CN113086988B - Y-type molecular sieve, preparation and application thereof in cracking - Google Patents

Y-type molecular sieve, preparation and application thereof in cracking Download PDF

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CN113086988B
CN113086988B CN201911336168.9A CN201911336168A CN113086988B CN 113086988 B CN113086988 B CN 113086988B CN 201911336168 A CN201911336168 A CN 201911336168A CN 113086988 B CN113086988 B CN 113086988B
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秦波
高杭
杜艳泽
柳伟
王仲义
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Abstract

The invention discloses a Y-type molecular sieve, a preparation method thereof and an application thereof in cracking, wherein the outer surface of the Y-type molecular sieve presents rhombohedral nanocrystals, and the size of the surface nanocrystals is 30 to 800nm; according to the preparation method of the Y-type molecular sieve, the synthetic liquid of the molecular sieve contains the surfactant S and the low-carbon alcohol M, the Y-type molecular sieve has more contactable areas and more contactable active sites, and the performance of the catalyst is remarkably improved when the molecular sieve is used in a hydrocracking process.

Description

Y-type molecular sieve, preparation and application thereof in cracking
Technical Field
The invention relates to a Y-type molecular sieve, a preparation method thereof and application thereof in cracking, in particular to a Y-type molecular sieve, a preparation method thereof and application thereof in hydrocracking.
Background
The Y-type molecular sieve has the obvious advantages of large specific surface area, high hydrothermal stability, proper acidity, low synthesis cost and the like, and simultaneously has a 1.12nm super cage structure in a topological structure, so that the Y-type molecular sieve has an important position which cannot be replaced in the field of catalysis. At present, the method is applied to a plurality of fields such as petroleum refining, sewage treatment, waste gas treatment and the like.
The size of the crystal grain of the Y-type molecular sieve is generally from hundreds of nanometers to a plurality of micrometers, the size of a pore channel is smaller than 1.3nm, and when molecules are diffused in the pore channel of the molecular sieve, the molecules continuously collide with the pore wall, so that the macromolecules are difficult to leave the pore channel of the molecular sieve, side reactions are generated, and carbon deposition of a catalyst is caused. The conventional micron-sized Y-shaped molecular sieve has small specific surface area, so that the loss of the active center on the inner surface of the molecular sieve is caused, and the effective utilization rate of an active site is reduced. The problems of longer diffusion path of reactants, larger diffusion resistance, low effective utilization rate of active centers and the like caused by the microporous structure of the micron-sized Y-shaped molecular sieve occur, so that the application of the micron-sized Y-shaped molecular sieve in the industry is limited to a great extent, and particularly, the reaction of oil macromolecules in the field of petroleum refining is limited. At present, researchers usually adopt two methods of preparing a hierarchical pore Y-type molecular sieve and shortening the length of a pore channel, namely a nanoscale Y-type molecular sieve to solve a plurality of problems of a micron-sized Y-type molecular sieve.
The preparation method of the hierarchical pore Y-shaped molecular sieve is mainly characterized in that the molecular sieve is placed in an acid environment or an alkaline environment through a post-treatment method to achieve the purposes of dealuminization and desiliconization, and a mesoporous structure is introduced into a molecular sieve framework. Or adding a template agent in the process of forming the molecular sieve initial gel, and removing the template agent in the molecular sieve framework through high-temperature roasting to form defect sites and introduce the defect sites into secondary holes. In both methods, a secondary pore structure can be formed in a molecular sieve framework, but secondary mesopores are introduced less, secondary pores are formed on the surface of the molecular sieve more, and the effect of diffusing macromolecules into molecular sieve pores is not great.
Compared with the preparation method of the hierarchical pore Y-shaped molecular sieve, the nanoscale Y-shaped molecular sieve has the advantages of high specific surface area, high load capacity, shorter pore channel structure and the like. The grain size of the nano-scale Y-shaped molecular sieve is beneficial to improving the accessibility of an active center, effectively reducing the diffusion path of macromolecules in a molecular sieve pore channel and improving the diffusion efficiency. Especially, when the grain size is less than 100nm, the external specific surface area is obviously increased, the pore channel is obviously shortened, and the catalytic performance is greatly improved. However, the too small grain size easily causes problems such as grain agglomeration and difficult solid-liquid separation, which affects its wide industrial application. At present, the synthesis method of the nano-scale Y-type molecular sieve mainly adopts direct hydrothermal synthesis by utilizing a template agent, seed crystals or microwave, ultrasonic equipment intervention and the like.
CN100551825 discloses an initial gel preparation process under the gravity condition of a rotating bed, which is complex in process flow and not beneficial to large-scale industrial production. CN101723400 discloses a preparation method of a small-grain Y-type molecular sieve with the grain diameter of 100nm to 700nm, and the small grains prepared by the synthesis method are highly dispersed, are not beneficial to separation and have lower yield. CN 10669860 discloses a method for preparing a nano Y molecular sieve by using an ultrasonic drying treatment, which can collect the product by filtration, but the synthesis process is complex and is not beneficial to industrial mass production. CN105621446 discloses a method for synthesizing a nano Y-shaped molecular sieve by using modified kaolin as a raw material, wherein the grain size of the synthesized Y-shaped molecular sieve is smaller and ranges from 30 to 100nm, but the synthesized raw material is special and the product yield is lower.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Y-type molecular sieve, a preparation method thereof and an application thereof in cracking, wherein the Y-type molecular sieve has more accessible areas and more accessible active sites, and the performance of the catalyst is remarkably improved when the molecular sieve is used in a hydrocracking process.
The Y-type molecular sieve has an outer surface in the shape of a rhombohedral nanocrystal, and the size of the nanocrystal on the surface ranges from 30 to 800nm, preferably from 50 to 500nm. The specific surface area of the molecular sieve is 650 to 1000m 2 Per g, preferably 700 to 900m 2 (ii)/g; the total pore volume is 0.30 to 0.48ml/g, preferably 0.32 to 0.42ml/g.
A preparation method of a Y-type molecular sieve comprises the following steps of preparing a molecular sieve synthetic solution containing a surfactant S and a low-carbon alcohol M, wherein the synthetic solution comprises the following components in molar terms:n(Na 2 O):n(Al 2 O 3 ): n(SiO 2 ):n (H 2 O):n(S):n(M) =5 to 12n(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(S):n(M)=6~10:1:8~10:200~280:0.12~0.20:0.12~0.40。
In the above method, the surfactant S is a nonionic surfactant, an ionic surfactant (including a cationic surfactant and an anionic surfactant), an amphoteric surfactant or a complex surfactant, preferably an ionic surfactant, and more preferably C n H 2n+1 (CH 3 ) 3 NBr。
In the above method, the lower alcohol M is a monohydric saturated alcohol such as methanol, ethanol, propanol, etc., preferably a monohydric saturated alcohol having less than 6 carbon atoms, and more preferably ethanol.
In the method, the molecular sieve synthetic solution generates gel, and the final molecular sieve is obtained after crystallization and drying. The crystallization temperature is 20 to 100 ℃, the crystallization time is 20 to 28h, the drying temperature is 90 to 120 ℃, and the drying time is 8 to 24h. The crystallization is preferably a multi-stage crystallization process from low temperature to high temperature, and preferably a two-stage constant temperature crystallization process. The two-stage constant temperature crystallization process comprises the following steps: the first-stage constant temperature is 20-60 ℃, preferably 30-50 ℃, and the constant temperature crystallization time is 8-168 hours, preferably 12-96 hours; the second section has a constant temperature of 60-100 ℃, preferably 70-90 ℃, and a constant temperature crystallization time of 5-120 hours, preferably 12-96 hours.
In the method, the molecular sieve synthetic solution is subjected to heat treatment at 25-45 ℃, preferably 30-40 ℃ for 1-36 hours, preferably 5-28 hours. The thermal treatment process facilitates the formation of an appropriate molecular sieve precursor.
The preparation process of the Y-type molecular sieve provided by the embodiment of the invention comprises the following steps:
(1) Under the condition of stirring, adding distilled water to an aluminum source for dissolving, adding alkali for stirring until the solution is clear, continuously adding a surfactant S and low molecular alcohol M, slowly and uniformly stirring, adding a silicon source into the system, and uniformly stirring;
(2) Preheating the solution at a certain temperature for a certain time to form a solutionn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) =5 to 12n(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 6 to 10, wherein the ratio of (1) to 0.12 to 10) to 0.20.
In the step (1), the aluminum source comprises one or more of aluminum chloride, aluminum sulfate, aluminum nitrate and sodium aluminate, preferably sodium aluminate.
In the above method, the surfactant S is an ionic surfactant (including a cationic surfactant and an anionic surfactant), preferably a cationic surfactant, and more preferably C n H 2n+1 (CH 3 ) 3 NBr。
In the above method, the lower alcohol is a monohydric saturated alcohol such as methanol, ethanol, propanol, etc., preferably a monohydric saturated alcohol having less than 6 carbon atoms, and more preferably ethanol.
In the above-mentioned process step (1), the surfactant S is an ionic surfactant, preferably a cationic surfactant, more preferably C n H 2n+1 (CH 3 ) 3 NBr, where n can be 1 to 20.
In the step (1), the silicon source includes silica sol, water glass, silica gel, white carbon black, and the like, preferably silica sol; the aluminum source is sodium metaaluminate, aluminum sheet and aluminum sulfate, preferably sodium metaaluminate; the base is sodium hydroxide.
In the step (1), adding the surfactant S and the low molecular alcohol, and stirring for 0.5 to 4 hours, preferably 0.5 to 2hours; after the silicon source is added to the system, the mixture is stirred for 0.5 to 4 hours, preferably 0.5 to 2hours. Wherein, the low molecular alcohol and the surfactant M act together to provide favorable conditions for the growth of the nanometer molecular sieve precursor.
In the step (2), the preheating temperature of the solution is 25-45 ℃; the time is from 1 to 36 hours, preferably from 5 to 28 hours.
In the step (2), the two-stage constant temperature crystallization process comprises: the first-stage constant temperature is 20-60 ℃, preferably 30-50 ℃, and the constant temperature crystallization time is 8-168 hours, preferably 12-96 hours; the second-stage constant temperature is 60-100 ℃, preferably 70-90 ℃, and the constant temperature crystallization time is 5-120 hours, preferably 12-96 hours.
The application of the Y-type molecular sieve in preparing a hydrocracking catalyst.
A hydrocracking catalyst comprises hydrogenation active metal, a Y-type molecular sieve and amorphous silicon-aluminum, wherein the hydrogenation active metal is one or more of VIB group Mo and W, and one or more of VIII group Co and Ni. Wherein the content of the Y-type molecular sieve is 30 to 70 percent, the content of the VIB group metal oxide is 12 to 18 percent, and the content of the VIII group metal oxide is 3 to 9 percent. (component content is relative to the total weight of the hydrocracking catalyst).
The method prepares the highly dispersed molecular sieve precursor, inhibits the rapid aggregation of the molecular sieve precursor, and finally the molecular sieve is formed by clustering and combining a plurality of nanocrystal Y-type molecular sieve particles to grow into the nano polycrystal Y-type molecular sieve consisting of a plurality of nanocrystal particles. The nano crystal particles are stacked to form a nano cluster, and a mesoporous structure is formed among the crystal particles in the stacking process, so that the problems of low hydrothermal stability and difficult solid-liquid recovery of the nano molecular sieve can be solved, the nano crystal particles have the advantages of high specific surface area (especially external specific surface area) and short pore passage of the nano molecular sieve, the mesoporous structure provides a friendly reaction environment for macromolecules, and the catalytic performance of the nano Y-shaped molecular sieve is comprehensively improved.
Drawings
Fig. 1 is an XRD diffractogram of the nano polycrystalline Y-type molecular sieve prepared in example 1.
Fig. 2 is an SEM image of the nano polycrystalline Y-type molecular sieve prepared in example 1.
FIG. 3 is an SEM image of the Y-type molecular sieve prepared in example 7.
Fig. 4 is an SEM image of the Y-type molecular sieve prepared in comparative example 1.
Detailed Description
The following examples and comparative examples are given to further illustrate the effects and effects of the method of the present invention, but the following examples are not intended to limit the method of the present invention, and all% are mass percentages unless otherwise specified in the present application.
Example 1
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH to stir until the sodium aluminate is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring, adding a silicon source into the system, and uniformly stirring;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 8. The first section has constant temperature of 30 ℃ and constant temperature crystallization time of 48 hours; the second stage has constant temperature of 70 deg.c and constant crystallizing time of 48 hr.
Example 2
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH to stir until the sodium aluminate is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring, adding a silicon source into the system, and uniformly stirring;
(2) The solution was preheated at 45 ℃ for 12h, the composition of the solution formed at the end beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 8. The first section has a constant temperature of 40 ℃ and a constant temperature crystallization time of 24 hours; the second stage constant temperature is 90 deg.C, and the constant temperature crystallization time is 18 hr.
Example 3
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH to stir until the sodium aluminate is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring, adding a silicon source into the system, and uniformly stirring;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) =8And (3) carrying out two-stage constant temperature crystallization process on the glue, washing the obtained solid product to be neutral, filtering and drying to obtain the target product. The first section has constant temperature of 30 ℃ and constant temperature crystallization time of 48 hours; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
Example 4
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH, stirring the mixture until the mixture is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring the mixture, adding a silicon source into the system, and uniformly stirring the mixture;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 8. The first section has constant temperature of 30 ℃ and constant temperature crystallization time of 48 hours; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
Example 5
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH, stirring the mixture until the mixture is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring the mixture, adding a silicon source into the system, and uniformly stirring the mixture;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 5. The first stage has constant temperature of 30 deg.c and constant crystallization time of 48 hr; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
Example 6
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH, stirring the mixture until the mixture is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring the mixture, adding a silicon source into the system, and uniformly stirring the mixture;
(2) Preheating the solution at 20 deg.C for 20 hr to obtain a solution with a composition ofn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 12. The first section has constant temperature of 30 ℃ and constant temperature crystallization time of 48 hours; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
Example 7
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH to stir until the sodium aluminate is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring, adding a silicon source into the system, and uniformly stirring;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 8. The constant temperature of the system is 70 ℃, and the constant temperature crystallization time is 120 hours.
Example 8
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH, stirring the mixture until the mixture is clear, continuously adding CTAB and ethanol, slowly and uniformly stirring the mixture, adding a silicon source into the system, and uniformly stirring the mixture;
(2) The solution composition isn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) = 8. First, theThe constant temperature is 30 ℃ for a period of 48 hours; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
Comparative example 1
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH, stirring the mixture until the mixture is clear, continuously adding CTAB, slowly and uniformly stirring the mixture, adding a silicon source into the system, and uniformly stirring the mixture;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB) = 8. The first section has constant temperature of 30 ℃ and constant temperature crystallization time of 48 hours; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
Comparative example 2
(1) Under the condition of stirring, adding distilled water into sodium aluminate to dissolve the sodium aluminate, adding NaOH, stirring until the sodium aluminate is clear, continuously adding ethanol, slowly and uniformly stirring, adding a silicon source into the system, and uniformly stirring;
(2) The solution was preheated at 35 ℃ for 16h, the composition of the solution formed beingn(Na 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O): n(C 2 H 5 OH) = 8. The first section has constant temperature of 30 ℃ and constant temperature crystallization time of 48 hours; the second stage constant temperature is 70 deg.C, and the constant temperature crystallization time is 48 hr.
The invention adopts a kneading method to prepare the catalyst, and the evaluation reaction process conditions are as follows: under the conditions that the reaction pressure is 12 to 18 MPa and the volume ratio of hydrogen to oil is 1: 1500. the volume airspeed is 0.5 to 1.5 h < -1 >, the nitrogen content of the refined oil is 5 mug/g, and the one-way conversion rate of the cracking section is controlled to be 65% under the process conditions of single-section one-time passing.
The application of the rhombohedral nano Y-shaped molecular sieve in preparing the hydrocracking catalyst comprises the following steps:
the invention adopts a kneading method to prepare the hydrocracking catalyst. And (2) fully and uniformly mixing the synthesized rhombohedral nano Y-shaped molecular sieve, amorphous silicon-aluminum, VIB group metal oxide, VIII group metal oxide and sesbania powder under the bonding action of inorganic acid, rolling, forming, drying at 120 ℃ for 12-24 h, and roasting at 550 ℃ in a muffle furnace for 3-12 h to obtain the hydrocracking catalyst. The hydrocracking catalyst properties are shown in Table 2, the process conditions and feed oil properties are shown in Table 3, and the catalyst evaluation results are shown in Table 4.
TABLE 1 structural Properties of the products of the examples and comparative examples
Figure 546905DEST_PATH_IMAGE001
TABLE 2 hydrocracking catalyst Properties
Figure 1
TABLE 3 hydrocracking catalyst evaluation of Process conditions and feedstock oil Properties
Figure 883394DEST_PATH_IMAGE004
TABLE 4 results of evaluation of hydrocracking catalysts
Figure 882574DEST_PATH_IMAGE006
The evaluation experiment result shows that when the conversion rate is controlled to be 65%, compared with the catalyst prepared in the comparative example 1, the reaction temperature of the catalyst can be reduced by 4 to 16 ℃, the BMCI (molar ratio) of tail oil is reduced by 2.4 to 10.7, the yield of heavy naphtha is improved by 5 to 12 percent, and the content of cycloalkanes with more than two rings can be reduced by 6 to 16 percent. The surface contact area of the rhombohedral nano Y-shaped molecular sieve obtained by the method is increased, the accessibility of active sites is improved, and the catalyst is beneficial to reactant reaction and product diffusion in the hydrocracking reaction process, so that the yield of heavy naphtha is improved, and the BMCI value of tail oil is reduced.

Claims (8)

1. A preparation method of a Y-type molecular sieve is characterized by comprising the following steps: the outer surface of the molecular sieve presents rhombohedral nanocrystals, and the size of the surface nanocrystals is 30 to 800nm; the preparation method of the Y-type molecular sieve comprises the following steps:
(1) Under the condition of stirring, adding distilled water to an aluminum source for dissolving, adding alkali for stirring until the solution is clear, continuously adding a surfactant S and a low-carbon alcohol M, slowly stirring uniformly, adding a silicon source into the system, and stirring uniformly;
(2) Preheating the solution at a certain temperature for a certain time to obtain a solution with a composition of n (Na) 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(CTAB):n(C 2 H 5 OH) =5 to 12, 1 to 6 to 11 to 180 to 0.3, and the gel is subjected to two-section constant temperature crystallization processes, the obtained solid product is washed to be neutral, filtered and dried to obtain a target product;
the surfactant S is C n H 2n+1 (CH 3 ) 3 NBr, wherein n is 1 to 20;
the lower alcohol M is one of methanol, ethanol or propanol;
in the step (2), the preheating temperature of the solution is 25-45 ℃; the time is 1 to 36 hours;
in the step (2), the crystallization is a two-stage constant temperature crystallization process of firstly low temperature and then high temperature: the first-stage constant temperature is 20-60 ℃, and the constant temperature crystallization time is 8-168 hours; the second section has a constant temperature of 60-100 ℃ and a constant crystallization time of 5-120 hours.
2. The method of claim 1, wherein: composition n (Na) of the solution in molar terms 2 O):n(Al 2 O 3 ):n(SiO 2 ):n(H 2 O):n(S):n(M)=6~10:1:8~10:200~280:0.12~0.20:0.12~0.40。
3. The method of claim 1, wherein: the drying temperature is 90 to 120 ℃, and the drying time is 8 to 24h.
4. The method of claim 1, wherein: in the step (1), the aluminum source comprises one or more of aluminum chloride, aluminum sulfate, aluminum nitrate and sodium aluminate.
5. The method of claim 1, wherein: adding a surfactant S and low-carbon alcohol into the mixture in the step (1), and stirring the mixture for 0.5 to 4 hours; and adding a silicon source into the system, and stirring for 0.5 to 4 hours.
6. A Y-type molecular sieve prepared by the method of any one of claims 1 to 5.
7. The molecular sieve of claim 6, characterized in that: the specific surface area of the molecular sieve is 650 to 1000m 2 (iv) g; the total pore volume is 0.30 to 0.48mL/g.
8. Use of the molecular sieve of claim 6 or 7 in the preparation of a hydrocracking catalyst.
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