CN114195164A - Composite material with step pore structure distribution and preparation method thereof - Google Patents

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

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CN114195164A
CN114195164A CN202010983029.1A CN202010983029A CN114195164A CN 114195164 A CN114195164 A CN 114195164A CN 202010983029 A CN202010983029 A CN 202010983029A CN 114195164 A CN114195164 A CN 114195164A
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composite material
pore structure
pore
crystallization
stepped
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CN114195164B (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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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J35/615—
    • B01J35/617—
    • B01J35/633—
    • B01J35/647—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The invention discloses a composite material with a step pore structure distribution and a preparation method thereof. The method comprises the following steps: 1) mixing a template agent F127 or P123 with a corresponding silicon source in an acid 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 a white precipitate; 3) and (3) putting the obtained precipitate 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 pore structure. The composite material has the aperture of 15-20 nm accounting for more than 20 percent, the aperture of 48-53 nm accounting for more than 15 percent, and the specific surface area of 400-600 m2A pore volume of 1.0 to 2.0cm3(ii) in terms of/g. The composite material has the characteristics of large specific surface area, stepped pore structure, adjustable pore diameter and the like, so the composite material is widely applied to the fields of catalysis, absorption and separation, biological medicine and the like, and is more generally applied to petroleum refining.

Description

Composite material with step pore 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 step pore structure distribution and a preparation method thereof.
Background
In recent years, haze weather covers all big cities in China, and great harm is caused to the health and the traveling of people. Research has found that motor vehicle exhaust is one of the main sources of weather causing haze, and sulfides in motor vehicle exhaust are one of the main pollutants. China's gasoline is mainly composed of FCC gasoline, accounting for about 80%, and features high sulfur, high olefine and high octane number. Moreover, as the feedstock for FCC processing moves toward heaviness, further increases in sulfur and olefin content in FCC gasoline will result. Therefore, the desulfurization, olefin reduction and octane number maintenance of the FCC gasoline become key problems to be solved by the clean gasoline production technology in China.
The study of support materials has been one of the major points in the long-term research on hydrodesulfurization catalysts. For supported catalysts, the support material has a significant effect on the catalytic performance of the catalyst. The carrier not only needs to provide larger specific surface area to fully utilize the active components of the catalyst and reduce economic cost, but also can improve the performance of the catalyst by interacting with the active components, for example, the carrier can be used as a framework of the catalyst to improve the stability and mechanical strength of the catalyst, ensure that the catalyst has certain shape and size, meet the requirement of fluid mechanical conditions in an industrial reactor, reduce fluid flow resistance and the like. At present, the most commonly used catalyst support material is gamma-Al2O3Activated carbon and molecular sieves, and the like. In recent years, it has been found that a mesoporous material such as SBA-15, SBA-15 or mesoporous silica foams (MCFs) is mixed or compounded with a microporous material such as ZSM-5 or Beta as a carrier. CN106433758A discloses a FCC gasoline hydrodesulfurization process, the catalyst comprises a carrier 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 assistant, and the catalytic assistant is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4A mixture of (a). The process can reduce the total sulfur content in FCC gasoline to below 5ppm so as to meet the national five standards of gasoline. Meanwhile, the octane number of the FCC gasoline is not obviously reduced by the process. However, the carrier material prepared by the method is simply mixed or compounded, a gradual-change stepped hole structure cannot be formed, and the synthesis of the carrier material has a further improved space.
The stepped pore carrier material has the characteristics of large specific surface area, stepped pore structure, adjustable pore diameter and the like, so the composite material is widely applied to the fields of catalysis, absorption separation, biological medicine and the like, and is more generally applied to petroleum refining. Macropores in the stepped pore material can effectively increase the permeability of the catalyst, prevent carbon deposit from blocking pore channels in the reaction process, cover active sites and prolong the service life of the catalyst; the small holes can increase the specific surface area of the material, contain more active components, improve the efficiency of the catalyst and further increase the catalytic performance of the catalyst.
Disclosure of Invention
The invention aims to provide a composite material with a step pore 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 having a distribution of a stepped pore structure, comprising the steps of:
step 1: adding a silicon source into F127 or P123 serving as a template agent under an acidic environment, and heating and stirring the mixed solution until the mixed solution is uniform to obtain a mixed solution;
step 2: uniformly dropwise adding the pore-expanding agent into the mixed solution obtained in the step (1), uniformly stirring, and standing for a period of time to obtain a white precipitate;
and step 3: putting 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 pore structure;
according to the composite material with the distributed stepped pore structure, preferably, the content of SBA-15 in the composite material is 28-44 wt%, the content of MCFs is 26-44 wt%, the pore structure of the composite carrier material is the stepped pore structure, and the pore diameter is 18-50 nm.
According to the composite material with the step hole structure distribution, the specific surface area of the composite material is preferably 480-520 m2A pore volume of 1.5 to 1.8 cm/g3And g, the aperture of 15-20 nm accounts for more than 20%, and the aperture of 48-53 nm accounts for more than 15%.
According to the preparation method of the composite material with the gradient pore structure distribution, disclosed by the invention, in the step 1, preferably, the acid environment is pH 1-3.
In the preparation method of the composite material with the distributed stepped pore 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 of the silicon source is 10-50 wt% of the template agent.
According to the preparation method of the composite material with the step pore structure distribution, disclosed by the invention, in the step 1, the heating temperature is preferably 30-60 ℃.
According to the preparation method of the composite material with the step pore 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 of the pore-expanding agent is 30-60 wt% of the template agent.
According to the preparation method of the composite material with the distributed stepped 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 h, preferably 6 h.
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 are novel mesoporous materials with ultra-large pore diameter, uniform pore size distribution, large pore volume and high specific surface, and two mesoporous materials with different pore sizes and pore channel structures are mixed or compounded with alumina powder, so that the acidity of a hydrofining catalyst can be changed, the dispersion degree of active components is improved, and the reduction vulcanization of metal components is promoted. Therefore, the preparation of the mesoporous composite carrier with high specific surface area, a 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 gradient pore structure distribution composite material provided by the invention, SBA-15 is a mesoporous material with a body-centered cubic structure; MCFs are novel mesoporous materials with ultra-large pore diameters, uniform pore diameter distribution, large pore volume and high specific surface, the pore diameters of the MCFs account for more than 20% in the range of 15-20 nm, the pore diameters of the MCFs account for more than 15% in the range of 48-53 nm, and the synergistic improvement of the hydrofining effect can be achieved.
(2) The composite material with the step pore structure distribution provided by the invention has the characteristics of large specific surface area, step pore structure, adjustable pore diameter and the like, so that the composite material is widely applied to the fields of catalysis, absorption and separation, biological medicine and the like, and is more generally applied to petroleum refining.
Drawings
FIG. 1 is a graph of the pore size distribution of the composite material of example 1 of the present invention;
FIG. 2 is an SEM image of a composite material of example 1 of the present invention.
As can be seen from FIG. 1, the pore size of the synthesized composite material has a stepped pore structure, and the distribution is relatively concentrated, and most of the pore size is 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 make the technical contents of the present invention more clearly understood, the technical contents of the present invention will be further explained below.
The invention discloses a preparation method of a composite material with step pore structure distribution. The method comprises the following steps: 1) mixing a template agent F127 or P123 with a corresponding silicon source in an acid 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 a white precipitate; 3) and (3) putting the obtained precipitate 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 pore structure. The specific surface area of the composite material is 400-600 m2A pore volume of 1.0 to 2.0cm3The pore diameter is more than 20 percent in 15-20 nm and more than 15 percent in 48-53 nm.
The invention provides a preparation method of a composite material with step pore structure distribution, which comprises the following specific preparation steps:
step 1: adding a silicon source into F127 or P123 serving as a template agent under an acidic environment, and heating and stirring the mixed solution until the mixed solution is uniform to obtain a mixed solution;
step 2: uniformly dropwise adding the pore-expanding agent into the mixed solution obtained in the step (1), uniformly stirring, and standing for a period of time to obtain a white precipitate;
and step 3: putting 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 pore 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 of the pore-expanding agent is 30-60 wt% of the template agent.
The specific surface of the composite material prepared in the step 3 is preferably 400-600 m2A pore volume of 1.0-2.0 cm3The pore diameter is more than 20 percent in 15-20 nm and more than 15 percent in 48-53 nm.
The preparation method of the composite material with the step pore structure distribution has the characteristics of large specific surface area, step pore structure, adjustable pore diameter and the like, so the composite material is widely applied to the fields of catalysis, absorption separation, biological medicine and the like, and is more generally applied to petroleum refining. For example, the catalyst is used for the hydrodesulfurization reaction of catalytic gasoline or catalytic heavy gasoline, the sulfur content of the raw material is less than 1000mg/kg, the olefin content is less than 45 v%, the sulfur content of the product blending component is less than 15mg/kg, the olefin content is reduced by less than 10 v%, and the octane number loss is less than 2.0.
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1:
preparation of MCFs-SBA-15 composite material
Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with certain concentration and 2g P123 template agent, and stirring in a water bath at 35 ℃ until a uniform solution is formed;
secondly, 30 wt% of a pore-expanding agent mesitylene of the template agent is weighed and slowly dripped into the uniform solution obtained in the first step, and water bath stirring is continued to obtain a mixed solution;
thirdly, weighing tetraethyl orthosilicate (TEOS) with the weight percent of template agent of 10 percent, slowly dripping the TEOS into the mixed solution obtained in the second step, placing the TEOS in a sealed environment, continuing to stir in water bath, then transferring the TEOS into a crystallization kettle, and placing the TEOS in a 120 ℃ oven for crystallization for 24 hours;
and fourthly, after the crystallization process is finished, taking out the crystallization kettle to carry out cooling water cooling treatment, filtering and washing the product, drying the product for about 12 hours at the temperature of 120 ℃, and roasting the product for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 2:
preparation of MCFs-SBA-15 composite material
Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with certain concentration and 2g P123 template agent, and stirring in a water bath at 35 ℃ until a uniform solution is formed;
secondly, weighing 30 wt% of template agent mesitylene as a pore-expanding agent, slowly dripping the mesitylene into the uniform solution obtained in the step I, and continuously stirring in a water bath to obtain a mixed solution;
thirdly, weighing 30 wt% of water glass of a template agent, slowly dripping the water glass into the mixed solution obtained in the second step, placing the mixed solution in a sealed environment, continuously stirring the mixed solution in a water bath, transferring the mixed solution into a crystallization kettle, and placing the crystallized solution in a 120 ℃ oven for crystallization for 24 hours;
and fourthly, after the crystallization process is finished, taking out the crystallization kettle to carry out cooling water cooling treatment, filtering and washing the product, drying the product for about 12 hours at the temperature of 120 ℃, and roasting the product for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 3:
preparation of MCFs-SBA-15 composite material
Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with certain concentration and 2g P123 template agent, and stirring in a water bath at 35 ℃ until a uniform solution is formed;
secondly, weighing 30 wt% of template agent mesitylene as a pore-expanding agent, slowly dripping the mesitylene into the uniform solution obtained in the step I, and continuously stirring in a water bath to obtain a mixed solution;
thirdly, weighing 50 wt% of sodium silicate as a template agent, slowly dropwise adding the sodium silicate into the mixed solution obtained in the second step, placing the mixed solution in a sealed environment, continuously stirring the mixed solution in a water bath, then transferring the mixed solution into a crystallization kettle, and placing the crystallized solution in a 120 ℃ oven for crystallization for 24 hours;
and fourthly, after the crystallization process is finished, taking out the crystallization kettle to carry out cooling water cooling treatment, filtering and washing the product, drying the product for about 12 hours at the temperature of 120 ℃, and roasting the product for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 4:
preparation of MCFs-SBA-15 composite material
Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with certain concentration and 2g P123 template agent, and stirring in a water bath at 35 ℃ until a uniform solution is formed;
secondly, weighing a pore-expanding agent cyclohexane with the weight percent of that of the template agent 45, slowly dripping the pore-expanding agent cyclohexane into the uniform solution obtained in the step I, and continuously stirring in a water bath to obtain a mixed solution;
thirdly, weighing tetraethyl orthosilicate (TEOS) with the weight percent of template agent of 10 percent, slowly dripping the TEOS into the mixed solution obtained in the second step, placing the TEOS in a sealed environment, continuing to stir in water bath, then transferring the TEOS into a crystallization kettle, and placing the TEOS in a 120 ℃ oven for crystallization for 24 hours;
and fourthly, after the crystallization process is finished, taking out the crystallization kettle to carry out cooling water cooling treatment, filtering and washing the product, drying the product for about 12 hours at the temperature of 120 ℃, and roasting the product for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 5:
preparation of MCFs-SBA-15 composite material
Taking P123 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with certain concentration and 2g P123 template agent, and stirring in a water bath at 35 ℃ until a uniform solution is formed;
secondly, weighing a pore-expanding agent 1,3, 5-triisopropylbenzene with the weight percent of the template agent 60% and slowly dropwise adding the pore-expanding agent into the uniform solution obtained in the first step, and continuously stirring the mixture in a water bath to obtain a mixed solution;
thirdly, weighing tetraethyl orthosilicate (TEOS) with the weight percent of template agent of 10 percent, slowly dripping the TEOS into the mixed solution obtained in the second step, placing the TEOS in a sealed environment, continuing to stir in water bath, then transferring the TEOS into a crystallization kettle, and placing the TEOS in a 120 ℃ oven for crystallization for 24 hours;
and fourthly, after the crystallization process is finished, taking out the crystallization kettle to carry out cooling water cooling treatment, filtering and washing the product, drying the product for about 12 hours at the temperature of 120 ℃, and roasting the product for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the SBA-15-MCFs composite material.
Example 6:
preparation of MCFs-SBA-15 composite material
Taking F127 as a template agent, weighing 40g of deionized water, 60g of hydrochloric acid with certain concentration and 2g F127 template agent, and stirring in a water bath at 35 ℃ until a uniform solution is formed;
secondly, weighing a pore-expanding agent 1,3, 5-triisopropylbenzene with the weight percent of the template agent 60% and slowly dropwise adding the pore-expanding agent into the uniform solution obtained in the first step, and continuously stirring the mixture in a water bath to obtain a mixed solution;
thirdly, weighing tetraethyl orthosilicate (TEOS) with the weight percent of template agent of 10 percent, slowly dripping the TEOS into the mixed solution obtained in the second step, placing the TEOS in a sealed environment, continuing to stir in water bath, then transferring the TEOS into a crystallization kettle, and placing the TEOS in a 120 ℃ oven for crystallization for 24 hours;
and fourthly, after the crystallization process is finished, taking out the crystallization kettle to carry out cooling water cooling treatment, filtering and washing the product, drying the product for about 12 hours at the temperature of 120 ℃, and roasting the product for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the SBA-15-MCFs composite material.
The composite material has the aperture of 15-20 nm accounting for more than 20 percent, the aperture of 48-53 nm accounting for more than 15 percent, and the specific surface area of 400-600 m2A pore volume of 1.0 to 2.0cm3(ii) in terms of/g. The composite material has the characteristics of large specific surface area, stepped pore structure, adjustable pore diameter and the like, so the composite material is widely applied to the fields of catalysis, absorption and separation, biological medicine and the like, and is more generally applied to petroleum refining.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention.

Claims (13)

1. The preparation method of the composite material with the step pore 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 under an acidic environment, and heating and stirring the mixed solution until the mixed solution is uniform to obtain a mixed solution;
step 2: uniformly dropwise adding the pore-expanding agent into the mixed solution obtained in the step (1), uniformly stirring, and standing to obtain a white precipitate;
and step 3: and (3) putting 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.
2. The method for preparing the composite material with the stepped pore structure distribution according to claim 1, wherein the pH value of the acidic environment in the step 1 is 1-3.
3. The method of 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 the composite material with the distribution of the stepped pore structure as claimed in claim 1, wherein the silicon source is added in an amount of 10-50 wt% of the template.
5. The method for preparing a composite material with a stepped pore structure distribution according to claim 1, wherein the heating temperature in step 1 is 30-60 ℃.
6. The method of claim 1, wherein the pore-expanding agent is at least one of hexane, cyclohexane, 1,3, 5-triisopropylbenzene and mesitylene.
7. The preparation method of the composite material with the stepped pore structure distribution according to claim 1, wherein the addition amount of the pore-expanding agent is 30-60 wt% of the template agent.
8. The method for preparing the composite material with the stepped 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.
9. The method for preparing the composite material with the stepped 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.
10. The method for preparing the composite material with the distribution of the stepped pore structure according to claim 1, wherein the roasting temperature in the step 3 is 550-750 ℃, and the roasting time is 3-6 h.
11. The method for preparing the composite material with the stepped pore structure distribution according to claim 1, wherein the content of SBA-15 in the SBA-15 and MCFs composite material is 28-44 wt%, and the content of MCFs is 26-44 wt%.
12. A composite material with a stepped pore structure distribution, which is prepared by the preparation method of the composite material with the stepped pore structure distribution as claimed in any one of claims 1 to 11, and the specific surface area of the composite material is 400-600 m2The pore diameter is 18nm to 50nm, and the pore volume is 1.0 cm to 2.0cm3And g, the aperture of 15-20 nm accounts for more than 20%, and the aperture of 48-53 nm accounts for more than 15%.
13. The composite material with the distribution of the stepped pore structure according to claim 12, wherein the specific surface area of the composite material is 480-520 m2A pore volume of 1.5 to 1.8 cm/g3/g。
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