CN1299986C - Organic and inorganic carbon hybridized silicon zeolite solid acid cellular material and its prepn - Google Patents
Organic and inorganic carbon hybridized silicon zeolite solid acid cellular material and its prepn Download PDFInfo
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- CN1299986C CN1299986C CNB2004100890372A CN200410089037A CN1299986C CN 1299986 C CN1299986 C CN 1299986C CN B2004100890372 A CNB2004100890372 A CN B2004100890372A CN 200410089037 A CN200410089037 A CN 200410089037A CN 1299986 C CN1299986 C CN 1299986C
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- zeolite
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Abstract
The present invention relates to novel full silicon organic and inorganic carbon hybridization zeolite solid acid and a preparation method thereof, which belongs to the technical field of a microporous material. The material is obtained in a mode that a full silicon zeolite molecular sieve is mixed with an aldehyde solution or solid to carry out hydrothermal reaction or gas/solid phase reaction, and an aldehyde group partially replaces framework oxygen. The solid acidity of a novel catalyzing material and the property of a pore canal can be regulated and controlled by changing the length of an alkyl group carbon chain of the C1-C3 of aldehyde and the structure of base zeolite, and therefore, the requirement for the acidity of the material, a pore structure and surface property in practical application is satisfied. The material has the advantages of mild synthetic condition, good repetitiveness, simple and convenient preparation, low price and no environmental pollution, and is suitable for industrialized production.
Description
Technical field
The invention belongs to the poromerics technical field, be specifically related to a kind of novel total silicon organic inorganic hybridization zeolite solid acid and preparation method thereof.This material has wide application prospects at aspects such as catalysis, absorption and alkalescence separation.
Background technology
Traditional solid acid comprises a variety of, such as naturally occurring clay class mineral and zeolite, metal oxides such as silicon oxide, aluminum oxide, inorganic substance such as sulfide, vitriol, nitrate.They all have different acid sitess and different selectivity as an acidic catalyst.The acid sites of aluminum oxide is because there are two acid maximum value in the incomplete coordinate aluminium atom that dehydration forms about 773K and 993K; The acid sites of zeolite mainly is the Br nsted acid position and the Lewis acid position of skeleton, and the difference of wherein cationic difference and silica alumina ratio can cause different strength of acid.Usually by introducing other central atom or alkaline earth metal cation, solid acid that can the modulation zeolite.But the introducing of inorganic atoms is easy to cause the pollution of catalyst system on the one hand, and mineral ion is easy to run off in the aqueous solution on the other hand, so can cause the instability of zeolite acidity.
In the last few years since organic inorganic hybridization ordered mesoporous material (PMOs) in catalysis, ion-exchange, semi-conductor, the widespread use of aspects such as chemical sensitisation and nano molecular sieve and receive more and more people's concern.The introducing of organic group can change a lot of character of material, such as fractionation by adsorption character, and character such as surface properties even electrochemistry and machinery.
Report such as Shiyou Guan (J.Am.Chem.Soc.2000,122,5660-5661) with containing BTME ((CH
3O)
3Si-CH
2-CH
2-Si (OCH
3)
3)-ATME (C
nH
2n+1N
+(CH
3)
3)-NaOH-H
2The system of O has been synthesized in the 368K original position and has been contained (Si-CH
2-CH
2-Si) the organic inorganic hybridization mesopore molecular sieve of structure.But do not reporting special nature aspect the acid matter.
All different with traditional solid acid zeolite and organic inorganic hybridization ordered mesoporous material, but total silicon organic inorganic hybridization zeolite solid acid had both had the stable solid acid of modulation and good pore passage structure, simultaneously since its acid sites with above the two is all different, can not take place to pollute and loss.Have high reactivity, highly selective, reaction conditions gentleness, product as catalyzer and be easy to advantages such as separation, be expected to become environmental friendliness catalytic material of new generation.Has very strong application prospect in absorption with aspects such as alkaline organic molecule separate.
Summary of the invention
The objective of the invention is to propose that a kind of catalytic performance is good, the novel total silicon organic inorganic hybridization zeolite solid acid of low cost of manufacture and preparation method thereof.
The total silicon organic inorganic hybridization zeolite solid acid that the present invention proposes is that the skeleton oxygen that contains 1-20% in the oxygen total silicon poromerics is substituted by the aldehydes organo-functional group and obtains, and wherein aldehyde radical is RCHO, and R is C here
0-C
2Hydro carbons, as formaldehyde, propionic aldehyde etc.
In the above-mentioned total silicon organic inorganic hybridization zeolite solid acid, described skeleton contains the not aluminiferous total silicon zeolite molecular sieve that oxygen total silicon poromerics is meant crystalline state.
The preparation method of above-mentioned total silicon organic inorganic hybridization zeolite solid acid cellular material is as follows:
The oxygen containing total silicon microporous substrate of skeleton material is mixed with the solid or the solution of organic carbon hydridization agent-aldehydes, place reactor to carry out hydro-thermal reaction, temperature 20-200 ℃, time 1.5-50 hour, obtain the total silicon zeolite solid acid cellular material.
The solid or the solution of the agent of aldehydes hydridization are placed the reactor bottom, and base material places the upper strata, and the steam and the base material generation gas/solid state reaction that produce when utilizing heating are prepared into the total silicon zeolite solid acid cellular material.
In the aforesaid method, the oxygen containing total silicon microporous substrate of described skeleton material can adopt commodity total silicon zeolite molecular sieve, for example: base material and aldehydes organic carbon hydridization agent hydro-thermal reaction or generation gas/solid state reactions such as total silicon MF1 zeolite, Framework of Siliceous FER zeolite make organic and inorganic carbon hybridized silicon zeolite solid acid cellular material.MFI zeolite with the formaldehyde effect is an example, and as Fig. 1, shown in 2,3, the MFI zeolite after the effect has kept perfect skeleton and open duct, NH
3-TPD proves that it has very strong acid matter.
Poromerics of the present invention has many superiority such as high reactivity, highly selective, reaction conditions gentleness, product be easily separated as catalyzer, adsorption separating agent.
Preparation methods of the present invention is easy, the reaction conditions gentleness, and production cost is low, and the total silicon organic inorganic hybridization zeolite solid acid that obtains can be used as catalyzer, sorbent material and alkaline separating agent, and is applied widely, has favorable industrial application prospect.
Description of drawings
Fig. 1 is the XRD figure of MFI type zeolite after the formaldehyde effect.
Fig. 2 is the NH of MFI zeolite after the formaldehyde effect
3-TPD figure.
Fig. 3 is the normal hexane absorption figure of MFI zeolite after the formaldehyde effect.
Embodiment
Further describe the present invention below by embodiment:
Embodiment 1:
Substrate all-silica MFI type zeolite according to the following steps with the formaldehyde effect, preparation all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid:
1, the solid with polyoxymethylene adds thermal depolymerization at 90 ℃～150 ℃, collects with liquid nitrogen.
2, the steam importing with formaldehyde monomers fills in the container of all-silica MFI zeolite, and room temperature reaction 2h obtains reaction product, and reaction product is washed after filtration, and oven dry obtains all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 2:
Substrate MFI type zeolite according to the following steps with the formaldehyde effect, preparation all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid:
1, the solid with polyoxymethylene places the reactor bottom, and base material places the upper strata, and the centre separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 3:
Substrate MFI type zeolite according to the following steps with the acetaldehyde effect, preparation all-silica MFI type zeolite solid acid:
1, the solution of acetaldehyde is mixed with all-silica MFI type zeolite places reactor.Or the solution of acetaldehyde placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 4:
Substrate MFI type zeolite according to the following steps with the propionic aldehyde effect, preparation all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid:
1, the solution of propionic aldehyde is mixed with all-silica MFI type zeolite places reactor.Or the solution of propionic aldehyde placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains all-silica MFI type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 5:
Substrate FER type zeolite according to the following steps with the formaldehyde effect, preparation Framework of Siliceous FER type organic and inorganic carbon hydridization solid acid:
1, the solid of polyoxymethylene adds thermal depolymerization at 90 ℃～150 ℃, collects with liquid nitrogen.
2, the steam importing with formaldehyde monomers fills in the container of Framework of Siliceous FER type zeolite, and room temperature is carried out absorption reaction 2h and obtained reaction product, and reaction product is washed after filtration, and oven dry obtains Framework of Siliceous FER type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 6:
Substrate FER type zeolite according to the following steps with the formaldehyde effect, preparation Framework of Siliceous FER type organic and inorganic carbon hybrid zeolite solid acid:
1, the solid with polyoxymethylene places the reactor bottom, and base material places the upper strata, and the centre separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains Framework of Siliceous FER type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 7:
Substrate FER type zeolite according to the following steps with the acetaldehyde effect, preparation Framework of Siliceous FER type organic and inorganic carbon hybrid zeolite solid acid:
1, the solution of acetaldehyde is mixed with Framework of Siliceous FER type zeolite places reactor.Or the solution of acetaldehyde placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains Framework of Siliceous FER type zeolite organic and inorganic carbon hydridization solid acid.
Embodiment 8:
Substrate FER type zeolite according to the following steps with the propionic aldehyde effect, preparation Framework of Siliceous FER type organic and inorganic carbon hybrid zeolite solid acid:
1, the solution of propionic aldehyde is mixed with Framework of Siliceous FER type zeolite places reactor.Or the solution of propionic aldehyde placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains Framework of Siliceous FER type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 9:
Substrate total silicon BEA type (β type) zeolite according to the following steps with the formaldehyde effect, preparation total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid:
1, the solid of formaldehyde adds thermal depolymerization at 90 ℃～150 ℃, collects with liquid nitrogen.
2, the steam importing with formaldehyde monomers fills in the container of total silicon BEA type zeolite, and room temperature is carried out absorption reaction 2h and obtained reaction product, and reaction product is washed after filtration, and oven dry obtains total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 10:
Substrate BEA type zeolite according to the following steps with the formaldehyde effect, preparation total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid:
1, the solid with polyoxymethylene places the reactor bottom, and base material places the upper strata, and the centre separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 11:
Substrate BEA type zeolite according to the following steps with the acetaldehyde effect, preparation total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid:
1, the solution of acetaldehyde is mixed with total silicon BEA type zeolite places reactor.Or the solution of acetaldehyde placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid.
Embodiment 12:
Substrate BEA type zeolite according to the following steps with the propionic aldehyde effect, preparation total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid:
1, the solution of propionic aldehyde is mixed with Framework of Siliceous FER type zeolite places reactor.Or the solution of propionic aldehyde placed the reactor bottom, base material places the upper strata, middlely separates with screen cloth.
2, reactor is placed 200 ℃ of baking ovens, reaction is 2 days under self-generating pressure, and reaction product is washed after filtration, and oven dry obtains total silicon BEA type organic and inorganic carbon hybrid zeolite solid acid.
Claims (5)
1, a kind of organic and inorganic carbon hybridized silicon zeolite solid acid cellular material is characterized in that the skeleton oxygen that skeleton contains 1-20% in the oxygen total silicon poromerics is substituted by the aldehydes organo-functional group, and wherein aldehyde radical is RCHO, and R is C here
0-C
2Hydro carbons.
2, poromerics according to claim 1 is characterized in that it is the not aluminiferous total silicon zeolite molecular sieve of crystalline state that described skeleton contains the oxygen poromerics.
3, a kind of preparation method of organic and inorganic carbon hybridized silicon zeolite solid acid cellular material as claimed in claim 1, it is characterized in that solid or aqueous solution with oxygen containing total silicon poromerics of skeleton and the agent of aldehydes hydridization, place reactor, carry out hydro-thermal reaction, temperature 20-200 ℃, time 1.5-50 hour, obtain organic and inorganic carbon hybridized silicon zeolite solid acid cellular material.
4, the preparation method of poromerics as claimed in claim 3, when it is characterized in that hydro-thermal reaction the agent of aldehydes hydridization is placed the reactor bottom, the oxygen containing total silicon poromerics of skeleton places the upper strata, the steam and the base material generation gas/solid state reaction that produce when utilizing heating are prepared into organic and inorganic carbon hybridized silicon zeolite solid acid cellular material.
5, poromerics as claimed in claim 1 is in the application of catalysis or separation field.
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|---|---|---|---|
| CNB2004100890372A CN1299986C (en) | 2004-12-02 | 2004-12-02 | Organic and inorganic carbon hybridized silicon zeolite solid acid cellular material and its prepn |
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|---|---|---|---|
| CNB2004100890372A CN1299986C (en) | 2004-12-02 | 2004-12-02 | Organic and inorganic carbon hybridized silicon zeolite solid acid cellular material and its prepn |
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| CN1299986C true CN1299986C (en) | 2007-02-14 |
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| CN104148118B (en) * | 2014-08-12 | 2016-05-11 | 福州大学 | A kind of method of utilizing the reactive halide of water to prepare modified aluminium oxide supports |
| CN111905801A (en) * | 2020-08-17 | 2020-11-10 | 鲁雪 | Visible-light-driven photocatalyst, and preparation method and application thereof |
| CN114408938A (en) * | 2021-08-19 | 2022-04-29 | 复榆(张家港)新材料科技有限公司 | All-silicon FER zeolite and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051310A (en) * | 1988-05-20 | 1991-05-15 | 日本化学工业株式会社 | The method that keeps activety of zeolite catalyst |
| CN1436726A (en) * | 2003-02-25 | 2003-08-20 | 大连理工大学 | Prepn process of superfine zeolite powder |
-
2004
- 2004-12-02 CN CNB2004100890372A patent/CN1299986C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051310A (en) * | 1988-05-20 | 1991-05-15 | 日本化学工业株式会社 | The method that keeps activety of zeolite catalyst |
| US5068442A (en) * | 1988-05-20 | 1991-11-26 | Nitto Kagaku Kogyo Kabushiki Kaisha | Method for maintaining the activity of zeolite catalysts |
| CN1436726A (en) * | 2003-02-25 | 2003-08-20 | 大连理工大学 | Prepn process of superfine zeolite powder |
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