CN103432988B - Composite of the coated sieve particle of fento and preparation method thereof - Google Patents
Composite of the coated sieve particle of fento and preparation method thereof Download PDFInfo
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- CN103432988B CN103432988B CN201310383259.4A CN201310383259A CN103432988B CN 103432988 B CN103432988 B CN 103432988B CN 201310383259 A CN201310383259 A CN 201310383259A CN 103432988 B CN103432988 B CN 103432988B
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Abstract
The invention discloses the composite of the coated sieve particle of fento, comprise the fiber of micron order diameter and the sieve particle of micro-meter scale, the sieve particle of described micro-meter scale is evenly coated in the fibroplastic tridimensional network of micron order diameter.The invention also discloses the preparation method of above-mentioned composite, first the cellulose adhesive of special ratios, fento, molecular sieve or molecular sieve catalyst are mixed with suitable quantity of water, stir and form homogeneous slurry; Then wet papermaking process is utilized to make presoma; Presoma is dry, and under specified temp and atmosphere sinter molding.Composite material preparation process of the present invention is simple, with low cost, there is thinner thickness and controllable, voidage is high and adjustable, mechanical strength is high, long service life and the good characteristic of pliability, be applied to fixed bed energy enhancing mass and heat transfer, reduce molecular sieve or molecular sieve catalyst particle wearing and tearing, reduce bed pressure drop, improve adsoption catalysis efficiency, have a extensive future.
Description
Technical field
The present invention relates to the technical field of molecular sieves compound material and preparation thereof, particularly the composite and preparation method thereof of the coated sieve particle of fento.
Background technology
Molecular sieve is the crystal of three-dimensional aluminosilicates metal structure that sial tetrahedron is formed, and is the homogeneous strong polar adsorbent of a kind of pore size, and selective absorption separating power is strong and have the characteristic of absorption, catalytic reaction and ion-exchange.Since the nearly century, a large amount of researcher is devoted to study the molecular sieve that can be applicable to adsorbing separation and catalytic field.The molecular sieve be successfully 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 the highest due to aluminium content in aluminosilicate tetrahedron, thus has very high adsorptive selectivity to the molecule of water and polarity, industrially Chang Zuowei dehumidizer and cleanser.X-type and Y zeolite are faujasite-type molecular sieves, have the characteristic of selective absorption, be thus commonly used for desulfurizing agent to some sulphur component in oil, liquefied petroleum gas, natural gas.In addition, because the aperture of X-type and Y zeolite is comparatively large, usually at 0.8 ran, be thus also well suited for as catalytic cracking catalyst.ZSM-5 molecular sieve can as the carrier of catalyst, by ion-exchange or infusion process by some metallic element loads on ZSM-5 molecular sieve, excellent catalytic activity can be made it have, 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 there is the deficiency that heat-resistant stability, antiacid alkali ability, chemical stability, mechanical strength and mar proof are poor.Particularly in actual use procedure, when molecular sieve is as filler in ADSORPTION IN A FIXED BED catalytic reactor, due to the shortcoming of fixed bed reactors ubiquity poor heat transfer, time exothermic heat of reaction amount is very large, may occur that reaction temperature sharply rises and exceedes the situation of allowed band, and cause the destructurized of molecular sieve, adsoption catalysis performance can be had a strong impact on.Simultaneously because fluid flows in fixed bed, 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 practical application cost.In addition, because fluid is by producing larger pressure drop during particles filled fixed bed, absorption and catalytic reaction efficiency can also be affected.
In order to solve the problem, Auburn university of the U.S. (U.S.Patents NO.5,304,330; NO.5,080,963; NO.5,102,745; NO.5,096,663 and NO.6,231,792) invent a kind of sintered fiber composite with tridimensional network and preparation method thereof in the nineties.Brave and the South China Science & Engineering University in East China Normal University road opens and understands equality people (Chinese application number 200510028873.4, publication number CN1762909A; 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) prepare glass fibre, ceramic fibre and metallic fiber coated Si O
2, Al
2o
3and the composite of activated carbon granule, at metal fiber carrier synthesizing molecular sieve film on the surface, but the process that synthesizing molecular sieve film adopts is comparatively complicated, and length consuming time, the molecular screen membrane mechanical strength of synthesis is poor, easy appearance is damaged, and may be difficult to maintain absorption/catalytic performance in practical application, the scope of application is very limited.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide the composite of the coated sieve particle of a kind of fento, good mechanical property, the wearing and tearing of molecular sieve can be reduced, reducing use cost.
Another object of the present invention is to the preparation method of the composite that the coated sieve particle of above-mentioned fento is provided.
Object of the present invention is achieved through the following technical solutions:
The composite of the coated sieve particle of fento, comprises the fiber of micron order diameter and the sieve particle of micro-meter scale, and the sieve particle of described micro-meter scale is evenly 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.
The modified molecular screen particle that described sieve particle is A type, MFI type, MOR type, P type or ETS-4 type molecular sieve are obtained by ion-exchange or infusion process.
Described sieve particle is that load has the A type of catalyst granules, MFI type, MOR type, P type or ETS-4 type sieve particle.
The preparation method of the composite of the coated sieve particle of above-mentioned fento, comprises the following steps:
(1) cellulose adhesive, the fiber of micron order diameter, sieve particle are mixed with water, stir and form homogeneous slurry; Wherein the fiber of cellulose adhesive, micron order diameter, the mass ratio of sieve particle are 1:1 ~ 3:1 ~ 5;
(2) utilize wet papermaking process by step (1) gained slurries handsheet, make paper-like composite;
(3) by step (2) gained paper-like composite dry 10 ~ 24h at 100 ~ 200 DEG C;
(4) by the paper-like composite after step (3) process, at 400 DEG C ~ 1000 DEG C, in nitrogen or hydrogen atmosphere, 50min ~ 150min is sintered, the composite of the obtained coated sieve particle of fento.
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 500 ~ 1500 turns per minute.
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 poor, sieve particle is coated on inside fento material, and the mechanical performance of sieve particle obtains reinforcement, sieve particle can maintain its good absorption/catalytic performance, reduces use cost.
2, the present invention adopts wet papermaking process and sintering technology to prepare the composite of the coated sieve particle of fento, and preparation technology is simple, easily realizes industrialization and with low cost.
3, the composite structure of the coated sieve particle of fento that prepared by the present invention is evenly distributed, thinner thickness and controllable, and voidage is high and adjustable, can be cut into arbitrary shape according to actual needs, and pliability is good, and mechanical strength is high, long service life.
4, the composite being prepared by the present invention the coated sieve particle of fento applies to fixed bed, can enhancing mass and heat transfer, effectively can reduce bed pressure drop; Effectively can also reduce the wearing and tearing of molecular sieve or molecular sieve catalyst particle, reduce costs.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
1g needle-leaved wood fibre adhesive, 3g ceramic fibre and 5gNaX sieve particle are joined in suitable quantity of water, stirs 15min in standard fibre dissociation device high speed (500 turns per minute), form homogeneous slurry.Wherein ceramic fibre diameter is 5 microns, molecular sieve particle diameter 100 ~ 200 microns.Slurries handsheet machine after mixing is carried out handsheet, after drainage, forms wet cake.This filter cake is squeezed under 3bar pressure, dry 24h at 100 DEG C.By dried composite at N
2sinter 150 minutes in 400 DEG C under gas shielded, specific gas flow rate controls at 200ml/min, obtained fento coated NaX sieve particle composite.Fento coated NaX sieve particle composite prepared by the present embodiment, NaX sieve particle is evenly 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, turns in standard fibre dissociation device high speed (1500 turns per minute) and stir 15min, form the slurries mixed.The wherein diameter 5 microns of stainless steel fibre, CuY molecular sieve particle diameter 100 ~ 200 microns.Slurries handsheet machine after mixing is carried out handsheet, after drainage, forms wet cake.This filter cake is squeezed under 5bar pressure, dry 10h at 200 DEG C.Dried composite is sintered 50 minutes in 1000 DEG C under hydrogen shield, and specific gas flow rate controls at 200ml/min, obtained fento coated CuY molecular sieve catalyst particle composite.Fento coated CuY molecular sieve catalyst particle composite prepared by the present embodiment, CuY molecular sieve catalyst particle is evenly 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, stirs 10min in standard fibre dissociation device high speed, form homogeneous slurry.Wherein stainless steel fibre diameter is 5 microns, molecular sieve particle diameter 50 ~ 100 microns.Slurries handsheet machine after mixing is carried out handsheet, after drainage, forms wet cake.This filter cake is squeezed under 5bar pressure, dry 24h at 120 DEG C.By dried composite at N
2sinter 30 minutes in 1000 DEG C under gas shielded, specific gas flow rate controls at 200ml/min, obtained fento coated Fe-ZSM-5 molecular sieve catalyst particle composite.Fento coated Fe-ZSM-5 molecular sieve catalyst particle composite prepared by the present embodiment, Fe-ZSM-5 molecular sieve catalyst particle is evenly 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 A type, MFI type, MOR type, P type or ETS-4 type molecular sieve are obtained by ion-exchange or infusion process; Or load has the A type of catalyst granules, MFI type, MOR type, P type or ETS-4 type sieve particle.
In above-described embodiment, cellulose adhesive also can be carboxyethyl cellulose adhesive or carboxylic propyl methocel adhesive.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the preparation method of the composite of the coated sieve particle of fento, is characterized in that, comprise the following steps:
(1) cellulose adhesive, the fiber of micron order diameter, sieve particle are mixed with water, stir and form homogeneous slurry; Wherein the fiber of cellulose adhesive, micron order diameter, the mass ratio of sieve particle are 1:1 ~ 3:1 ~ 5;
(2) utilize wet papermaking process by step (1) gained slurries handsheet, make paper-like composite;
(3) by step (2) gained paper-like composite dry 10 ~ 24h at 100 ~ 200 DEG C;
(4) by the paper-like composite after step (3) process, at 400 DEG C ~ 1000 DEG C, in nitrogen or hydrogen atmosphere, 50min ~ 150min is sintered, the composite of the obtained coated sieve particle of fento;
The composite of the coated sieve particle of described fento, comprises the fiber of micron order diameter and the sieve particle of micro-meter scale, and the sieve particle of described micro-meter scale is evenly coated in the fibroplastic tridimensional network of micron order diameter.
2. the preparation method of the composite of the coated sieve particle of fento according to claim 1, it is characterized in that, described cellulose adhesive is native cellulose adhesive, carboxymethyl cellulose gum stick, carboxyethyl cellulose adhesive or carboxylic propyl methocel adhesive.
3. the preparation method of the composite of the coated sieve particle of fento according to claim 1, is characterized in that, described stirring, is specially:
Stir speed (S.S.) is 500 ~ 1500 turns per minute.
4. the preparation method of the composite of the coated sieve particle of fento according to claim 1, is characterized in that, described fiber is ceramic fibre or metallic fiber.
5. the preparation method of the composite of the coated sieve particle of fento according to claim 1, is characterized in that, described sieve particle is A type, MFI type, MOR type, P type or ETS-4 type sieve particle.
6. the preparation method of the composite of the coated sieve particle of fento according to claim 1, it is characterized in that, described sieve particle is A type, modified molecular screen particle that MFI type, MOR type, P type or ETS-4 type molecular sieve are obtained by ion-exchange or infusion process.
7. the preparation method of the composite of the coated sieve particle of fento according to claim 1, is characterized in that, described sieve particle is that load has the A type of catalyst granules, MFI type, MOR type, P type or ETS-4 type sieve particle.
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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 |
|---|
| 微纤复合材料的制备与应用研究;刘剑;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20121115(第11期);第1页1.1节、第4页1.2.2.1节 * |
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