CN102745710A - Preparation method of hierarchical pore structure titanium-silicon molecular sieve material - Google Patents
Preparation method of hierarchical pore structure titanium-silicon molecular sieve material Download PDFInfo
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- CN102745710A CN102745710A CN2011101002778A CN201110100277A CN102745710A CN 102745710 A CN102745710 A CN 102745710A CN 2011101002778 A CN2011101002778 A CN 2011101002778A CN 201110100277 A CN201110100277 A CN 201110100277A CN 102745710 A CN102745710 A CN 102745710A
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Abstract
The invention relates to a preparation method of an hierarchical pore structure titanium-silicon molecular sieve material, and aims to mainly solve the problem of difficult obtaining of a titanium-silicon molecular sieve material having macropores, mesopores and micropores in the prior art. The method of the invention adopts a technical scheme consisting of: subjecting the mixture of a phase separation inducer R1, a structure directing agent R2, a catalyst R3, an alcohol R4, an acid, water, a silicon source and an aluminum source to a hydrolysis reaction so as to obtain a titanium-silicon oxide material precursor I; conducting gelation and aging on the titanium-silicon oxide material precursor I to obtain a titanium-silicon oxide material precursor II; drying and roasting the titanium-silicon oxide material precursor II so as to obtain a mesopore/macropore composite pore structure titanium-silicon oxide III; and putting the titanium-silicon oxide material III at the upper part of a reaction kettle, adding an organic ammonium solution to the bottom of the reaction vessel, then carrying out crystallization, washing, drying and roasting, thus obtaining the hierarchical pore structure titanium-silicon molecular sieve material. The technical scheme of the invention well solves the problem, and can be used in industrial production of hierarchical pore structure titanium-silicon molecular sieve materials.
Description
Technical field
The present invention relates to a kind of preparation method of hierarchical porous structure titanium-silicon molecular screen material.
Background technology
Titanium silicon (TS-1) molecular sieve is because it has suitable acid site distribution and special characteristics such as pore structure; In epoxidation reaction of olefines, shown excellent catalytic performance, but because the problem of aspects such as pore structure, pattern and preparation method makes the application of TS-1 molecular sieve be restricted.At first be the pore structure aspect, because traditional T S-1 molecular sieve only has microvoid structure, this has greatly limited mass transfer and the diffusion of macromole such as heavy oil component in catalyzer, thereby has suppressed reactive behavior, selectivity and the life-span of catalyzer.Next is the pattern aspect; Traditional molecular sieve is a powder; Have only through complicated forming step just can be applied in the industrial production, yet the affiliation that adds of a large amount of stickers causes the obstruction in duct and the embedding of active sites in the moulding process, thereby cause the reduction of catalytic activity.Be the preparation method at last; Traditional method for preparing the TS-1 molecular sieve is a hydrothermal synthesis method; This method prepares molecular sieve process more complicated, need to use in a large number the organic amine template that can pollute environment, and needs at last just can obtain molecular sieve through numerous and diverse sepn process.
For overcoming the above problems; Recent study personnel have proposed to be equipped with gas phase crystallization legal system the idea of composite hole zeolite integral material, promptly prepare a kind of catalyzer through gas phase crystallization method, make it have integrated pattern and have two simultaneously to overlap different pore canal system (Holland B T; Abrams L; Stein A.J.Am.Chem.Soc.1999,121,4308-4309).Wherein micro-pore zeolite provides active active site for reaction, and to be material provide enough diffusion admittances in macroporous/mesoporous duct.This composite holes integral material has had high diffusion of macroporous/mesoporous material and the highly active advantage of zeolitic material simultaneously, has avoided complicated moulding process again.In addition, compare with traditional hydrothermal synthesis method, the molecular sieve and the mother liquor of gas phase crystallization method gained are direct separation, can save numerous and diverse sepn process, thereby reduce the consumption of organic formwork agent, and easy recovery and recycling organic formwork agent.In addition, gas phase crystallization method can not produce a large amount of waste liquids, and is environmentally friendly, is a kind of easy, economic method, and has been successfully applied to the preparation of multiple molecular sieve.People such as Zhao Tianbo are flooded the back through the silicone monolith with original position carbon distribution in silicone monolith or the hole and are assisted rotating crystal method to obtain micropore/macropore Si-Al molecular sieve (Yangchuan Tong by water vapour in containing the molecular sieve precursor solution in aluminium source; Tianbo Zhao; Fengyan Li; Yue Wang.Chem.Mater.2006,18,4218-4220; Qian Lei, Tianbo Zhao, Fengyan Li, Lingling Zhang, Yue Wang.Chem.Commun., 2006,1769-1771).
Although the various countries researchist develops the compound method of numerous hierarchical porous structure Si-Al molecular sieves, do not appear in the newspapers so far about the preparation of hierarchical porous structure HTS integral material.This shows that it is simple to develop a kind of preparation process, environmentally friendly and preparation method that have a hierarchical porous structure HTS integral material of better mass-transfer performance realizes and enlarges its actual key in application place.
Summary of the invention
Technical problem to be solved by this invention be difficult to obtain to have macropore simultaneously in the prior preparation method, the problem of the amorphous ti silica integral material of mesoporous and micropore, a kind of preparation method of new hierarchical porous structure HTS integral material is provided.This method can prepare have macropore simultaneously, mesoporous and micropore the amorphous ti silica integral material.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of hierarchical porous structure HTS integral material may further comprise the steps:
A) will be separated the mixture in inductor R1, structure directing agent R2, catalyzer R3, pure R4, acid, water, silicon source and titanium source under 0～40 ℃ of condition hydrolysis reaction 5～60 minutes amorphous ti silica material presoma I, the mixture weight ratio consists of: R1/SiO
2=0.01～1.0, R2/SiO
2=0.3～2.5, R3/SiO
2=0～0.1, R4/SiO
2=0～10, H
2O/SiO
2=3.0～20, H
+/ SiO
2=0.01～0.45, TiO
2/ SiO
2=0.002～0.4;
B) above-mentioned amorphous ti silica material presoma I gel under 30～100 ℃ of temperature is aging, aging 2～96 hours, obtain amorphous ti silica material presoma II;
C) amorphous ti silica material presoma II makes amorphous ti silica material III after drying, roasting;
D) amorphous ti silica material III is placed the top of reaction kettle, the reaction kettle bottom adds organic amine solution, 100～200 ℃ of following crystallization after 0.5～12 day; To sample wash, drying and roasting obtain hierarchical porous structure HTS integral material;
The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, T 46155 or polyethylene oxide at least a, its molecular-weight average is 3000～100000;
Structure directing agent R2 is selected from triblock copolymer, chain alkyl trimethylammonium halogenation ammonia ((CH
3)
nN
+(CH
3)
3X
-), at least a in Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid; Wherein triblock copolymer is a polyoxyethylene-poly-oxypropylene polyoxyethylene, and its molecular-weight average is 1500～12000; The carbon chain lengths of chain alkyl trimethylammonium halogenation ammonia is 8～18, and X is Cl or Br;
Catalyzer R3 is selected from least a in Neutral ammonium fluoride, Potassium monofluoride, ammonium chloride, ammonium phosphate, the volatile salt;
Alcohol R4 is selected from least a in Virahol, the isopropylcarbinol;
Acid is selected from least a in nitric acid, phosphoric acid, hydrochloric acid or the acetic acid.
In the technique scheme, silicon source preferred version is to be selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate, positive silicic acid four butyl esters.Titanium source preferred version is at least a for being selected from titanous chloride, titanium isopropylate or the titanium isobutoxide.Mixture weight than forming preferable range is in the step a): R1/SiO
2=0.02～0.9, R2/SiO
2=0.25～2.4, R3/SiO
2=0.001～0.9, H
2O/SiO
2=2.9～19, H
+/ Si0
2=0.02～0.40, TiO
2/ SiO
2=0.003～0.35.Gel aging temperature preferable range is 40～80 ℃ in the step b), and the digestion time preferable range is 12～72 hours.In the step c), the drying temperature preferable range is 25～80 ℃, and time of drying, preferable range was 1～7 day; The maturing temperature preferable range is 550～800 ℃, and the roasting time preferable range is 2～10 hours.Organic amine template preferred version is at least a in tetrapropyl oxyammonia, 4-propyl bromide, triethylamine or the quadrol in the step d).The crystallization temperature preferable range is 120～180 ℃ in the step d), and the crystallization time preferable range is 1～10 day.
In the inventive method, I puts in the mould of random shape with amorphous ti silica material presoma, just can obtain the composite holes amorphous ti silica integral material of respective shapes.
At present, the molecular sieve integral material of hierarchical porous structure mainly concentrates on the sieve and silica-sesquioxide, reports less for the preparation method of the amorphous ti silica molecular sieve integral material of hierarchical porous structure.The present invention at first makes the amorphous amorphous ti silica integral material with co-continuous macroporous structure through sol-gel method; Then with the hole wall zeolitization; Obtain forming certain hierarchical porous structure HTS integral material; And through regulating the humidity of crystallization process, crystallization time and temperature can obtain the molecular sieve integral material of different crystallization degrees.The material specific surface area that this method obtains is up to 670～1000 meters
2/ gram, pore volume is 0.6～1.5 meter
2/ gram, wherein micropore size is distributed as 0.2～0.9 nanometer; Mesoporous pore size distribution is 2～40 nanometers; Macropore diameter is distributed as 0.5～40 micron.It is simple that this method prepares process, control easily, and the percent crystallinity height has been obtained better technical effect.
Description of drawings
ESEM (SEM) photo of the composite pore structural titanium-silicon molecular screen material that Fig. 1 obtains for [embodiment 1].
X diffraction (XRD) collection of illustrative plates of the composite pore structural titanium-silicon molecular screen material that Fig. 2 obtains for [embodiment 1].
The UV spectrum of the composite pore structural titanium-silicon molecular screen material that Fig. 3 obtains for [embodiment 1].
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
In the salpeter solution of 0.1mol/L, add 1g triblock copolymer P123, stir under the room temperature that to add the 0.4g molecular weight behind the 1h be 10000 polyoxyethylene glycol (PEG) and a spot of ammonium fluoride, after stirring it is cooled to 0 ℃.In mixing solutions, add the methyl silicate (TMOS) and the aqueous isopropanol that contains the calculated amount titanium isopropylate of 5ml then, behind the vigorous stirring 10min, mixed solution is poured in the mould of sealing, leave standstill the 48h that wears out at 60 ℃.After handling through the demoulding, washing, drying etc. then,, obtain mesopore/macropore amorphous ti silica integral material at 450 ℃ of roasting 5h; Be placed on the top of reaction kettle then, reaction kettle bottom adds organic amine solution, 150 ℃ of following crystallization after 3 days; To sample wash, drying and roasting obtain hierarchical porous structure HTS integral material.
The weight ratio of each component is: R1/SiO
2=0.2, R2/SiO
2=05, R3/SiO
2=0.005, R4/SiO
2=2, H
2O/SiO
2=5, H
+/ SiO
2=0.05, TiO
2/ SiO
2=0.01.
[embodiment 2～28]
According to each Step By Condition of [embodiment 1], make composite pore structural amorphous ti silica material, just change parameters such as raw material (table 1) proportioning, gel aging temperature, crystallization temperature, crystallization time, specifically list in table 1.The synthetic product has and the similar crystalline structure of [embodiment 1] product through characterizing its result of explanation, and its concrete reaction conditions is seen table 2.
Claims (8)
1. the preparation method of a hierarchical porous structure titanium-silicon molecular screen material may further comprise the steps:
A) will be separated the mixture in inductor R1, structure directing agent R2, catalyzer R3, pure R4, acid, water, silicon source and titanium source under 0～40 ℃ of condition hydrolysis reaction 5～60 minutes amorphous ti silica material presoma I, the mixture weight ratio consists of: R1/SiO
2=0.01～1.0, R2/SiO
2=0.3～2.5, R3/SiO
2=0～0.1, R4/SiO
2=0～10, H
2O/SiO
2=3.0～20, H
+/ SiO
2=0.01～0.45, TiO
2/ SiO
2=0.002～0.4;
B) above-mentioned amorphous ti silica material presoma I gel under 30～100 ℃ of temperature is aging, aging 2～96 hours, obtain amorphous ti silica material presoma II;
C) amorphous ti silica material presoma II makes amorphous ti silica material III after drying, roasting;
D) amorphous ti silica material III is placed the top of reaction kettle, the reaction kettle bottom adds organic amine solution, 100～200 ℃ of following crystallization after 0.5～12 day; To sample wash, drying and roasting obtain hierarchical porous structure HTS integral material;
The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, T 46155 or polyethylene oxide at least a, its molecular-weight average is 3000～100000;
Structure directing agent R2 is selected from triblock copolymer, chain alkyl trimethylammonium halogenation ammonia ((CH
3)
nN
+(CH
3)
3X
-), at least a in Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid; Wherein triblock copolymer is a polyoxyethylene-poly-oxypropylene polyoxyethylene, and its molecular-weight average is 1500～12000; The carbon chain lengths of chain alkyl trimethylammonium halogenation ammonia is 8～18, and X is Cl or Br;
Catalyzer R3 is selected from least a in Neutral ammonium fluoride, Potassium monofluoride, ammonium chloride, ammonium phosphate, the volatile salt;
Alcohol R4 is selected from least a in Virahol, the isopropylcarbinol;
Acid is selected from least a in nitric acid, phosphoric acid, hydrochloric acid or the acetic acid.
2. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that the silicon source is selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters.
3. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that the titanium source is at least a in titanium tetrachloride, titanous chloride, titanium isopropylate or the titanium isobutoxide.
4. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that the mixture weight ratio consists of in the step a): R1/SiO
2=0.01～1.0, R2/SiO
2=0.3～2.5, R3/SiO
2=0～0.1, H
2O/SiO
2=3.0～20, H
+/ SiO
2=0.01～0.45, TiO
2/ SiO
2=0.002～0.4.
5. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that the gel aging temperature is 40～80 ℃ in the step b), digestion time is 12～72 hours.
6. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that in the step c) that drying temperature is 25～80 ℃, be 1～7 day time of drying; Maturing temperature is 550～800 ℃, and roasting time is 2～10 hours.
7. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that organic amine template in the step d) is selected from least a in tetrapropyl oxyammonia, 4-propyl bromide, triethylamine or the quadrol.
8. according to the preparation method of the said hierarchical porous structure HTS of claim 1 integral material, it is characterized in that crystallization temperature is 100～200 ℃ in the step d), crystallization time is 0.5～12 day.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104445257A (en) * | 2014-11-25 | 2015-03-25 | 河北美邦工程科技有限公司 | Preparation method for high-stable-activity titanium silicalite molecular sieve catalyst |
| CN105289738A (en) * | 2015-11-26 | 2016-02-03 | 上海师范大学 | Chiral ethylenediamine Ru complex modified polyethylene glycol functional meso-porous silicon nanospheres and preparation method thereof |
| CN106745037A (en) * | 2016-11-18 | 2017-05-31 | 长江大学 | A kind of multi-stage porous titanium si molecular sieves and preparation method thereof |
| CN108529643A (en) * | 2018-06-14 | 2018-09-14 | 辽宁科技大学 | A method of preparing titanium doped mesopore molecular sieve |
| CN108993610A (en) * | 2018-07-10 | 2018-12-14 | 大连理工大学 | The preparation method and its usage of the amorphous mesoporous titanium-silicon material of hybrid inorganic-organic |
| CN110194465A (en) * | 2019-05-31 | 2019-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nanometer hierarchical pore TS-1 molecular sieve and products thereof and application |
| CN112744834A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Titanium-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method |
-
2011
- 2011-04-20 CN CN201110100277.8A patent/CN102745710B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 杨贺勤: "复合孔结构整体材料的制备、表征及应用", 《中国博士学位论文全文数据库》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104445257A (en) * | 2014-11-25 | 2015-03-25 | 河北美邦工程科技有限公司 | Preparation method for high-stable-activity titanium silicalite molecular sieve catalyst |
| CN105289738A (en) * | 2015-11-26 | 2016-02-03 | 上海师范大学 | Chiral ethylenediamine Ru complex modified polyethylene glycol functional meso-porous silicon nanospheres and preparation method thereof |
| CN106745037A (en) * | 2016-11-18 | 2017-05-31 | 长江大学 | A kind of multi-stage porous titanium si molecular sieves and preparation method thereof |
| CN108529643A (en) * | 2018-06-14 | 2018-09-14 | 辽宁科技大学 | A method of preparing titanium doped mesopore molecular sieve |
| CN108529643B (en) * | 2018-06-14 | 2020-01-03 | 辽宁科技大学 | Method for preparing titanium-doped mesoporous molecular sieve |
| CN108993610A (en) * | 2018-07-10 | 2018-12-14 | 大连理工大学 | The preparation method and its usage of the amorphous mesoporous titanium-silicon material of hybrid inorganic-organic |
| CN110194465A (en) * | 2019-05-31 | 2019-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nanometer hierarchical pore TS-1 molecular sieve and products thereof and application |
| CN112744834A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Titanium-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method |
| CN112744834B (en) * | 2019-10-30 | 2022-07-15 | 中国石油化工股份有限公司 | Titanium-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method |
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