CN114195164B - Composite material with step hole structure distribution and preparation method thereof - Google Patents

Composite material with step hole structure distribution and preparation method thereof Download PDF

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CN114195164B
CN114195164B CN202010983029.1A CN202010983029A CN114195164B CN 114195164 B CN114195164 B CN 114195164B CN 202010983029 A CN202010983029 A CN 202010983029A CN 114195164 B CN114195164 B CN 114195164B
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composite material
structure distribution
pore structure
pore
crystallization
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CN114195164A (en
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宋绍彤
钟海军
吕忠武
何盛宝
葛少辉
赵秦峰
袁晓亮
鞠雅娜
李阳
李天舒
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Petrochina Co Ltd
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a composite material with step hole structure distribution and a preparation method thereof. The method comprises the following steps: 1) Mixing template F127 or P123 with corresponding silicon sources in an acidic environment, heating and stirring until the mixture is uniform; 2) Uniformly dripping a pore-expanding agent into the mixed solution obtained in the step 1), uniformly stirring, and standing for a period of time to obtain white precipitate; 3) And (3) placing the obtained precipitate into a crystallization kettle for crystallization, and crystallizing, filtering, drying and roasting to obtain the SBA-15 and MCFs composite material which has a step hole structure. In the invention, the aperture of the composite material between 15 and 20nm accounts for more than 20 percent, the aperture of the composite material between 48 and 53nm accounts for more than 15 percent, and the specific surface area is between 400 and 600m 2 Per gram, the pore volume is 1.0-2.0 cm 3 And/g. The composite material has the characteristics of large specific surface area, step hole structure, adjustable pore diameter and the like, so that the composite material is widely applied to the fields of catalysis, absorption and separation, biomedical treatment and the like, and is more commonly applied to petroleum refining in particular.

Description

Composite material with step hole structure distribution and preparation method thereof
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a composite material with gradient pore structure distribution and a preparation method thereof, which are widely applied to the fields of catalysis, absorption and separation, biomedical treatment and the like, and particularly are more commonly applied to petroleum refining.
Background
It has been found that motor vehicle exhaust is one of the major sources of haze causing weather and that sulfides in motor vehicle exhaust are one of the major pollutants. The gasoline composition in China is mainly FCC gasoline, and accounts for about 80%, and is characterized by being deficient in high sulfur, high olefin and high octane number. Moreover, as FCC processed feedstocks move toward heavies, the sulfur and olefin content of FCC gasoline will increase further. Therefore, the desulfurization, olefin reduction and octane number maintenance of FCC gasoline become key problems to be solved by clean gasoline production technology in China.
In the course of long-term research on hydrodesulfurization catalysts, research on support materials is one of the important points. For supported catalysts, the support material has an important influence on the catalytic performance of the catalyst. The carrier not only needs to provide a larger specific surface area to fully utilize the active components of the catalyst and reduce the economic cost, but also can improve the performance of the catalyst by interacting with the active components, such as being used as a framework of the catalyst, improving the stability and the mechanical strength of the catalyst, ensuring that the catalyst has a certain shape and size to meet the requirements of fluid mechanics conditions in an industrial reactor,reducing the resistance of fluid flow, and the like. Currently, the most commonly used catalyst support materials are gamma-Al 2 O 3 Activated carbon, molecular sieves, and the like. In recent years, it has been found that mesoporous materials such as SBA-15, SBA-15 and mesoporous silica foam (MCFs) are mixed or compounded with microporous materials such as ZSM-5 and Beta to serve as carriers. CN106433758A discloses a FCC gasoline hydrodesulfurization process, the catalyst comprising a support and an active component; the carrier is a compound or a mixture of MSU-G, SBA-15 and HMS, the catalyst also contains a catalytic auxiliary agent, and the catalytic auxiliary agent is Cr 2 O 3 、ZrO 2 、CeO 2 、V 2 O 5 And NbOPO 4 Is a mixture of (a) and (b). The process can reduce the total sulfur content in FCC gasoline to below 5ppm to meet the national five standards of gasoline. At the same time, the process also does not obviously reduce the octane number of FCC gasoline. However, the carrier material prepared by the method is simply mixed or compounded, a gradual step hole structure cannot be formed, and a further lifting space is formed by the carrier material.
The stepped hole carrier material has the characteristics of large specific surface area, stepped hole structure, adjustable pore diameter and the like, so that the stepped hole carrier material is widely applied to the fields of catalysis, absorption separation, biomedicine and the like, and is more commonly applied to petroleum refining in particular. The macropores in the stepped pore material can effectively increase the permeability of the catalyst, prevent carbon deposition in the reaction process from blocking pore channels, cover active sites and prolong the service life of the catalyst; the pores can increase the specific surface area of the material, contain more active components, promote the catalyst efficiency, and then increase the catalytic performance of the catalyst.
Disclosure of Invention
The invention aims to provide a composite material with step hole structure distribution and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a composite material with a hierarchical pore structure distribution, comprising the following steps:
step 1: adding a silicon source into F127 or P123 serving as a template agent in an acidic environment, heating and stirring the mixed solution until the mixed solution is uniform, and obtaining a mixed solution;
step 2: uniformly dripping the pore-expanding agent into the mixed solution in the step 1, uniformly stirring, and standing for a period of time to obtain white precipitate;
step 3: placing the precipitate obtained in the step 2 into a crystallization kettle for crystallization, and obtaining the SBA-15 and MCFs composite material after crystallization, suction filtration, drying and roasting, wherein the material has a step hole structure;
in the composite material with the distributed cascade pore structure, preferably, the content of SBA-15 in the composite material is 28-44 wt% and the content of MCFs in the composite material is 26-44 wt%, the pore structure of the composite carrier material is a cascade pore structure, and the pore diameter is 18-50 nm.
The composite material with the distributed step hole structure of the invention preferably has the specific surface area of 480-520 m 2 Per gram, the pore volume is 1.5-1.8 cm 3 And/g, the aperture of 15-20 nm is more than 20%, and the aperture of 48-53 nm is more than 15%.
In the preparation method of the composite material with the distributed step hole structure, preferably, in the step 1, the acidic environment is pH 1-3.
In the preparation method of the composite material with the distributed step hole structure, preferably, in the step 1, the silicon source is at least one of tetraethyl orthosilicate, water glass, silica gel and sodium silicate, and the addition amount is 10-50wt% of the template agent.
In the preparation method of the composite material with the distributed step hole structure, in the step 1, the heating temperature is preferably 30-60 ℃.
In the preparation method of the composite material with the step hole structure distribution, preferably, in the step 2, the pore-expanding agent is at least one of hexane, cyclohexane, 1,3, 5-triisopropylbenzene and mesitylene, and the addition amount is 30-60 wt% of the template agent.
In the preparation method of the composite material with the distributed step hole structure, preferably, in the step 3, the crystallization temperature is 100-200 ℃, and the crystallization time is 12-48 hours, preferably 24 hours; the drying temperature is 100-150 ℃ and the drying time is 3-12 h; the roasting temperature is 550-750 ℃, and the roasting time is 3-6 hours, preferably 6 hours.
The mesoporous molecular sieve SBA-15 has high specific surface area, good hydrothermal stability and larger pore diameter, and is beneficial to the diffusion of oil molecules in pore channels; MCFs is a novel mesoporous material with ultra-large pore diameter, uniform pore diameter distribution, large pore volume and high specific surface, and two mesoporous materials with different pore diameters and pore channel structures are mixed or compounded with alumina powder, so that the acidity of a hydrofining catalyst can be changed, the dispersity of active components is improved, and the reduction and vulcanization of metal components are promoted. Therefore, the preparation of the mesoporous composite carrier with high specific surface area, stepped pore structure and good stability becomes an important way for improving the activity of the hydrofining catalyst.
The invention has the following advantages:
(1) In the step hole structure distribution composite material provided by the invention, SBA-15 is a mesoporous material with a body-centered cubic structure; MCFs is a novel mesoporous material with ultra-large pore diameter, uniform pore diameter distribution, large pore volume and high specific surface, the pore diameter is more than 20% at 15-20 nm, the pore diameter is more than 15% at 48-53 nm, and the synergistic improvement of hydrofining effect can be realized.
(2) The gradient pore structure distribution composite material provided by the invention has the characteristics of large specific surface area, gradient pore structure, adjustable pore diameter and the like, so that the gradient pore structure distribution composite material is widely applied to the fields of catalysis, absorption separation, biomedical treatment and the like, and is more commonly applied to petroleum refining in particular.
Drawings
FIG. 1 is a graph showing pore size distribution of a composite material according to example 1 of the present invention;
fig. 2 is an SEM image of the composite material of example 1 of the present invention.
As can be seen from fig. 1, the synthesized composite pore diameter exhibits a stepped pore structure, and the distribution is relatively concentrated, with most of the pore diameter concentrated between 18nm and 55 nm.
As can be seen from fig. 2, the synthesized composite material exhibits a spherical particle morphology with a high degree of dispersion.
Detailed Description
In order to more clearly understand the technical contents of the present invention, the technical contents of the present invention will be further explained below.
The invention discloses a preparation method of a composite material with step hole structure distribution. The method comprises the following steps: 1) Mixing template F127 or P123 with corresponding silicon sources in an acidic environment, heating and stirring until the mixture is uniform; 2) Uniformly dripping a pore-expanding agent into the mixed solution obtained in the step 1), uniformly stirring, and standing for a period of time to obtain white precipitate; 3) And (3) placing the obtained precipitate into a crystallization kettle for crystallization, and crystallizing, filtering, drying and roasting to obtain the SBA-15 and MCFs composite material which has a step hole structure. The specific surface area of the composite material is 400-600 m 2 Per gram, the pore volume is 1.0-2.0 cm 3 And/g, the aperture is more than 20% of 15-20 nm, and the aperture is more than 15% of 48-53 nm.
The preparation method of the composite material with the step hole structure distribution comprises the following specific preparation steps:
step 1: adding a silicon source into F127 or P123 serving as a template agent in an acidic environment, heating and stirring the mixed solution until the mixed solution is uniform, and obtaining a mixed solution;
step 2: uniformly dripping the pore-expanding agent into the mixed solution obtained in the step 1, uniformly stirring, and standing for a period of time to obtain white precipitate;
step 3: placing the precipitate obtained in the step 2 into a crystallization kettle for crystallization, and obtaining the SBA-15 and MCFs composite material after crystallization, suction filtration, drying and roasting, wherein the material has a step hole structure;
according to the preparation method, the silicon source in the step 1 is one or more of tetraethyl orthosilicate, water glass, silica gel and sodium silicate.
The pore-expanding agent in the step 2 is one or more of hexane, cyclohexane, 1,3, 5-triisopropylbenzene and mesitylene, and the addition amount is 30-60 wt% of the template agent.
The specific surface of the composite material prepared in the step 3 is preferably 400-600 m 2 Per gram, pore volume of 1.0-2.0 cm 3 And/g, the aperture is more than 20% of 15-20 nm, and the aperture is more than 15% of 48-53 nm.
The preparation method of the composite material with the gradient pore structure distribution has the characteristics of large specific surface area, gradient pore structure, adjustable pore diameter and the like, so that the preparation method is widely applied to the fields of catalysis, absorption separation, biomedical treatment and the like, and is more common in petroleum refining. For example, the catalyst is used for catalyzing the hydrodesulfurization reaction of gasoline or heavy gasoline, the sulfur content of the raw material is less than 1000mg/kg, the olefin content is less than 45v%, the sulfur content of the blending component of the product is less than 15mg/kg, the olefin content is reduced by less than 10v%, and the octane number loss is less than 2.0.
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Example 1:
preparation of MCFs-SBA-15 composite material
(1) Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with a certain concentration and 2g of P123 template agent, and stirring at the water bath temperature of 35 ℃ until a uniform solution is formed;
(2) slowly dripping 30wt% of pore-enlarging agent mesitylene of the template agent into the uniform solution obtained in the step (1), and continuing water bath stirring to obtain a mixed solution;
(3) weighing 10wt% of template agent tetraethyl orthosilicate (TEOS), slowly dripping the template agent into the mixed solution in the step (2), placing the mixed solution in a sealed environment, continuing water bath stirring, transferring the mixed solution into a crystallization kettle, and placing the crystallization kettle in a baking oven at 120 ℃ for crystallization for 24 hours;
(4) and after the crystallization process is finished, taking out the crystallization kettle to perform cooling water cooling treatment, filtering and washing the product, drying for about 12 hours at 120 ℃, and roasting for 6 hours in a muffle furnace at 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 2:
preparation of MCFs-SBA-15 composite material
(1) Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with a certain concentration and 2g of P123 template agent, and stirring at the temperature of 35 ℃ in a water bath until a uniform solution is formed;
(2) slowly dripping 30wt% of template agent, namely mesitylene serving as a pore-enlarging agent into the uniform solution obtained in the step (1), and continuing water bath stirring to obtain a mixed solution;
(3) weighing 30wt% of water glass of a template agent, slowly dripping the water glass into the mixed solution in the step (2), placing the water glass in a sealed environment, continuing water bath stirring, transferring the water glass into a crystallization kettle, and placing the crystallization kettle in a 120 ℃ oven for crystallization for 24 hours;
(4) and after the crystallization process is finished, taking out the crystallization kettle to perform cooling water cooling treatment, filtering and washing the product, drying for about 12 hours at 120 ℃, and roasting for 6 hours in a muffle furnace at 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 3:
preparation of MCFs-SBA-15 composite material
(1) Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with a certain concentration and 2g of P123 template agent, and stirring at the water bath temperature of 35 ℃ until a uniform solution is formed;
(2) slowly dripping 30wt% of template agent, namely mesitylene serving as a pore-enlarging agent into the uniform solution obtained in the step (1), and continuing water bath stirring to obtain a mixed solution;
(3) weighing 50wt% sodium silicate of a template agent, slowly dripping the sodium silicate into the mixed solution in the step (2), placing the mixed solution in a sealed environment, continuing water bath stirring, transferring the mixed solution into a crystallization kettle, and placing the crystallization kettle in a 120 ℃ oven for crystallization for 24 hours;
(4) and after the crystallization process is finished, taking out the crystallization kettle to perform cooling water cooling treatment, filtering and washing the product, drying for about 12 hours at 120 ℃, and roasting for 6 hours in a muffle furnace at 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 4:
preparation of MCFs-SBA-15 composite material
(1) Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with a certain concentration and 2g of P123 template agent, and stirring at the water bath temperature of 35 ℃ until a uniform solution is formed;
(2) slowly dropwise adding 45wt% of template agent cyclohexane serving as a pore-enlarging agent into the uniform solution obtained in the step (1), and continuing water bath stirring to obtain a mixed solution;
(3) weighing 10wt% of template agent tetraethyl orthosilicate (TEOS), slowly dripping the template agent into the mixed solution in the step (2), placing the mixed solution in a sealed environment, continuing water bath stirring, transferring the mixed solution into a crystallization kettle, and placing the crystallization kettle in a baking oven at 120 ℃ for crystallization for 24 hours;
(4) and after the crystallization process is finished, taking out the crystallization kettle to perform cooling water cooling treatment, filtering and washing the product, drying for about 12 hours at 120 ℃, and roasting for 6 hours in a muffle furnace at 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 5:
preparation of MCFs-SBA-15 composite material
(1) Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with a certain concentration and 2g of P123 template agent, and stirring at the water bath temperature of 35 ℃ until a uniform solution is formed;
(2) weighing 60wt% of template agent, namely 1,3, 5-triisopropylbenzene, slowly dropwise adding the template agent into the uniform solution obtained in the step (1), and continuing water bath stirring to obtain a mixed solution;
(3) weighing 10wt% of template agent tetraethyl orthosilicate (TEOS), slowly dripping the template agent into the mixed solution in the step (2), placing the mixed solution in a sealed environment, continuing water bath stirring, transferring the mixed solution into a crystallization kettle, and placing the crystallization kettle in a baking oven at 120 ℃ for crystallization for 24 hours;
(4) and after the crystallization process is finished, taking out the crystallization kettle to perform cooling water cooling treatment, filtering and washing the product, drying for about 12 hours at 120 ℃, and roasting for 6 hours in a muffle furnace at 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 6:
preparation of MCFs-SBA-15 composite material
(1) Taking F127 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with a certain concentration and 2g of F127 template agent, and stirring at the temperature of 35 ℃ in a water bath until a uniform solution is formed;
(2) weighing 60wt% of template agent, namely 1,3, 5-triisopropylbenzene, slowly dropwise adding the template agent into the uniform solution obtained in the step (1), and continuing water bath stirring to obtain a mixed solution;
(3) weighing 10wt% of template agent tetraethyl orthosilicate (TEOS), slowly dripping the template agent into the mixed solution in the step (2), placing the mixed solution in a sealed environment, continuing water bath stirring, transferring the mixed solution into a crystallization kettle, and placing the crystallization kettle in a baking oven at 120 ℃ for crystallization for 24 hours;
(4) and after the crystallization process is finished, taking out the crystallization kettle to perform cooling water cooling treatment, filtering and washing the product, drying for about 12 hours at 120 ℃, and roasting for 6 hours in a muffle furnace at 550 ℃ to obtain the SBA-15-MCFs composite material.
In the invention, the aperture of the composite material between 15 and 20nm accounts for more than 20 percent, the aperture of the composite material between 48 and 53nm accounts for more than 15 percent, and the specific surface area is between 400 and 600m 2 Per gram, the pore volume is 1.0-2.0 cm 3 And/g. The composite material has the characteristics of large specific surface area, step hole structure, adjustable pore diameter and the like, so that the composite material is widely applied to the fields of catalysis, absorption and separation, biomedical treatment and the like, and is more commonly applied to petroleum refining in particular.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (12)

1. The preparation method of the composite material with the step hole structure distribution is characterized by comprising the following steps of:
step 1: adding a silicon source into F127 or P123 serving as a template agent in an acidic environment, heating and stirring the mixed solution until the mixed solution is uniform, and obtaining a mixed solution;
step 2: uniformly dripping the pore-expanding agent into the mixed solution in the step 1, uniformly stirring, and standing to obtain white precipitate;
step 3: placing the precipitate obtained in the step 2 into a crystallization kettle for crystallization, and obtaining the SBA-15 and MCFs composite material after crystallization, suction filtration, drying and roasting;
wherein the pore-expanding agent is at least one of hexane, cyclohexane, 1,3, 5-triisopropylbenzene and mesitylene.
2. The method for preparing a composite material with a hierarchical pore structure distribution according to claim 1, wherein the pH value of the acidic environment in step 1 is 1 to 3.
3. The method of preparing a composite material having a hierarchical pore structure distribution according to claim 1, wherein the silicon source is at least one of tetraethyl orthosilicate, water glass, silica gel, and sodium silicate.
4. The method for preparing a composite material with a hierarchical pore structure distribution according to claim 1, wherein the addition amount of the silicon source is 10-50 wt% of the template agent.
5. The method of preparing a composite material having a hierarchical pore structure distribution according to claim 1, wherein the heating temperature in step 1 is 30 ℃ to 60 ℃.
6. The method for preparing a composite material with a hierarchical pore structure distribution according to claim 1, wherein the addition amount of the pore expanding agent is 30-60 wt% of the template agent.
7. The method for preparing a composite material with a gradient pore structure distribution according to claim 1, wherein the crystallization temperature in the step 3 is 100-200 ℃ and the crystallization time is 12-48 h.
8. The method for preparing a composite material with a hierarchical pore structure distribution according to claim 1, wherein the drying temperature in the step 3 is 100-150 ℃ and the drying time is 3-12 h.
9. The method for preparing a composite material with a hierarchical pore structure distribution according to claim 1, wherein the baking temperature in the step 3 is 550-750 ℃ and the baking time is 3-6 h.
10. The method for preparing a composite material with a hierarchical pore structure distribution according to claim 1, wherein the content of SBA-15 in the composite material of SBA-15 and MCFs is 28-44 wt% and the content of MCFs is 26-44 wt%.
11. A composite material with a gradient pore structure distribution, which is characterized in that the specific surface area of the composite material is 400-600 m and is prepared by a preparation method of the composite material with the gradient pore structure distribution as set forth in any one of claims 1-10 2 Per g, pore diameter of 18 nm-50 nm, pore volume of 1.0-2.0 cm 3 And/g, the aperture of 15-20 nm is more than 20%, and the aperture of 48-53 nm is more than 15%.
12. The composite material with the gradient pore structure distribution according to claim 11, wherein the specific surface area of the composite material is 480-520 m 2 Per gram, the pore volume is 1.5-1.8 cm 3 /g。
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