CN102247875A - Preparation method of heteropoly acid / alumina mesoporous composite material - Google Patents
Preparation method of heteropoly acid / alumina mesoporous composite material Download PDFInfo
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- CN102247875A CN102247875A CN 201010180185 CN201010180185A CN102247875A CN 102247875 A CN102247875 A CN 102247875A CN 201010180185 CN201010180185 CN 201010180185 CN 201010180185 A CN201010180185 A CN 201010180185A CN 102247875 A CN102247875 A CN 102247875A
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Abstract
The invention relates to a preparation method of a heteropoly acid / alumina mesoporous composite material, which is characterized in that the method comprises the following steps: dissolving aluminum isopropoxide in anhydrous alcohol, adjusting the pH value by nitric acid, adding heteropoly acid; stirring at room temperature for 4-8 hours to obtain a solution (1); dissolving a polyoxyethylene- polyoxypropylene-polyoxyethylene triblock copolymer (P123) into anhydrous alcohol to obtain a solution (2); slowly adding the solution (2) into the solution (1), stirring for 4-8 hours to obtain a uniform sol; pouring the sol into a culture dish, preserving the culture dish at 60 DEG C for 36-58 hours to obtain a light yellow film sample, grinding the sample, calcining at 400-420 DEG C for 2-3 days to obtain the heteropoly acid / alumina mesoporous composite material. The invention can effectively protect the heteropoly acid structure from being destroyed, and the material prepared by the invention has the characteristics of high activity, good selectivity, easy separation and recovery, and recyclability, and can be used as a catalyst for fuel oil deep oxidation and desulphurization in the petroleum chemical industry field.
Description
Technical field:
The present invention relates to the preparation method of a kind of heteropoly acid/aluminium oxide mesoporous composite material, belong to petrochemical industry fuel oil deep oxidation desulfurization catalyst preparing technical field.
Background technology:
Institute's sulfur compound is the important pollution sources of urban atmosphere in the fuel oil, along with the 21 century people to the improving constantly of environmental protection requirement, make laws one after another the sulfur content in the fuel oil made strict regulations in countries in the world.Traditional hydrodesulfurization technology is very limited to the ability that removes of high-load benzothiophene, dibenzothiophenes and derivative thereof in the fuel oil, its reason mainly be since these sulfide molecules have high sterically hindered, inaccessible catalytic active center.In order to satisfy the requirement of low sulfuration, need to adopt high temperature, high pressure, bigger reaction vessel and have more active catalyst, will improve the production cost of finished product fuel oil greatly.Therefore, explore and the non-efficiently hydrogenated fuel oil of exploitation deep desulfuration technology, reach the fuel oil quality standard of hanging down sulfuration and not having sulfuration as early as possible and have important practical significance.
Oxidative desulfurization techniques is in recent years by a kind of non-hydrodesulfurization technology of extensive concern, it can carry out at normal temperatures and pressures, equipment investment is few, and more oxidized because substituting group dibenzothiophenes compounds has higher sulphur atom cloud density, thereby this method is considered to a kind of up-and-coming deep desulfuration technology.In recent years, the research system of oxidation sweetening has obtained widely expanding, and heteropoly acid is as the homogeneous oxidizing desulphurization catalyst, have the characteristics of efficient, cleaning and enjoy favor, yet in homogeneous catalytic reaction, the recovery of catalyst and regeneration is difficulty quite.Heteropoly acid is immobilized on appropriate carriers, then can realize heterogeneousization of homogeneous reaction.In addition, because the difficult sulfide that removes all is larger molecular organics in the fuel oil, catalyst must have enough big aperture can be near catalytic active center to satisfy organic sulfur compound.Therefore heteropoly acid is fixed on the complex mesoporous material for preparing on the mesoporous carrier and not only can improves the stability of heteropoly acid, and make composite possess the characteristic of heteropoly acid and mesoporous material larger aperture, duct queueing discipline, the narrow characteristics of pore-size distribution simultaneously.
Yet, present for the complex method of heteropoly acid and meso-porous alumina still based on traditional infusion process, this method often causes the destructurized of heteropoly acid owing to the strong excessively surface acidity of meso-porous alumina, thereby causes its catalytic activity to reduce, and can not adapt to the demand of practical application.
Summary of the invention:
In order to overcome the deficiencies in the prior art; the object of the present invention is to provide the preparation method of a kind of heteropoly acid/aluminium oxide mesoporous composite material; it at first prepares heteropoly acid and alumina precursor complex sol; self assembling process by the template agent prepares heteropoly acid/aluminium oxide mesoporous composite material then; thereby effectively protect the structure of heteropoly acid not to be destroyed, have high activity, selectivity good, be easy to separate reclaim, reusable characteristics.
The present invention realizes above-mentioned purpose by following technical solution.
The preparation method of a kind of heteropoly acid provided by the present invention/aluminium oxide mesoporous composite material comprises the steps:
1), aluminium isopropoxide is dissolved in the absolute ethyl alcohol, the pH value with the red fuming nitric acid (RFNA) regulator solution adds a certain amount of heteropoly acid then, at room temperature stirs 4--8 hour, obtains solution (1);
2), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) is dissolved in the absolute ethyl alcohol, obtain solution (2);
3), with above-mentioned steps 2) in the solution (2) that obtains slowly pour in the solution (1) that obtains in the step 1), continue to stir and obtained even colloidal sol in 4--8 hour;
4), the colloidal sol of gained is poured in the culture dish, preserved 36--48 hour for 60 ℃, obtain faint yellow film sample, sample is ground back calcining 2--3 days under 400-420 ℃ of condition, heating rate is 1--2.5 ℃/min; Promptly obtain heteropoly acid/aluminium oxide mesoporous composite material, its average pore size is 3--4nm, and specific area is 150--170m
2/ g.
Described heteropoly acid is a kind of in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, the silicomolybdic acid.
The percentage by weight of each component is in the described solution (1):
Aluminium isopropoxide: 10.2--13.8%;
Absolute ethyl alcohol: 76--82.3%;
Red fuming nitric acid (RFNA): 6.7--9.3%;
Heteropoly acid: 0.4--1.1%.
The percentage by weight of each component is in the described solution (2):
P123：14.1--20.8％；
Absolute ethyl alcohol: 79.2--85.9%.
Described solution (1) with the percentage by weight of (2) two kinds of each components that solution mixes of solution is:
Solution (1): 73.2--76.9%;
Solution (2): 23.1--26.8%.
The present invention has following beneficial effect compared with prior art:
The present invention at first prepares heteropoly acid and alumina precursor complex sol; self assembling process by the template agent prepares heteropoly acid/aluminium oxide mesoporous composite material then; thereby effectively protect the structure of heteropoly acid not to be destroyed; have high activity, selectivity good, be easy to separate reclaim, reusable characteristics, can be used as the catalyst of petrochemical industry fuel oil deep oxidation desulfurization.
The specific embodiment:
In order to understand the present invention better, the invention will be further described below in conjunction with specific embodiment:
Embodiment 1:
The 4.09g aluminium isopropoxide is dissolved in the 30g ethanol solution, adds 2.6g nitre acid for adjusting pH value, treat that aluminium isopropoxide dissolves the back fully and adds the 0.28g phosphotungstic acid, stirred 6 hours under the room temperature, obtain solution (1); Again 1.85g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) is dissolved in the 10g absolute ethyl alcohol, gets solution (2); Then solution (2) is slowly poured in the solution (1); Continue stirring and obtained even colloidal sol in 5 hours; At last gained colloidal sol is poured in the culture dish, preserved 48h for 60 ℃ and get faint yellow film sample; After the sample grinding, calcining is 3 days under 420 ℃ of conditions, promptly obtains containing the heteropoly acid/aluminium oxide mesoporous composite material of phosphotungstic acid.The average pore size of heteropoly acid/aluminium oxide mesoporous composite material is 3.2nm, and specific area is 160m
2/ g.
Embodiment 2:
The 2.0g aluminium isopropoxide is dissolved in the 16g ethanol solution, adds 1.5g nitre acid for adjusting pH value, treat that aluminium isopropoxide dissolves the back fully and adds the 0.15g phosphomolybdic acid, stirred 5 hours under the room temperature, get solution (1); Again 0.96g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) is dissolved in the 5g absolute ethyl alcohol, gets solution (2); Then solution (2) is slowly poured in the solution (1); Continue stirring and obtained even colloidal sol in 5 hours; At last gained colloidal sol is poured in the culture dish, preserved 48h for 60 ℃ and get faint yellow film sample; After the sample grinding, calcining is 3 days under 420 ℃ of conditions, promptly obtains containing the heteropoly acid/aluminium oxide mesoporous composite material of phosphomolybdic acid.The average pore size of heteropoly acid/aluminium oxide mesoporous composite material is 3.5nm, and specific area is 152m
2/ g.
Embodiment 3:
The 8.12g aluminium isopropoxide is dissolved in the 60g ethanol solution, adds 5.4g nitre acid for adjusting pH value, treat that aluminium isopropoxide dissolves the back fully and adds the 0.55g silico-tungstic acid, stirred 6 hours under the room temperature, get solution (1); Again 4.0g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) is dissolved in the 20g absolute ethyl alcohol, gets solution (2); Then solution (2) is slowly poured in the solution (1); Continue stirring and obtained even colloidal sol in 6 hours; At last gained colloidal sol is poured in the culture dish, preserved 36h for 60 ℃ and get faint yellow film sample; After the sample grinding, calcining is 3 days under 410 ℃ of conditions, promptly obtains containing the heteropoly acid/aluminium oxide mesoporous composite material of silico-tungstic acid.The average pore size of heteropoly acid/aluminium oxide mesoporous composite material is 3.0nm, and specific area is 162m
2/ g.
Embodiment 4:
The 4.09g aluminium isopropoxide is dissolved in the 32g ethanol solution, adds 3.0g nitre acid for adjusting pH value, treat that aluminium isopropoxide dissolves the back fully and adds the 0.30g silicomolybdic acid, stirred 6 hours under the room temperature, get solution (1); Again 1.90g polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) is dissolved in the 10g absolute ethyl alcohol, gets solution (2); Then solution (2) is slowly poured in the solution (1); Continue stirring and obtained even colloidal sol in 6 hours; At last gained colloidal sol is poured in the culture dish, preserved 48h for 60 ℃ and get faint yellow film sample; After the sample grinding, calcining is 3 days under 420 ℃ of conditions, promptly obtains containing the heteropoly acid/aluminium oxide mesoporous composite material of silicomolybdic acid.The average pore size of heteropoly acid/aluminium oxide mesoporous composite material is 3.3nm, and specific area is 158m
2/ g.
Embodiment 5:
0.20g among the embodiment 1 heteropoly acid/aluminium oxide mesoporous composite material is joined 20ml contain in the octane solution of dibenzothiophenes of 500 μ g/g sulphur, add the 20ml acetonitrile again, add 250 μ L, 30% hydrogen peroxide simultaneously as extraction phase; Final mixture is stirred 2h at 60 ℃ of constant temperature; After reaction finished, oil product separated after filtration, got the sample on upper strata; Wash with acetonitrile after the catalyst recovery; And sample is used for gas chromatographic analysis measures last sulfur content.The sulfur content of reaction back dibenzothiophenes is 5 μ g/g, and promptly the conversion ratio of dibenzothiophenes is 99.0%.
Embodiment 6:
0.20g among the embodiment 1 heteropoly acid/aluminium oxide mesoporous composite material is joined 20ml to be contained in the solution of the octane of dibenzothiophenes of 500 μ g/g sulphur and benzene (octane and benzene volume ratio are 5: 1), add the 20ml acetonitrile again as extraction phase, add 250 μ L, 30% hydrogen peroxide simultaneously; Final mixture is stirred 3h at 60 ℃ of constant temperature; After reaction finished, oil product separated after filtration, got the sample on upper strata; Wash with acetonitrile after the catalyst recovery; And sample is used for gas chromatographic analysis measures last sulfur content.The sulfur content of reaction back dibenzothiophenes is 15 μ g/g, and promptly the conversion ratio of dibenzothiophenes is 97.0%.
Claims (5)
1. the preparation method of heteropoly acid/aluminium oxide mesoporous composite material is characterized in that comprising the steps:
1), aluminium isopropoxide is dissolved in the absolute ethyl alcohol, the pH value with the red fuming nitric acid (RFNA) regulator solution adds a certain amount of heteropoly acid then, at room temperature stirs 4--8 hour, obtains solution (1);
2), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (P123) is dissolved in the absolute ethyl alcohol, obtain solution (2);
3), with above-mentioned steps 2) in the solution (2) that obtains slowly pour in the solution (1) that obtains in the step 1), continue to stir and obtained even colloidal sol in 4--8 hour;
4), the colloidal sol of gained is poured in the culture dish, preserved 36--48 hour for 60 ℃, obtain faint yellow film sample, sample is ground back calcining 2--3 days under 400-420 ℃ of condition, heating rate is 1--2.5 ℃/min; Promptly obtain heteropoly acid/aluminium oxide mesoporous composite material, its average pore size is 3--4nm, and specific area is 150--170m
2/ g.
2. the preparation method of a kind of heteropoly acid according to claim 1/aluminium oxide mesoporous composite material is characterized in that described heteropoly acid is a kind of in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, the silicomolybdic acid.
3. the preparation method of a kind of heteropoly acid according to claim 1/aluminium oxide mesoporous composite material is characterized in that the percentage by weight of each component in the described solution (1) is: aluminium isopropoxide: 10.2--13.8%; Absolute ethyl alcohol: 76--82.3%; Red fuming nitric acid (RFNA): 6.7--9.3%; Heteropoly acid: 0.4--1.1%.
4. the preparation method of a kind of heteropoly acid according to claim 1/aluminium oxide mesoporous composite material is characterized in that the percentage by weight of each component in the described solution (2) is: P123:14.1--20.8%; Absolute ethyl alcohol: 79.2--85.9%.
5. the preparation method of a kind of heteropoly acid according to claim 1/aluminium oxide mesoporous composite material is characterized in that the percentage by weight of (2) two kinds of each components that solution mixes of described solution (1) and solution is: solution (1): 73.2--76.9%; Solution (2): 23.1--26.8%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071449A (en) * | 2013-02-01 | 2013-05-01 | 武汉理工大学 | Preparation method and application of amino-functionalized mesoporous alumina-based bifunctional adsorbent |
| CN106984303A (en) * | 2017-04-28 | 2017-07-28 | 武汉理工大学 | A kind of mesoporous γ Al of grade hole macropore for supporting noble metal2O3Catalyst and preparation method thereof |
| CN110227429A (en) * | 2019-05-13 | 2019-09-13 | 广东工业大学 | A kind of difunctional solid catalyst of soda acid and its preparation method and application |
| CN111135865A (en) * | 2020-01-18 | 2020-05-12 | 燕山大学 | Preparation method of phosphotungstic acid modified MOFs-derived porous carbon oxidative desulfurization catalyst |
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| CN101289358A (en) * | 2008-05-23 | 2008-10-22 | 浙江工业大学 | Method for synthesizing linear alkylbenzene |
| WO2009136870A1 (en) * | 2008-05-05 | 2009-11-12 | Nanyang Technological University | Proton exchange membrane for fuel cell applications |
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2010
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| WO2009136870A1 (en) * | 2008-05-05 | 2009-11-12 | Nanyang Technological University | Proton exchange membrane for fuel cell applications |
| CN101289358A (en) * | 2008-05-23 | 2008-10-22 | 浙江工业大学 | Method for synthesizing linear alkylbenzene |
Non-Patent Citations (1)
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| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20080915 赵晓鹏 介孔材料固载磷钨酸机理及其催化氧化脱硫性能 第6.1.3节、表6-1 1-5 , 第09期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071449A (en) * | 2013-02-01 | 2013-05-01 | 武汉理工大学 | Preparation method and application of amino-functionalized mesoporous alumina-based bifunctional adsorbent |
| CN103071449B (en) * | 2013-02-01 | 2014-10-01 | 武汉理工大学 | Preparation method and application of amino-functionalized mesoporous alumina-based bifunctional adsorbent |
| CN106984303A (en) * | 2017-04-28 | 2017-07-28 | 武汉理工大学 | A kind of mesoporous γ Al of grade hole macropore for supporting noble metal2O3Catalyst and preparation method thereof |
| CN106984303B (en) * | 2017-04-28 | 2019-09-10 | 武汉理工大学 | A kind of foramen magnum-mesoporous γ-Al in grade hole supporting noble metal2O3Catalyst and preparation method thereof |
| CN110227429A (en) * | 2019-05-13 | 2019-09-13 | 广东工业大学 | A kind of difunctional solid catalyst of soda acid and its preparation method and application |
| CN111135865A (en) * | 2020-01-18 | 2020-05-12 | 燕山大学 | Preparation method of phosphotungstic acid modified MOFs-derived porous carbon oxidative desulfurization catalyst |
| CN111135865B (en) * | 2020-01-18 | 2021-06-22 | 燕山大学 | Preparation method of phosphotungstic acid modified MOFs-derived porous carbon oxidative desulfurization catalyst |
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Application publication date: 20111123 |