CN103432988A - Composite material of microfiber-coated molecular-sieve particles and preparation method of composite material - Google Patents
Composite material of microfiber-coated molecular-sieve particles and preparation method of composite material Download PDFInfo
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- CN103432988A CN103432988A CN2013103832594A CN201310383259A CN103432988A CN 103432988 A CN103432988 A CN 103432988A CN 2013103832594 A CN2013103832594 A CN 2013103832594A CN 201310383259 A CN201310383259 A CN 201310383259A CN 103432988 A CN103432988 A CN 103432988A
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Abstract
The invention discloses a composite material of microfiber-coated molecular-sieve particles. The composite material comprises fiber with micron-sized diameter and micro-scaled molecular-sieve particles, wherein the micro-scaled molecular-sieve particles are uniformly coated in a three-dimensional meshed structure formed by the fiber with the micron-sized diameter. The invention also discloses a preparation method of the composite material. The preparation method comprises the following steps: firstly mixing cellulose adhesive, microfiber, molecular sieve or molecular sieve catalyst with specific proportion with proper amount of water, and stirring to form uniform grout; then preparing a precursor by utilizing a wet-process papermaking process; and drying the precursor, sintering and forming under specific temperature and atmosphere. The composite material disclosed by the invention is simple in preparation process and low in cost, has the characteristics of small and adjustable thickness, high and adjustable void ratio, high mechanical strength, long service life and good flexibility, can be applied in a fixed bed, and has the advantages that mass transferring and heat transferring can be strengthened, the wear of the molecular sieves or the molecular sieve catalyst particles is reduced, the pressure drop of the bed layer is reduced, the adsorption efficiency and the catalytic efficiency are improved and the application prospect is wide.
Description
Technical field
The present invention relates to the technical field of molecular sieves compound material and preparation thereof, particularly fento coats composite of sieve particle and preparation method thereof.
Background technology
Molecular sieve is the crystal of the three-dimensional aluminosilicates metal structure that forms of sial tetrahedron, is a kind of strong polar adsorbent of pore size homogeneous, and the selective absorption separating power is strong and have a characteristic of absorption, catalytic reaction and ion-exchange.Since the nearly century, a large amount of researchers are devoted to the molecular sieve that research can be applicable to adsorbing separation and catalytic field.The molecular sieve successfully be synthesized at present mainly contains A type (NaA), MFI type (ZSM-5, silicate-1), FAU type (NaX, NaY), MOR type, CHA type (SAPO34), P type, ETS-4 type etc.Wherein A type molecular sieve is because aluminium content in the aluminosilicate tetrahedron is the highest, thereby the molecule of water and polarity is had to very high adsorptive selectivity, at industrial Chang Zuowei dehumidizer and cleanser.X-type and Y zeolite are the faujasite-type molecular sieves, some sulphur component in oil, liquefied petroleum gas, natural gas is had to the characteristic of selective absorption, thereby be commonly used for desulfurizing agent.In addition, because the aperture of X-type and Y zeolite is larger, usually in 0.8 nanometer left and right, thereby also be well suited for as catalytic cracking catalyst.ZSM-5 molecular sieve can be used as the carrier of catalyst, by ion-exchange or infusion process, some metallic elements are loaded on ZSM-5 molecular sieve, can make it there is excellent catalytic activity, be applied in the wet oxidation catalysis of the burning of volatile compound for catalysis or phenol.
Although molecular sieve is a kind of adsorbent and catalyst of extremely important and function admirable, also exists heat-resistant stability, antiacid alkali ability, chemical stability, mechanical strength and the poor deficiency of mar proof.Particularly in actual use procedure, molecular sieve is during as the filler in the ADSORPTION IN A FIXED BED catalytic reactor, due to the shortcoming that it is poor that the fixed bed reactors ubiquity conducts heat, when the exothermic heat of reaction amount is very large, may occur reaction temperature sharply to rise and surpass the situation of allowed band, and cause the destructurized of molecular sieve, can have a strong impact on the adsoption catalysis performance.Because fluid flows in fixed bed, the sieve particle filler there will be the problem of mutual extrusion friction, causes sieve particle to wear and tear, and causes the loss of material, can improve the practical application cost simultaneously.In addition, produce larger pressure drop during by particles filled fixed bed due to fluid, also can affect absorption and catalytic reaction efficiency.
In order to address the above problem, U.S. Auburn university (U.S.Patents NO.5,304,330; NO.5,080,963; NO.5,102,745; NO.5,096,663 and NO.6,231,792) invented a kind of sintered fiber composite with tridimensional network and preparation method thereof in the nineties.Meeting equality people (Chinese application number 200510028873.4, publication number CN1762909A open in road Yong He South China Science & Engineering University of East China Normal University; Application number 200610025844.7, publication number CN1836779A; Application number 200710026410.3, publication number CN101007270A; Application number 201210213680.6, publication number CN102728399A; Application number 201110376722.3, publication number CN102512978A) glass fibre, ceramic fibre and metallic fiber coated Si O have been prepared
2, Al
2o
3and the composite of activated carbon granule, synthesizing molecular sieve film on the metal fiber carrier surface, but the process that synthesizing molecular sieve film adopts is comparatively complicated, and length consuming time, synthetic molecular screen membrane mechanical strength is poor, breakage easily occurs, in practical application, may be difficult to maintain absorption/catalytic performance, the scope of application is very limited.
Summary of the invention
Above-mentioned shortcoming and deficiency in order to overcome prior art, the object of the present invention is to provide a kind of fento to coat the composite of sieve particle, and good mechanical property, can reduce the wearing and tearing of molecular sieve, reduces use cost.
Another object of the present invention is to provide above-mentioned fento to coat the preparation method of the composite of sieve particle.
Purpose of the present invention is achieved through the following technical solutions:
Fento coats the composite of sieve particle, the fiber that comprises the micron order diameter and the sieve particle of micro-meter scale, and the sieve particle of described micro-meter scale evenly is coated in the fibroplastic tridimensional network of micron order diameter.
Described fiber is ceramic fibre or metallic fiber.
Described sieve particle is A type, MFI type, MOR type, P type or ETS-4 type sieve particle.
Described sieve particle is the modified molecular screen particle that A type, MFI type, MOR type, P type or ETS-4 type molecular sieve obtain by ion-exchange or infusion process.
Described sieve particle is A type, MFI type, MOR type, P type or the ETS-4 type sieve particle that load has catalyst granules.
Above-mentioned fento coats the preparation method of the composite of sieve particle, comprises the following steps:
(1) fiber of cellulose adhesive, micron order diameter, sieve particle are mixed with water, stir and form homogeneous slurry; Wherein the mass ratio of the fiber of cellulose adhesive, micron order diameter, sieve particle is 1:1～3:1～5;
(2) utilize wet papermaking process by step (1) gained slurries handsheet, make paper shape composite;
(3) by step (2) gained paper shape composite dry 10～24h under 100～200 ℃;
(4), by the paper shape composite after step (3) is processed, under 400 ℃～1000 ℃, sintering 50min～150min in nitrogen or hydrogen atmosphere, make the composite that fento coats sieve particle.
Described cellulose adhesive is native cellulose adhesive, carboxymethyl cellulose gum stick, carboxyethyl cellulose adhesive or carboxylic propyl methocel adhesive.
Described stirring is specially:
Stir speed (S.S.) is per minute 500～1500 to turn.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, the present invention directly adopts sieve particle as raw material, the well-regulated pore passage structure of sieve particle tool, good absorption/catalysis energy-absorbing, but bad mechanical strength own, heat resistance and resistance to acids and bases are poor, and sieve particle is coated on to fento material the inside, and the mechanical performance of sieve particle has obtained reinforcement, sieve particle can maintain its good absorption/catalytic performance, has reduced use cost.
2, the present invention adopts wet papermaking process and sintering technology to prepare the composite that fento coats sieve particle, and preparation technology is simple, easily realizes industrialization and with low cost.
3, the composite structure that the fento that prepared by the present invention coats sieve particle is evenly distributed, thinner thickness and can regulating and controlling, and voidage is high and can regulate, and can be cut into according to actual needs arbitrary shape, and pliability is good, and mechanical strength is high, long service life.
4, prepared by the present invention to the composite that fento coats sieve particle and apply to fixed bed, can enhancing mass and heat transfer, can effectively reduce bed pressure drop; Can also effectively reduce the wearing and tearing of molecular sieve or molecular sieve catalyst particle, reduce costs.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
1g needle-leaved wood fibre adhesive, 3g ceramic fibre and 5gNaX sieve particle are joined in suitable quantity of water, in standard fibre dissociation device high speed (per minute 500 turn), stir 15min, form homogeneous slurry.Wherein the ceramic fibre diameter is 5 microns, 100～200 microns of molecular sieve particle diameters.Slurries after mixing are carried out to handsheet with the handsheet machine, form wet cake after drainage.This filter cake is squeezed under 3bar pressure to dry 24h under 100 ℃.By dried composite at N
2under gas protection, in 400 ℃ of sintering 150 minutes, specific gas flow rate was controlled at 200ml/min, makes fento and coats NaX sieve particle composite.Fento prepared by the present embodiment coats NaX sieve particle composite, and the NaX sieve particle evenly is coated in the tridimensional network of fento formation.
Embodiment 2
3g carboxymethyl cellulose adhesive, 3g stainless steel fibre and 3gCuY molecular sieve catalyst particle are joined in suitable quantity of water solution, in standard fibre dissociation device high speed (per minute 1500 turn), turn and stir 15min, form the slurries that mix.5 microns of the diameters of stainless steel fibre wherein, 100～200 microns of CuY molecular sieve particle diameters.Slurries after mixing are carried out to handsheet with the handsheet machine, form wet cake after drainage.This filter cake is squeezed under 5bar pressure to dry 10h under 200 ℃.By dried composite under hydrogen shield in 1000 ℃ of sintering 50 minutes, specific gas flow rate is controlled at 200ml/min, makes fento and coats CuY molecular sieve catalyst particle composite.Fento prepared by the present embodiment coats CuY molecular sieve catalyst particle composite, and the CuY molecular sieve catalyst particle evenly is coated in the tridimensional network of fento formation.
Embodiment 3
3g needle-leaved wood fibre adhesive, 5g stainless steel fibre and 3.5gFe-ZSM-5 molecular sieve catalyst particle are joined in suitable quantity of water solution, in standard fibre dissociation device high speed, stir 10min, form homogeneous slurry.Wherein the stainless steel fibre diameter is 5 microns, 50～100 microns of molecular sieve particle diameters.Slurries after mixing are carried out to handsheet with the handsheet machine, form wet cake after drainage.This filter cake is squeezed under 5bar pressure to dry 24h under 120 ℃.By dried composite at N
2under gas protection, in 1000 ℃ of sintering 30 minutes, specific gas flow rate was controlled at 200ml/min, makes fento and coats Fe-ZSM-5 molecular sieve catalyst particle composite.Fento prepared by the present embodiment coats Fe-ZSM-5 molecular sieve catalyst particle composite, and the Fe-ZSM-5 molecular sieve catalyst particle evenly is coated in the tridimensional network of fento formation.
In above-described embodiment, sieve particle is MFI type, MOR type, P type or ETS-4 type sieve particle; Or the modified molecular screen particle that obtains by ion-exchange or infusion process of A type, MFI type, MOR type, P type or ETS-4 type molecular sieve; Or load has A type, MFI type, MOR type, P type or the ETS-4 type sieve particle of catalyst granules.
In above-described embodiment, cellulose adhesive also can be carboxyethyl cellulose adhesive or carboxylic propyl methocel adhesive.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. fento coats the composite of sieve particle, it is characterized in that, and the fiber that comprises the micron order diameter and the sieve particle of micro-meter scale, the sieve particle of described micro-meter scale evenly is coated in the fibroplastic tridimensional network of micron order diameter.
2. fento according to claim 1 coats the composite of sieve particle, it is characterized in that, described fiber is ceramic fibre or metallic fiber.
3. fento according to claim 1 coats the composite of sieve particle, it is characterized in that, described sieve particle is A type, MFI type, MOR type, P type or ETS-4 type sieve particle.
4. fento according to claim 1 coats the composite of sieve particle, it is characterized in that, described sieve particle is the modified molecular screen particle that A type, MFI type, MOR type, P type or ETS-4 type molecular sieve obtain by ion-exchange or infusion process.
5. fento according to claim 1 coats the composite of sieve particle, it is characterized in that, described sieve particle is A type, MFI type, MOR type, P type or the ETS-4 type sieve particle that load has catalyst granules.
6. the described fento of claim 1～5 any one coats the preparation method of the composite of sieve particle, it is characterized in that, comprises the following steps:
(1) fiber of cellulose adhesive, micron order diameter, sieve particle are mixed with water, stir and form homogeneous slurry; Wherein the mass ratio of the fiber of cellulose adhesive, micron order diameter, sieve particle is 1:1～3:1～5;
(2) utilize wet papermaking process by step (1) gained slurries handsheet, make paper shape composite;
(3) by step (2) gained paper shape composite dry 10～24h under 100～200 ℃;
(4), by the paper shape composite after step (3) is processed, under 400 ℃～1000 ℃, sintering 50min～150min in nitrogen or hydrogen atmosphere, make the composite that fento coats sieve particle.
7. fento according to claim 6 coats the preparation method of the composite of sieve particle, it is characterized in that, described cellulose adhesive is native cellulose adhesive, carboxymethyl cellulose gum stick, carboxyethyl cellulose adhesive or carboxylic propyl methocel adhesive.
8. fento according to claim 6 coats the preparation method of the composite of sieve particle, it is characterized in that, described stirring is specially:
Stir speed (S.S.) is per minute 500～1500 to turn.
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| CN201310383259.4A CN103432988B (en) | 2013-08-28 | 2013-08-28 | Composite of the coated sieve particle of fento and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481629A (en) * | 2015-12-17 | 2016-04-13 | 华南理工大学 | Method for separation and purification of high purity alkane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304330A (en) * | 1989-05-24 | 1994-04-19 | Auburn University | Preparation of mixed fiber composite structures |
| CN1762909A (en) * | 2005-08-17 | 2006-04-26 | 华东师范大学 | Sintered microfibrillar structure micrometer size granule porous composite material and production method |
| CN101007270A (en) * | 2007-01-19 | 2007-08-01 | 华南理工大学 | Composite material of micro-fiber encapsulated active carbon or active carbon catalyst and preparation method thereof |
-
2013
- 2013-08-28 CN CN201310383259.4A patent/CN103432988B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304330A (en) * | 1989-05-24 | 1994-04-19 | Auburn University | Preparation of mixed fiber composite structures |
| CN1762909A (en) * | 2005-08-17 | 2006-04-26 | 华东师范大学 | Sintered microfibrillar structure micrometer size granule porous composite material and production method |
| CN101007270A (en) * | 2007-01-19 | 2007-08-01 | 华南理工大学 | Composite material of micro-fiber encapsulated active carbon or active carbon catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘剑: "微纤复合材料的制备与应用研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481629A (en) * | 2015-12-17 | 2016-04-13 | 华南理工大学 | Method for separation and purification of high purity alkane |
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