CN105732119B - Preparation method of composite material with ZSM-5 molecular sieve coating coated on surface of foam silicon carbide carrier - Google Patents
Preparation method of composite material with ZSM-5 molecular sieve coating coated on surface of foam silicon carbide carrier Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000006260 foam Substances 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 33
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims description 15
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 229920002521 macromolecule Polymers 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004411 aluminium Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 230000008595 infiltration Effects 0.000 claims description 6
- 238000001764 infiltration Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- -1 template Substances 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000005475 siliconizing Methods 0.000 abstract 2
- 239000013078 crystal Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 235000013339 cereals Nutrition 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000004484 Briquette Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 238000003618 dip coating Methods 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 235000016709 nutrition Nutrition 0.000 description 1
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- 210000004483 pasc Anatomy 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a ZSM-5 molecular sieve coating material on the surface of a foam silicon carbide carrier. In particular to a method for preparing silicon carbide ceramic as a carrier by adopting a macromolecule pyrolysis combined liquid phase siliconizing method, dissolving a small amount of residual silicon and aluminum left in the siliconizing process on the surface of the carrier in a solution containing an alkali source and a template agent, and assembling a ZSM-5 type molecular sieve in situ under the action of the template agent. The molecular sieve coating prepared by the method is firmly combined with a carrier, has good heat resistance and thermal shock resistance, and shows good performance in the reaction of preparing propylene from methanol.
Description
Technical field
The invention belongs to the technologies of preparing of structuring molecular sieve catalytic material, and it is strong to be especially to provide a kind of high interface cohesion
It spends, the preparation method of the foam silicon carbon carrier surface type ZSM 5 molecular sieve coating material of Load Balanced.
Background technology
Molecular sieve is the crystal aluminosilicate for having uniform crystal structure, it is characterised in that is had many by a large amount of small squares
The regular aperture that shape passage is connected with each other.Molecular sieve is due to its unique structure and performance and in fields such as petrochemical industry, environmental protection
It is widely used as catalyst, catalyst carrier and adsorbent.And carried molecular sieve is strong due to the height machinery for combining carrier
Degree, the specific separation of high thermal stability and molecular sieve, catalysis characteristics and as a new research hotspot of molecular sieve art.
By effort for many years, the mass transfer ability of molecular sieve catalyst and and catalyst stability all achieve very big carry
Height, but present research has focused largely on the modification to zeolite molecular sieve powder, it is related to influence Propylene Selectivity and catalyst
Some major issues in service life do not solve always.For the strong exothermal reaction carried out on particle packing fixed bed reactors, when
When loaded catalyst is larger, the heat of generation can not be taken away, and bed hot-spot causes catalyst inactivation.In addition, though boiling
Nanosizing, mesoporousization of stone molecular sieve make the mass transfer characteristic of zeolite catalyst be improved, but in actual application,
Binding agent must be added, particle is made in catalyst powder.In reactant and the granule proliferation catalyst of reaction product path compared with
It is long, secondary response generation long-chain macromolecule easily occurs, greatly weakens the effect of nanosizing, mesoporousization.Therefore, from basic
The upper mass transfer ability for improving zeolite catalyst simultaneously takes away rapidly the heat generated during the reaction, is one and urgently to be resolved hurrily asks
Topic.
The painting of ZSM-5 types zeolite molecular sieve, which is carried on foam silicon carbon carrier, two aspect benefits：First, reactant with it is anti-
It answers product diffusion length in ZSM-5 type zeolite molecular sieve coatings shorter, is conducive to improve selectivity；2nd, foam silicon carbon passes
Thermal energy power is good, and the heat for reacting generation can be taken away rapidly, prevent carbon distribution.
There are mainly two types of the preparation methods of molecular sieve coating：(1) carrier is exactly directly immersed in by dip coating, this method
In slurries containing molecular sieve and adhesive oxides, so that carrier table loads one layer of molecular sieve.The outstanding advantages of this method
It is easy to operate, is applicable to variously-shaped carrier.But its shortcomings that is to be not easy to form fine and close molecular screen membrane, and molecule
Combine not secured enough between screen layers and carrier, therefore some temperature changes are violent, air velocity is fast and mechanical shock is big
Reaction process, the load molecular sieve prepared by this method easily comes off.(2) in-situ synthesis, i.e., using fabricated in situ
Technology direct synthesis of molecular sieve on the surface of the carrier.The remarkable advantage of this method is by controlling synthesis condition that can control molecule
The orientation of growth of crystal and the thickness of molecule screening layered are sieved, so as to form fine and close molecular screen membrane in carrier surface.It
The characteristics of another is important is that molecular sieve layer combined with carrier surface must be than stronger.However, since fabricated in situ uses more
Na2SiO3, the diffluent silicon source such as ethyl orthosilicate, be easy to cause that the load of carrier upper and lower surface is uneven, has molecular sieve in solution
The shortcomings of crystal is remaining.
The content of the invention
It is an object of the invention to provide a kind of preparation sides of foam silicon carbon carrier surface ZSM-5 molecular sieve coating material
Method, molecular sieve coating prepared by this method is firmly combined with carrier, has good heat resistance and thermal shock resistance, in methanol system
Preferable performance is shown in propylene reaction.
The technical scheme is that：
A kind of preparation method of foam silicon carbon carrier surface ZSM-5 molecular sieve coating material is pyrolyzed using macromolecule and tied
It closes liquid Si infiltration method and prepares silicon carbide ceramics as carrier, it is in the solution containing alkali source and template, carrier surface is a small amount of
Remaining silicon, aluminium dissolving, under the action of template, assemble in situ is into the method for ZSM-5 type molecular sieves.Molecular sieve and porous carbon
Chemical bond is realized between SiClx ceramics, there is high interface bond strength, there is good heat resistance and thermal shock resistance,
Preferable performance is shown in preparing propylene from methanol reaction.
Molecular sieve is the crystal aluminosilicate for having uniform crystal structure, it is characterised in that is had many by a large amount of small squares
The regular aperture that shape passage is connected with each other.Silicon carbide ceramics has macroporous structure, such as foaming structure, honeycomb.This
Molecular sieve/porous silicon carbide ceramic composite material obtained by sample is formed unique micropore/macroporous structure.Such structure has
Beneficial to reactant mass transfer wherein, be conducive to the progress of the reactions such as absorption, ion exchange, catalysis.In foam silicon carbon carrier table
There is the remaining silicon of 5-20wt% in face, the aluminium of 0.05-1wt%, and during hydrothermal synthesis, under the action of lye, sial species are molten
Solution.By the effect of template, type ZSM 5 molecular sieve crystal is preferentially in silicon carbide ceramics carrier surface forming core.Remaining sial
Constantly dissolving, the molecular sieve crystal that release silicate supplies preferential forming core with aluminate ion are grown up.The molecular sieve being prepared
Coating, Load Balanced, load capacity, molecular sieve crystal silica alumina ratio are controllable.Realizing between molecular sieve and foam silicon carbon carrier
It learns and combines, there is high interface bond strength between molecular sieve coating and porous silicon carbide ceramic carrier.
The preparation method of the foam silicon carbon carrier surface type ZSM 5 molecular sieve coating, using tetrapropyl ammonia bromide, four
Propyl ammonium hydroxide, tetraethyl ammonia bromide or tetraethyl ammonium hydroxide are as template；Using sodium hydroxide, potassium hydroxide or hydrogen
Lithia is as alkali source.Preparation process is as follows：
1) reaction solution is prepared
Template, alkali source, deionized water are mixed in proportion, rubbing between remaining silicon, template, alkali source and deionized water
You are than being 1：0.0375~1.0：0.1~1.0：10~200；Preferred molar ratio range is 1:(0.075~0.3)：(0.15
~0.45)：(50~100)；
2) hydrothermal synthesis
Foam silicon carbon carrier is introduced into reaction solution；The temperature of hydrothermal synthesis is 120~200 DEG C, the reaction time 10
~120 it is small when, pressure be solution self-generated pressure；
3) roast
First by the samples dried after cleaning；Then, in air atmosphere, at 300~800 DEG C, when roasting 6~20 is small, go
Template agent removing obtains molecular sieve coating.
In the present invention, the silicon carbide ceramics molecular sieve coating material on surface, because molecular sieve crystal and carborundum pottery
Remaining silicon in porcelain has similar chemical property.It is thus achieved that between molecular sieve crystal and porous silicon carbide ceramic matrix
With high interface bond strength.
The main component scope of ZSM-5 molecular sieve coating and technical parameter are as follows in the present invention：Molecular sieve crystal size is 5
~20 microns, load capacity is 5~20wt%, and coating layer thickness is 1~10 micron, gained molecular sieve coating and porous silicon carbide ceramic
The specific surface area that carrier forms composite material is 20~90m2/g.Sial atomic ratio is 11~300.
In the present invention, there is one layer of remaining silicon on properties of SiC foam ceramics skeleton surface, wherein containing aluminium.Surface silicon/aluminium layer comes
From the control to controllable infiltration reaction sintering technology.It is preferable to use Chinese invention patent applications for properties of SiC foam ceramics material
(CN1600742A) a kind of preparation method of the properties of SiC foam ceramics material for the high strength dense mentioned in, Chinese invention patent
Method system described in " controllable conductive silicon carbide foam ceramic material of a kind of resistivity and preparation method thereof " (CN1962544)
It is standby.It after foamed plastics is cut out, immerses in slurry, after taking-up, removes extra slurry, semi-solid preparation, then high temperature, high pressing
Change；Foams after curing are pyrolyzed, are obtained and the equiform foam-like being made of carborundum and pyrolytic carbon of original foam
Carbon skeleton；Mill opens carbon skeleton centre bore, and in silicon carbide slurry pressure injection to carbon skeleton centre bore and center will be filled with pressure injection method
Then hole is pyrolyzed；By siliconising process, carbon and gas phase or liquid phase pasc reaction generation carborundum in carbon skeleton, and with foam bone
Original silicon carbide silicon particle in frame combines, so as to obtain the foam silicon carbide ceramics of high strength dense.Ceramics muscle of the invention
Consistency is high, microscopic structure uniform strength is high.It, can be not anti-in silicon carbide ceramics vector surface residual by controlling siliconising process
The silicon layer of the 5-20wt% of carborundum should be generated.The addition of aluminium can select to add aluminium powder when prepared by slurry or in siliconising
Aluminium element is adulterated in the liquid-phase silicone of journey, total carrier is accounted for containing a small amount of aluminium, content in the vector surface residual silicon layer finally prepared
0.05-1wt%.Using polygonal closed-loop as elementary cell, each elementary cell mutually interconnects prepared foam silicon carbide ceramics
It connects to form three-dimensional networks；Form relative density >=99% of the ceramic muscle of polygon closing ring element, crystallite dimension model
It is trapped among 50nm~10 μm.
The present invention is a kind of by the use of foam silicon carbon vector surface residual silicon, aluminium species as silicon and aluminum source, is containing template
Hydrothermal synthesis in the solution of agent, control molecular sieve are released for the nutriment of molecular sieve nuclei growth in the preferential forming core of carrier surface
Put the controllable molecular sieve coating technology of preparing of speed.The thyrite has macroporous structure, and molecular sieve has
Microcellular structure, molecular sieve/composite silicon carbide ceramic material of so gained are formed unique micropore/macroporous structure.So
Structure be conducive to reactant mass transfer wherein, be conducive to the progress of the reactions such as absorption, ion exchange, catalysis.Due to surface silicon
There is similar chemical property between molecular sieve crystal, so that having between molecular sieve coating and carrier better than other preparations
The interfacial combined function of method.Meanwhile molecular sieve coating load prepared by this method is uniform, molecular sieve carried amount and grain size
Controllably, and carrier material intensity is not affected by influence.
The present invention has the advantages that：
1st, interface bond strength height, Load Balanced, carrier material intensity are not affected by and significantly affect.
The present invention is pyrolyzed by using macromolecule combines properties of SiC foam ceramics prepared by the reaction of controllable infiltration as carrier,
Due to the nutriment dissolved in situ of synthesis of molecular sieve, recrystallization so that molecular sieve crystal is preferentially in silicon carbide ceramics surface shape
Core.Molecular sieve crystal it is carrier loaded uniformly, be firmly combined with, see Fig. 1,2.
2nd, sial atomic ratio, grain size and molecular sieve carried amount are controllable, are shown preferably in preparing propylene from methanol reaction
Performance.
The present invention can control the silica alumina ratio of ZSM-5 coatings by controlling the composition of remaining silicon.Control architecture agent and alkali source
Composition, the rate of release of silicate and aluminate can be controlled, prepare the type ZSM 5 molecular sieve of different grain sizes.
Description of the drawings
Fig. 1 is the macro morphology of foam silicon carbon carrier surface molecular sieve coating；
Fig. 2 is the fracture apperance of foam silicon carbon carrier surface molecular sieve coating；
Fig. 3 is the nitrogen adsorption desorption curve of ZSM-5/ foam silicon carbons.
Specific embodiment
The present invention is described in detail below by embodiment.
Embodiment 1
Foam silicon carbon carrier (selects surface residual silicone content 5wt%, aluminium content 0.05wt%, foam silicon carbon has
Three-dimensional net structure, pore fraction 80%, mesh size 5mm) surface type ZSM 5 molecular sieve coating material preparation method：
Molar ratio between remaining silicon, aluminium, tetrapropylammonium hydroxide, sodium hydroxide and deionized water is 1： 0.0375：
0.1：96.Properties of SiC foam ceramics is fixed on polytetrafluoro supporting rack away from 1 centimeters of reactor bottom, and silico briquette is placed in reaction kettle bottom
Portion；Liquor capacity is 300 milliliters, and reactor volume is 500 milliliters.Temperature used in hydro-thermal reaction is 165 DEG C, the time 120
Hour, pressure is the self-generated pressure that solution boils generate.After reaction is completed, sample is repeatedly clear in 100 DEG C of deionized water
Wash for several times, then with power be 40Hz supersonic wave cleaning machines, clean 20 minutes, with remove residual solution and with matrix Weak link
Molecular sieve crystal.Sample after cleaning is put into drying baker, when drying 12 is small under the conditions of 100 DEG C.Sample is in Muffle furnace after drying
In, when 600 DEG C of roastings 6 are small (heating rate be 2 DEG C/min, furnace cooling).Obtained ZSM-5 types molecular sieve coating and foam
The specific surface area for the composite material that silicon carbide ceramics is formed is 40m2/ g, the load capacity of molecular sieve is 7%, grain size 8
~10 microns, the thickness of the present embodiment molecular sieve coating is 8~12 microns.Through 600 DEG C of thermal shock tests, there is not molecular sieve
Crystal lacks and molecular sieve layer obscission.
Embodiment 2
Foam silicon carbon carrier (selects surface residual silicone content 8wt%, aluminium content 0.2wt%, foam silicon carbon is with three
Tie up network structure, pore fraction 90%, mesh size 2mm) preparation method of surface type ZSM 5 molecular sieve coating material：
Molar ratio between remaining silicon, tetrapropylammonium hydroxide, sodium hydroxide and deionized water is 1：1：0.15：120.Bubble
Foam silicon carbide ceramics is fixed on polytetrafluoro supporting rack away from 1 centimeters of reactor bottom, and silico briquette is placed in reactor bottom；Solution body
Product is 300 milliliters, and reactor volume is 500 milliliters.Temperature used in hydro-thermal reaction is 150 DEG C, and when the time is 92 small, pressure is
The self-generated pressure that solution boils generate.After reaction is completed, sample cleans for several times repeatedly in 100 DEG C of deionized water, then uses
Power is 40Hz supersonic wave cleaning machines, is cleaned 20 minutes, to remove residual solution and molecular sieve crystal with matrix Weak link.
Sample after cleaning is put into drying baker, when drying 12 is small under the conditions of 100 DEG C.Sample is in Muffle furnace after drying, 550 DEG C of roastings
12 it is small when (heating rate be 1 DEG C/min, furnace cooling).Obtained ZSM-5 types molecular sieve coating and properties of SiC foam ceramics institute
The specific surface area of the composite material of composition is 50m2/ g, the load capacity of molecular sieve is 11%, and grain size is 5~8 microns, this reality
The thickness for applying a molecular sieve coating is 3~6 microns.Through 600 DEG C of thermal shock tests, there is not molecular sieve crystal missing and molecule
Screen layers obscission.
Embodiment 3
Foam silicon carbon carrier (selects surface residual silicone content 20wt%, aluminium content 1wt%, foam silicon carbon is with three
Tie up network structure, pore fraction 85%, mesh size 3mm) preparation method of surface type ZSM 5 molecular sieve coating material：
Molar ratio between remaining silicon, aluminium, tetrapropylammonium hydroxide, sodium hydroxide and deionized water is 1： 0.2：1：
200.Properties of SiC foam ceramics is fixed on polytetrafluoro supporting rack away from 1 centimeters of reactor bottom, and silico briquette is placed in reactor bottom；
Liquor capacity is 300 milliliters, and reactor volume is 500 milliliters.Temperature used in hydro-thermal reaction is 175 DEG C, when the time is 92 small,
Pressure is the self-generated pressure that solution boils generate.After reaction is completed, sample cleans number repeatedly in 100 DEG C of deionized water
It is secondary, then with power be 40Hz supersonic wave cleaning machines, it cleans 20 minutes, to remove residual solution and molecule with matrix Weak link
Sieve crystal.Sample after cleaning is put into drying baker, when drying 12 is small under the conditions of 100 DEG C.Sample is in Muffle furnace after drying,
When 650 DEG C of roastings 5 are small (heating rate be 1 DEG C/min, furnace cooling).Obtained ZSM-5 types molecular sieve coating is carbonized with foam
The specific surface area for the composite material that silicon ceramics are formed is 80m2/ g, the load capacity of molecular sieve is 15%, and grain size is 6~8
Micron, the thickness of the present embodiment molecular sieve coating is 5~7 microns.Through 600 DEG C of thermal shock tests, there is not molecular sieve crystal and lack
Mistake and molecular sieve layer obscission.
Embodiment 4
Foam silicon carbon carrier (selects surface residual silicone content 20wt%, aluminium content 1wt%, foam silicon carbon is with three
Tie up network structure, pore fraction 85%, mesh size 3mm) preparation method of surface type ZSM 5 molecular sieve coating material：
Molar ratio between remaining silicon, aluminium, tetrapropyl ammonia bromide, potassium hydroxide and deionized water is 1：0.2： 1：200.
Properties of SiC foam ceramics is fixed on polytetrafluoro supporting rack away from 1 centimeters of reactor bottom, and silico briquette is placed in reactor bottom；Solution
Volume is 300 milliliters, and reactor volume is 500 milliliters.Temperature used in hydro-thermal reaction is 120 DEG C, when the time is 60 small, pressure
The self-generated pressure generated for solution boils.After reaction is completed, sample cleans for several times repeatedly in 100 DEG C of deionized water, then
It is 40Hz supersonic wave cleaning machines with power, cleans 20 minutes, removes residual solution and molecular sieve crystal with matrix Weak link.
Sample after cleaning is put into drying baker, when drying 12 is small under the conditions of 100 DEG C.Sample is in Muffle furnace after drying, 300 DEG C of roastings
20 it is small when (heating rate be 1 DEG C/min, furnace cooling).Obtained type ZSM 5 molecular sieve coating and properties of SiC foam ceramics institute
The specific surface area of the composite material of composition is 65m2/ g, the load capacity of molecular sieve is 10%, and grain size is 6~8 microns, this reality
The thickness for applying a molecular sieve coating is 5~7 microns.Through 600 DEG C of thermal shock tests, there is not molecular sieve crystal missing and molecule
Screen layers obscission.
Embodiment 5
Foam silicon carbon carrier (selects surface residual silicone content 20wt%, aluminium content 1wt%, foam silicon carbon is with three
Tie up network structure, pore fraction 85%, mesh size 3mm) preparation method of surface type ZSM 5 molecular sieve coating material：
Molar ratio between remaining silicon, aluminium, tetraethyl ammonium hydroxide, lithium hydroxide and deionized water is 1： 0.2：1：
200.Properties of SiC foam ceramics is fixed on polytetrafluoro supporting rack away from 1 centimeters of reactor bottom, and silico briquette is placed in reactor bottom；
Liquor capacity is 300 milliliters, and reactor volume is 500 milliliters.Temperature used in hydro-thermal reaction is 200 DEG C, when the time is 10 small,
Pressure is the self-generated pressure that solution boils generate.After reaction is completed, sample cleans number repeatedly in 100 DEG C of deionized water
It is secondary, then with power be 40Hz supersonic wave cleaning machines, it cleans 20 minutes, to remove residual solution and molecule with matrix Weak link
Sieve crystal.Sample after cleaning is put into drying baker, when drying 12 is small under the conditions of 100 DEG C.Sample is in Muffle furnace after drying,
When 800 DEG C of roastings 6 are small (heating rate be 1 DEG C/min, furnace cooling).Obtained ZSM-5 types molecular sieve coating is carbonized with foam
The specific surface area for the composite material that silicon ceramics are formed is 25m2/ g, the load capacity of molecular sieve is 5%, and grain size is micro- for 6~8
Rice, the thickness of the present embodiment molecular sieve coating is 5~7 microns.Through 600 DEG C of thermal shock tests, there is not molecular sieve crystal missing
And molecular sieve layer obscission.
Embodiment 6
Catalyst uses the ZSM-5/ foam SiC structural catalysts prepared in embodiment 3, enterprising in fixed bed reactors
Row preparing propylene from methanol reacts.Reaction condition is as follows：Reaction temperature is 500 DEG C, and reaction raw materials are methanol, uses nitrogen as dilution
Gas, the ratio that methanol gaseous volume accounts for total tolerance (methanol gaseous volume adds nitrogen volume) are 90%.Feedstock quality air speed is
15h-1.Reaction product uses Varian CP-3800 type gas chromatographs, with plot Q capillary columns and hydrogen flame detector (FID) point
Analysis.
Methanol conversion is 97.5% in above-mentioned reaction, Propylene Selectivity 45%, propylene, the mass ratio (P/E of ethylene
Than) it is 4.5.
Embodiment the result shows that, foam silicon carbon prepared by liquid Si infiltration is combined as carrier using macromolecule pyrolysis, with
Its surface residual silicon, aluminium are as nutrition species, in the effect of template and alkali source to can be in foam silicon carbon carrier surface system
It is standby go out Load Balanced, be firmly combined with, there is the type ZSM 5 molecular sieve coating of good preparing propylene from methanol catalytic performance.
Claims (5)
1. a kind of preparation method in composite material of the foam silicon carbon carrier surface coated with ZSM-5 molecular sieve coating, special
Sign is, is pyrolyzed using macromolecule and prepares silicon carbide ceramics as carrier with reference to liquid Si infiltration method, is containing alkali source and template
Solution in, using the silicon of vector surface residual, aluminium as silicon source and silicon source, fabricated in situ type ZSM 5 molecular sieve；
Used foam silicon carbon carrier combines liquid Si infiltration method using macromolecule pyrolysis and prepares, in vector surface residual 5-
The silicon of 20wt%, the aluminium of 0.05-1.0wt%；Foam silicon carbon has three-dimensional net structure, pore fraction 80-90%, mesh
Size 2-5mm.
2. the composite material described in accordance with the claim 1 that ZSM-5 molecular sieve coating is coated in foam silicon carbon carrier surface
Preparation method, it is characterised in that：Using tetrapropyl ammonia bromide, tetrapropylammonium hydroxide, tetraethyl ammonia bromide or tetraethyl hydrogen
Amine-oxides are as template.
3. the composite material described in accordance with the claim 1 that ZSM-5 molecular sieve coating is coated in foam silicon carbon carrier surface
Preparation method, it is characterised in that：Using sodium hydroxide, potassium hydroxide or lithium hydroxide as alkali source.
4. the composite material described in accordance with the claim 1 that ZSM-5 molecular sieve coating is coated in foam silicon carbon carrier surface
Preparation method, preparation process is as follows：
1) reaction solution is prepared
Template, alkali source, deionized water are mixed in proportion, between vector surface residual silicon, template, alkali source and deionized water
Molar ratio be 1：0.0375~1.0：0.1~1.0：10~200；
2) hydrothermal synthesis
Foam silicon carbon carrier is introduced into reaction solution；The temperature of hydrothermal synthesis is 120~200 DEG C, and the reaction time is 10~120
Hour, pressure is solution self-generated pressure；
3) roast
First by the samples dried after cleaning；Then, in air atmosphere, at 300~800 DEG C, when roasting 6~20 is small, mould is removed
Plate agent obtains molecular sieve coating.
5. according to the composite material that ZSM-5 molecular sieve coating is coated in foam silicon carbon carrier surface described in claim 4
Preparation method, it is characterised in that：Molar ratio 1 between vector surface residual silicon, template, alkali source and deionized water:0.075
~0.3：0.15~0.45：50~100.
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| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN103896300A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Preparation method of high-performance SAPO (silicoaluminophosphate)-34 molecular sieve membrane |
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| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN103896300A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Preparation method of high-performance SAPO (silicoaluminophosphate)-34 molecular sieve membrane |
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