 hours, the core crystallinity of the composite molecular sieve is 96-108%, preferably 98-105%.
2. The molecular sieve of claim 1, wherein: the mass ratio of the core shell in the composite molecular sieve is 1:1-1:9; the total acid amount of the composite molecular sieve is 0.07-0.35 mmol/g; wherein the acid content is 60-95% below 350 ℃; the Al-SBA-15 molecular sieve is characterized in that the weight of the Al-SBA-15 molecular sieve is taken as a reference, and the mass content of Al calculated by alumina is 2.45-10.05%.
3. The molecular sieve of claim 2, wherein: the mass ratio of the core shell in the composite molecular sieve is 1:2-1:4; the total acid amount of the composite molecular sieve is 0.09-0.32 mmol/g; wherein the acid content is 65-90% below 350 ℃; the Al-SBA-15 molecular sieve is characterized in that the weight of the Al-SBA-15 molecular sieve is taken as a reference, and the mass content of Al calculated by alumina is 2.83-8.50%.
4. The molecular sieve of claim 1, wherein: the specific surface area of the composite molecular sieve is 310-470 m 2 Per gram, the pore volume is 0.31-0.68 cm 3 Preferably, the specific surface area of the composite molecular sieve is 330-460 m 2 Per gram, the pore volume is 0.32-0.65 cm 3 /g。
5. The molecular sieve of claim 1, wherein: siO of the composite molecular sieve 2 /Al 2 O 3 Molar (mol)The ratio is 40 to 120, preferably 50 to 110.
6. A process for preparing a molecular sieve according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
preparing a nuclear molecular sieve HZSM-23 molecular sieve:
(1) preparing a mixed solution A containing a first template agent and amorphous silica-alumina and/or an amorphous silica-alumina precursor;
(2) adding an alkali source and a silicon source into the mixed solution in the step (1);
(3) crystallizing, washing, drying, roasting and exchanging ammonium of the material obtained in the step (2) to obtain the HZSM-23 molecular sieve;
preparation of HZSM-23@Al-SBA-15 composite molecular sieve
(1) Adding a silicon source into an acid solution, stirring for a period of time, and standing and aging to obtain a silicon source hydrolysate;
(2) and (3) uniformly mixing the hydrolysate obtained in the step (2) and the step (1) with the HZSM-23 molecular sieve obtained in the step (1) and the step (3), a second template agent and aluminum isopropoxide to obtain a mixed slurry B, and washing, drying and roasting after crystallization to obtain the HZSM-23@Al-SBA-15 composite molecular sieve.
7. The method according to claim 6, wherein: in the step (1) (1), the first template agent is one or more of isopropylamine, pyrrolidine, N-dimethylformamide and dimethylamine.
8. The method according to claim 6, wherein: in step (1) (1), silicon (in terms of silicon oxide) in the mixed solution a: the molar ratio of aluminum (calculated as aluminum oxide) is 1 (0.10-0.85), preferably 1 (0.20-0.79), and more preferably 1 (0.24-0.78); the aluminum (in terms of alumina): the molar ratio of the template agent is 1 (10-100), preferably 1 (15-85), and more preferably 1 (20-65).
9. The method according to claim 6, wherein: in the step (1) (1), preparing an amorphous silicon aluminum precursor by a carbonization method, and then adding a first template agent into the amorphous silicon aluminum precursor to obtain the mixed solution.
10. The method according to claim 6, wherein: in the step (1) (1), the mixed solution A is stirred for 0.2 to 2 hours at the temperature of 10 to 35 ℃.
11. The method according to claim 6, wherein: in the steps (1) and (2), based on aluminum (calculated as aluminum oxide) in the mixed solution A in the step (1) and (1), the mixed solution A is prepared according to SiO 2 :Al 2 O 3 :R 2 O (alkali source, wherein R is alkali metal, such as sodium, potassium) H 2 O=1 (0.0025-0.025): 0.015-0.08): 30-80, template agent (SDA)/SiO 2 Total feed mole ratio of =0.10-1.8, preferably SiO 2 /Al 2 O 3 50-200, H 2 O/SiO 2 30-60, R 2 O/SiO 2 And (3) adding an alkali source and a supplementary silicon source into the materials in the step (1) (1) at a ratio of 0.025-0.06.
12. The method according to claim 6, wherein: in the step (1) and the step (2), the silicon source is one or more of fumed silica, silica sol and water glass, and the alkali source is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
13. The method according to claim 6, wherein: in the step (1) and (3), the crystallization conditions are as follows: crystallizing at 150-200deg.C for 8-72 hr; the drying temperature is 80-120 ℃ and the drying time is 4-8 hours; the roasting temperature is 530-570 ℃ and the roasting time is 3-6 hours.
14. The method according to claim 6, wherein: in the steps (1) and (3), the ammonium exchange is carried out by adopting a conventional method, and Na in the ZSM-23 molecular sieve after the ammonium exchange 2 The mass content of O is lower than 0.2%; then washing, drying and roasting, wherein the drying temperature is 80-120 ℃ and the time is 4-8 hours; the roasting temperature is 530-570 ℃ and the roasting time is 3-6 hours.
15. The method according to claim 6, wherein: in the step (2) (1), the silicon source is one or two of ethyl orthosilicate and methyl orthosilicate, the acid is one or more of hydrochloric acid, nitric acid and sulfuric acid, and the pH of the acid solution is 1.0-4.0.
16. The method according to claim 6, wherein: in the step (2) (1), the stirring time is 4-10 hours, and the temperature is 20-45 ℃; and standing and aging for 8-48 hours.
17. The method according to claim 6, wherein: in the step (2) (2), the second template agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123); preferably, firstly, respectively dissolving aluminum isopropoxide and a template agent P123 in an acid solution, and then mixing with other raw materials; the acid is one or more of hydrochloric acid, nitric acid and sulfuric acid, and the molar concentration of hydrogen ions of the acid solution is 0.1-0.7 mol/L, preferably 0.2-0.6 mol/L.
18. The method according to claim 6, wherein: in the step (2) and (2), adding 0.15-0.55, preferably 0.18-0.50, of P123 and HZSM-23 in mass ratio; the mass ratio of the added silicon source to HZSM-23 is 1-4, preferably 1.2-3; the mass ratio of the added deionized water to HZSM-23 is 18-50, preferably 20-40; siO in silicon source 2 With Al in aluminum isopropoxide 2 O 3 The molar ratio is 15 to 120, preferably 20 to 100.
19. The method according to claim 6, wherein: in the step (2) and (2), the mixed solution B is continuously stirred for 6-8 hours at 15-30 ℃ before crystallization.
20. The method according to claim 6, wherein: in the step (2) and (2), the crystallization temperature of the mixed solution B is 80-120 ℃ and the crystallization time is 16-40 hours.
21. The method according to claim 6, wherein: in the step (2) (2), the drying temperature is 80-120 ℃ and the time is 4-8 hours; the roasting temperature is 530-570 ℃ and the roasting time is 3-6 hours.
22. The use of the HZSM-23@al-SBA-15 composite molecular sieve according to any of claims 1-5 for hydroisomerization of a naphthene-rich feedstock.
23. The reaction of claim 22, wherein: the content of naphthenes is 30-60%; the reaction temperature is 250-350 ℃ and the liquid space velocity is 0.5-1.5 h -1 The hydrogen-oil ratio is 600-1000, and the reaction hydrogen pressure is 3.5-5.0 Mpa.
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