CN102274744B - Porous carborundum surface single-layered and b-axis oriented ZSM-5 zeolite coating material and preparation method thereof - Google Patents
Porous carborundum surface single-layered and b-axis oriented ZSM-5 zeolite coating material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of a structured catalyst and an application thereof, in particular to a porous carborundum surface single-layered and b-axis oriented ZSM-5 zeolite coating material and a preparation method thereof. Foamy carborundum or honeycomb structured carborundum is taken as a carrier, wherein a porous layer which is composed of overlapped carborundum grains is formed on the outer surface of the carrier; a zeolite coating layer is uniformly formed in the zeolite coating; the zeolite coating layer has a single-layer structure; and a b axis of a zeolite crystalis vertical to the surface of the carborundum carrier. The preparation method comprises the following steps: growing a layer of seed crystal colloid in situ on a carborundum ceramic surface in advance; controlling the basicity of a secondary growing solution, the concentration of nutrient substances and an added quantity of alkali metallic ions; and realizing the controllable growth of zeolite crystal on the surface of the carborundum carrier. The channel of the structured catalyst is opened; the molecular diffusion property is excellent; a specific surface area and a load are bigger; a contact area between the zeolite crystal and the carborundum carrier is big; the strengthened mass transfer and heat transfer are boosted; and the contact time among the reactant, the reaction product and the catalyst is shortened.
Description
Technical field
The invention belongs to structure catalyst and applied technical field thereof, the concrete preparation method who relates to a kind of porous silicon carbide carrier surface individual layer, b axle orientation ZSM-5 type zeolite coating material.
Background technology
Zeolite crystal has unique structure and performance, is widely used in fields such as petrochemical industry, environmental protection as catalyst, catalyst carrier or adsorbent.Traditional zeolite crystal catalyst is all that the form with particle is applied in fixed bed, not only causes bed pressure drop to raise and causes the waste of the energy, and also produce larger concentration and thermograde in process of production, has reduced the catalytic efficiency of catalyst.Simultaneously, separation and the recovery difficult of zeolite crystal catalyst are large, cause catalyst loss and produce environmental pollution.
The support type zeolite has high mechanical properties, low pressure drop, high catalytic activity and high thermal stability, receives vast catalysis worker's concern.The ceramic materials such as the metal such as nickel, copper and aluminium oxide, cordierite are the carrier of useful as catalysts all.Metallic carrier has higher intensity and thermal conductivity, but its oxidation resistance is relatively poor; Although the ceramic material such as aluminium oxide, cordierite oxidation resistance is strong, its mechanical strength and thermal conductivity are poor.Silicon carbide ceramics has advantages of that high thermal conductivity and mechanical strength, anti-oxidant, chemical inertness, density are little, is a kind of novel carriers material that can replace the traditional catalyst carrier material.
The preparation method of support type zeolite molecular sieve coating mainly contains two kinds: (1) dip coating.This method is exactly that carrier directly is immersed in the slurries that contain zeolite crystal and adhesive oxides, thereby makes carrier table load one deck zeolite crystal.The outstanding advantages of the method is simple to operate, applicable to the carrier of various shapes.But its shortcoming is to be difficult for forming fine and close zeolite membrane, and firm not in conjunction with getting between zeolite coating and carrier, so the course of reaction violent in some variations in temperature, that air velocity is fast and mechanical shock is large, not ideal enough by the load zeolite coating of this method preparation.(2) in-situ synthesis.Being about to carrier immerses in the solution that contains zeolite growth desired nutritional material directly synthetic.The remarkable advantage of the method is that the zeolite molecular sieve layer is combined more firmly with carrier surface.But the zeolite coating of the method preparation is very fine and close, and intracrystalline pore is considerably less.For obtaining larger load capacity, the method for usually taking is in carrier surface growth in situ zeolite megacryst or thicker zeolite membrane.Like this, reactant and product are spread in zeolite crystal and zeolite coating be restricted, consequently, only have the active sites of close zeolite catalyst outer surface to be utilized, and zeolite crystal or zeolite coating inside can not be utilized, and reduced the utilization rate of catalyst.Simultaneously, because the zeolite crystal size is large or the zeolite coating is thicker, product can not in time break away from zeolite crystal, has improved the probability of happening of secondary response, has reduced selective to target product.Simultaneously, because the zeolite crystal size is large or the zeolite coating is thicker, make the heat transfer between zeolite coating and carrier limited, easily cause the hot-spot in the zeolite coating, make catalysqt deactivation.
Mobil company is in a kind of ZSM-5 zeolite molecular sieve of exploitation in 1972, it is the catalysis material that is most widely used up to now, be one of important component in oil fluid cracking (FCC) catalyst, and be applied in the oil refining process such as oil catalytic pyrolysis in hydrocracking and refining.Catalytic field in petrochemical industry, fine chemistry industry and environmental protection etc. also has numerous important application.ZSM-5 has two kinds and intersects the duct, and a kind of is circular straight hole road, and another kind is the oval duct of sinusoidal.The people such as Ivanova are applied to ZSM-5/ foam SiC composite to find in methanol-to-olefins (MTO) reaction, the zeolite coating is thinner, more be conducive to shorten the diffusion length of reactant and product, prevent the generation of secondary response, raising is selective to target product.But because ZSM-5 type zeolite crystal layer is thinner, zeolite crystal is lower in the load capacity of foam silicon carbon carrier surface growth, and the conversion ratio of methyl alcohol is lower.
Summary of the invention
The object of the present invention is to provide a kind of porous silicon carbide carrier surface individual layer, b axle oriented zeolite coating material and preparation method thereof, solve in prior art because ZSM-5 type zeolite crystal layer is thinner the problem such as zeolite crystal is lower in the load capacity of foam silicon carbon carrier surface growth, conversion ratio methyl alcohol is lower.The method is controlled basicity, nutriment concentration and the alkali metal ion addition of diauxic growth solution in advance at silicon carbide ceramics surface in situ growth one deck crystal seed colloid, realizes that zeolite crystal is at the controllable growth on Carboround surface.This structure catalyst is take foam silicon carbon or honeycomb carborundum as carrier, the porous layer that the carrier outer surface has one deck silicon-carbide particle overlap joint to form, and the zeolite coating evenly grows in porous layer.The zeolite coating is single layer structure, and zeolite crystal b axle is perpendicular to the Carboround superficial growth.
Technical scheme of the present invention is:
A kind of porous silicon carbide monolayer surface, b axle oriented zeolite coating material and preparation method thereof, the method adopts the carborundum that there is the foaming structure of the porous layer that one deck silicon-carbide particle overlap joint forms or honeycomb in the surface as carrier, and individual layer, b axle evenly grow in porous layer perpendicular to the zeolite crystal on silicon-carbide particle surface.ZSM-5 type zeolite crystal b axle is perpendicular to the silicon-carbide particle superficial growth, and most reactants and product are spread in the straight hole road of zeolite crystal, improved diffuser efficiency.Change aperture and the degree of depth of Carboround porous surface layer, can regulate and control the load capacity of zeolite crystal.And the aperture of porous layer is larger, when having improved the zeolite crystal load capacity, can not make reactant and product diffusion limited in structure catalyst.The support type structure catalyst that forms like this, the duct is open, specific area is larger, the molecular diffusion performance is good, zeolite crystal and Carboround contact area are large, are conducive to strengthen mass transfer, heat transfer, shorten the time of contact of reactant and product and catalyst, reduce the probability of happening of secondary response, raising is selective to target product.Due to the silicon carbide ceramics surface in situ crystal seed colloid of having grown, can realize that zeolite crystal is at the preferential growth on Carboround surface, control basicity, nutriment concentration and the alkali metal ion addition of diauxic growth solution, can realize the control of the zeolite crystal orientation of growth.The zeolite coating of preparation like this, the property of growing preferentially, crystal orientation are controlled, and load capacity, silica alumina ratio is adjustable.
In the present invention, the zeolite coating is single layer structure, zeolite crystal along the b axle perpendicular to the Carboround superficial growth.The silicon carbide ceramics carrier has macroporous structure, and Carboround is foaming structure or honeycomb; The muscle surface of foam silicon carbon carrier and the hole wall surface of honeycomb Carboround are the porous layer that the silicon-carbide particle overlap joint forms, and the aperture of porous layer is 3～50 microns, and the thickness of porous layer is 5～200 microns.Zeolite crystal evenly grows in Carboround porous surface layer, and zeolite crystal is adjustable in mass fraction is 0～50% (being preferably 2～10%) scope in the load capacity on Carboround surface.
In the present invention, zeolite crystal is ZSM-5 type zeolite.
In the present invention, the preparation method of porous silicon carbide carrier surface individual layer zeolite coating material, in advance at Carboround surface in situ growth one deck crystal seed colloid, control basicity, nutriment concentration and the alkali metal ion addition of diauxic growth solution, realize that zeolite crystal is at the controllable growth on Carboround surface.
Growth in situ crystal seed colloid adopts ethyl orthosilicate as the silicon source, and TPAOH is as template, and synthetic at the deionized water situ, preparation process is as follows:
1) solution preparation
Ethyl orthosilicate, TPAOH, deionized water are mixed in proportion, and the mol ratio between ethyl orthosilicate, TPAOH, deionized water is 1: 0.1～1.0: 10～100; Preferred mol ratio is 1: 0.2～0.4: 20～50;
2) Hydrothermal Synthesis
After the ethyl orthosilicate complete hydrolysis, mentioned solution and porous silicon carbide carrier are placed on Hydrothermal Synthesis in reactor; The temperature of Hydrothermal Synthesis is 100～170 ℃, and the reaction time is 0～12 (being preferably 2～4) hour, and pressure is the solution self-generated pressure.
The preparation of diauxic growth solution adopts ethyl orthosilicate as the silicon source, TPAOH is as template, sodium metaaluminate, aluminum nitrate, aluminum sulfate or aluminium isopropoxide are as the aluminium source, add alkali metal ion (sodium chloride or potassium chloride) balance skeleton electric charge, synthetic at the deionized water situ, preparation process is as follows:
1) solution preparation
Ethyl orthosilicate, TPAOH, aluminium source, alkali metal salt, deionized water are mixed in proportion, and the mol ratio between ethyl orthosilicate, TPAOH, aluminium source, alkali metal salt, deionized water is 1: 0.05～0.50: 0～0.1: 0～0.2: 100～500; Preferred mol ratio is 1: 0.085～0.38: 0～0.08: 0～0.15: 150～380;
2) Hydrothermal Synthesis
Carboround is put into mentioned solution, and the weight ratio of Carboround and reaction solution is 1: (5～50); The temperature of Hydrothermal Synthesis is 130～200 ℃, and the reaction time is 3～72 hours, and pressure is the solution self-generated pressure;
3) roasting
First with the cleaning of the sample after Hydrothermal Synthesis, drying; Then, under air atmosphere, at 500～600 ℃, template is removed in roasting 3～12 hours, obtains the ZSM-5 type zeolite coating material of individual layer, b axle orientation at the porous silicon carbide carrier surface.
In the present invention, the porous silicon carbide ceramic surface has the porous layer that is formed by the silicon-carbide particle overlap joint, and the formation of porous layer relies in the Carboround preparation process, adds appropriate silica flour or silica powder as pore creating material.
In the present invention, the properties of SiC foam ceramics material can use Chinese invention patent application (publication number: properties of SiC foam ceramics material of a kind of high strength dense of mentioning CN1600742A) and preparation method thereof.After foamed plastics is cut out, immerse in slip, after taking-up, remove unnecessary slip, semi-solid preparation, then high temperature, high-pressure curing; With the foams pyrolysis after solidifying, obtain the same with the original foam shape foam-like carbon skeleton that is formed by carborundum and RESEARCH OF PYROCARBON; The carbon skeleton centre bore left by mill, with the pressure injection method with the silicon carbide slurry pressure injection in the carbon skeleton centre bore and fill centre bore, then pyrolysis; Through the siliconising process, the carbon in carbon skeleton and gas phase or liquid-phase silicone are reacted the Formed SiClx, and combine with original silicon-carbide particle in foam framework, thereby obtain the foam silicon carbide ceramics of high strength dense.The preparation of honeycomb silicon carbide ceramics adopts powdered carbon and carborundum powder as raw material, and epoxy resin is as binding agent, by extrusion modling.After moulding, through the siliconising process, carbon and gas phase or liquid-phase silicone reaction Formed SiClx, and combining with original silicon-carbide particle in foam framework, thus obtain the foam silicon carbide ceramics of high strength dense.Process through taking out silicon again, can remove the remaining silicon that in silicon carbide ceramics, the siliconising process stays.Thereby, stayed the hole of 3～50 microns on the Carboround surface.
In the present invention, main component scope and the technical parameter of ZSM-5 type zeolite coating are as follows: molecular sieve crystal is of a size of (1.0～8.0) * (0.5～5.0) * (0.2～1.0) micron, load capacity is 0～50wt%, coating layer thickness is 0.2～1 micron, and the specific area of gained ZSM-5/ foam silicon carbon structure catalyst is 2～200m
2/ g, sial atomic ratio are 11～∞.
In the present invention, b axle orientation refers to that ZSM-5 type zeolite crystal b axle is perpendicular to the silicon-carbide particle superficial growth.
The present invention has following beneficial effect:
The first, the zeolite molecular sieve layer is thinner, and the low-carbon alkene that reaction is generated hightails zeolite catalyst, reduces the time of contact of reactant and zeolite catalyst, prevents the generation of the large molecular product such as alkane, aromatic hydrocarbon.As in methanol to olefins reaction, raising ZSM-5 type zeolite is selective to low-carbon alkene.In addition, thinner zeolite coating can prevent the generation of carbon distribution phenomenon, the extending catalyst life-span.
The second, ZSM-5 type zeolite molecular sieve has two kinds and intersects the duct, and a kind of is circular straight hole road, and another kind is the oval duct of sinusoidal.Along b axle oriented growth in carrier surface, gas permeation will be undertaken by the straight hole road of crystal as ZSM-5 type zeolite crystal, and diffusion length is the shortest, is the direction that is conducive to mass transfer most.Can make product hightail zeolite, the raising zeolite is selective to product.
Three, on the basis that does not affect intensity, by the aperture of adjustment Carboround porous surface layer and the thickness of porous layer, adjust the load capacity of ZSM-5 type zeolite molecular sieve.
For under the prerequisite that guarantees zeolite-loaded amount, improve reactant and the interior diffusivity of product in the zeolite coating.Grow perpendicular to carrier surface along the b axle as ZSM-5 type zeolite crystal, gas permeation will be undertaken by the straight hole road of crystal, and diffusion length is the shortest, is the direction that is conducive to mass transfer most.Adopt the surface to have the carborundum of the foaming structure of the porous layer that is formed by the silicon-carbide particle overlap joint or honeycomb as carrier in the present invention.In its porous layer, the zeolite coating of growth individual layer, b axle orientation.The support type structure catalyst that forms like this, the zeolite coating is very thin, and the duct that in zeolite crystal, mass-transfer efficiency is the highest is perpendicular to carrier surface, and the molecular diffusion performance is good.Zeolite crystal grows in Carboround porous surface layer, and the load capacity of zeolite crystal is larger, and the ZSM-5/ foam silicon carbon structure catalyst specific area that obtains is larger.Zeolite crystal b axle is grown perpendicular to carrier surface, zeolite crystal and Carboround contact area are large, be conducive to strengthen mass transfer, heat transfer, shorten the time of contact of reactant and product and catalyst, reduce the probability of happening of secondary response, under the prerequisite that guarantees conversion ratio, raising is selective to target product.
Description of drawings
Fig. 1 is the fracture apperance of foam silicon carbon carrier.Wherein, (a) figure is the macro morphology of fracture; (b) figure is the porous layer pattern;
Fig. 2 is surface and the fracture apperance of ZSM-5 type zeolite molecular sieve/foam silicon carbon composite.Wherein, (a) figure is surface topography; (b) figure is fracture apperance.
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The foam silicon carbon carrier is (in the present embodiment, the surperficial porous layer for the formation of silicon-carbide particle overlap joint of the muscle of foam silicon carbon carrier, the aperture of porous layer is 10～20 microns, the thickness of porous layer is 30～50 microns, the porosity of silicon carbide porous layer is 30%, sees Fig. 1) preparation method of monolayer surface, b axle orientation ZSM-5 type zeolite molecular sieve coating material:
At first, growth in situ zeolite seed crystal colloid.Ethyl orthosilicate, TPAOH, deionized water were mixed in 1: 0.32: 29 in molar ratio.After the ethyl orthosilicate complete hydrolysis, foam silicon carbon carrier and mentioned solution are placed in reactor, at 130 ℃, Hydrothermal Synthesis 3.5h.After growth in situ zeolite seed crystal colloid, get rid of unnecessary colloidal sol, drying at room temperature 12h with centrifuge.Preparation diauxic growth solution, ethyl orthosilicate, TPAOH, aluminum nitrate, sodium chloride, deionized water 1: 0.17: 0.013 in molar ratio: mix at 0.02: 200.The weight ratio of properties of SiC foam ceramics and reaction solution is 1: 25, and properties of SiC foam ceramics is fixed on apart from reactor bottom 2 centimeters with the polytetrafluoro bracing frame; Liquor capacity is 55 milliliters, and reactor volume is 100 milliliters.Hydro-thermal reaction temperature used is 170 ℃, and the time is 48 hours, and pressure is the self-generated pressure that the solution vaporization produces.After reaction was completed, sample cleaned for several times in the deionized water of 100 ℃ repeatedly, then is the 40Hz supersonic wave cleaning machine with frequency, cleaned 20 minutes, with remove residual solution with matrix a little less than the zeolite crystal that is connected.After cleaning, sample is put into drying baker, and drying is 12 hours under 100 ℃ of conditions.Dry rear sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, and is cooling with stove).The specific area of the ZSM-5/ foam silicon carbon structure catalyst that obtains is 30m
2/ g, the load capacity of zeolite is that the sial atomic ratio of 8%, ZSM-5 type zeolite crystal is 130, grain size is～2.3 * 1.2 * 0.8 μ m
3, coating layer thickness is 0.5～1.0 micron.In the present embodiment, ZSM-5 type zeolite crystal is Load Balanced in foam silicon carbon carrier surface porous layer, and zeolite crystal b axle is perpendicular to silicon-carbide particle superficial growth (seeing Fig. 2).
Embodiment 2
The foam silicon carbon carrier is (in the present embodiment, the surperficial porous layer for the formation of silicon-carbide particle overlap joint of the muscle of foam silicon carbon carrier, the aperture of porous layer is 30～40 microns, the thickness of porous layer is 80～100 microns, and the porosity of silicon carbide porous layer is 60%) preparation method of monolayer surface, b axle orientation ZSM-5 type zeolite molecular sieve coating material:
The method of growth in situ zeolite seed crystal colloid is with embodiment 1.Preparation diauxic growth solution, ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water 1: 0.17: 0.065 in molar ratio: 200 mix.The weight ratio of properties of SiC foam ceramics and reaction solution is 1: 25, and properties of SiC foam ceramics is fixed on apart from reactor bottom 1 centimeters with the polytetrafluoro bracing frame; Liquor capacity is 55 milliliters, and reactor volume is 100 milliliters.Hydro-thermal reaction temperature used is 170 ℃, and the time is 48 hours, and pressure is the self-generated pressure that the solution vaporization produces.After reaction was completed, sample cleaned for several times in the deionized water of 100 ℃ repeatedly, then is the 40Hz supersonic wave cleaning machine with frequency, cleaned 20 minutes, with remove residual solution with matrix a little less than the molecular sieve crystal that is connected.After cleaning, sample is put into drying baker, and drying is 12 hours under 100 ℃ of conditions.Dry rear sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, and is cooling with stove).The specific area of the ZSM-5/ foam silicon carbon structure catalyst that obtains is 75m
2/ g, the load capacity of zeolite is that the sial atomic ratio of 20%, ZSM-5 type zeolite crystal is 200, grain size is～3.2 * 1.8 * 1.0 μ m
3, coating layer thickness is 0.8～1.5 micron.In the present embodiment, ZSM-5 type zeolite crystal is Load Balanced in foam silicon carbon carrier surface porous layer, and zeolite crystal b axle is perpendicular to the silicon-carbide particle superficial growth.
Embodiment 3
The honeycomb Carboround is (in the present embodiment, the hole wall surface of honeycomb Carboround is the porous layer that the silicon-carbide particle overlap joint forms, the aperture of porous layer is 5～10 microns, the thickness of porous layer is 20～30 microns, and the porosity of silicon carbide porous layer is 60%) preparation method of monolayer surface, b axle orientation ZSM-5 type zeolite molecular sieve coating material:
The method of growth in situ zeolite seed crystal colloid is with embodiment 1.Preparation diauxic growth solution, ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water 1: 0.17: 0.065 in molar ratio: 200 mix.The weight ratio of honeycomb silicon carbide ceramics and reaction solution is 1: 25, and the honeycomb silicon carbide ceramics is fixed on apart from reactor bottom 1 centimeters with the polytetrafluoro bracing frame; Liquor capacity is 55 milliliters, and reactor volume is 100 milliliters.Hydro-thermal reaction temperature used is 170 ℃, and the time is 48 hours, and pressure is the self-generated pressure that the solution vaporization produces.After reaction was completed, sample cleaned for several times in the deionized water of 100 ℃ repeatedly, then is the 40Hz supersonic wave cleaning machine with frequency, cleaned 20 minutes, with remove residual solution with matrix a little less than the molecular sieve crystal that is connected.After cleaning, sample is put into drying baker, and drying is 12 hours under 100 ℃ of conditions.Dry rear sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, and is cooling with stove).The specific area of the ZSM-5/ honeycomb silicon carbide structure catalyst that obtains is 156m
2/ g, the load capacity of zeolite is that the sial atomic ratio of 40%, ZSM-5 type zeolite crystal is 195, grain size is～3.0 * 1.6 * 0.9 μ m
3, coating layer thickness is 0.6～1.2 micron.In the present embodiment, ZSM-5 type zeolite crystal is Load Balanced in honeycomb Carboround porous surface layer, and zeolite crystal b axle is perpendicular to the silicon-carbide particle superficial growth.
The embodiment result shows, in advance at porous silicon carbide surface in situ growth one deck crystal seed colloid, controls basicity, nutriment concentration and the alkali metal ion addition of diauxic growth solution, realizes that zeolite crystal is at the controllable growth on Carboround surface.Regulation and control porous silicon carbide carrier surface porosity can be adjusted the zeolite crystal load capacity.
In the present invention, this structure catalyst is take foam silicon carbon or honeycomb carborundum as carrier, the porous layer that the carrier outer surface has one deck silicon-carbide particle overlap joint to form, and the zeolite coating evenly grows in porous layer.The zeolite coating is single layer structure, and zeolite crystal b axle is perpendicular to the Carboround superficial growth.The method is controlled basicity, nutriment concentration and the alkali metal ion addition of diauxic growth solution in advance at silicon carbide ceramics surface in situ growth one deck crystal seed colloid, realizes that zeolite crystal is at the controllable growth on Carboround surface.This structure catalyst duct opening, the molecular diffusion performance is good, specific area and load capacity are larger, zeolite crystal and Carboround contact area are large, be conducive to strengthen mass transfer, heat transfer, shorten the time of contact of reactant and product and catalyst, reduce the probability of happening of secondary response, under the prerequisite that guarantees conversion ratio, raising is selective to target product.
Claims (3)
1. porous silicon carbide monolayer surface, b axle are orientated the preparation method of ZSM-5 zeolite coating material, it is characterized in that, in advance at Carboround surface in situ growth one deck crystal seed colloid, control basicity, nutriment concentration and the alkali metal ion addition of diauxic growth solution, realize that zeolite crystal is at the controllable growth on Carboround surface; Described b axle orientation refers to that ZSM-5 type zeolite crystal b axle is perpendicular to the silicon-carbide particle superficial growth;
Growth in situ crystal seed colloid adopts ethyl orthosilicate as the silicon source, and TPAOH is as template, and synthetic at the deionized water situ, preparation process is as follows:
1) solution preparation
Ethyl orthosilicate, TPAOH, deionized water are mixed in proportion, and the mol ratio between ethyl orthosilicate, TPAOH, deionized water is 1:0.1～1.0:10～100;
2) Hydrothermal Synthesis
After the ethyl orthosilicate complete hydrolysis, mentioned solution and porous silicon carbide carrier are placed on Hydrothermal Synthesis in reactor; The temperature of Hydrothermal Synthesis is 100～170 ℃, and the reaction time is 3.5～12 hours, and pressure is the solution self-generated pressure;
The preparation of diauxic growth solution adopts ethyl orthosilicate as the silicon source, TPAOH is as template, and sodium metaaluminate, aluminum nitrate, aluminum sulfate or aluminium isopropoxide add alkali metal ion balance skeleton electric charge as the aluminium source, synthetic at the deionized water situ, preparation process is as follows:
1) solution preparation
Ethyl orthosilicate, TPAOH, aluminium source, alkali metal salt, deionized water are mixed in proportion, and the mol ratio between ethyl orthosilicate, TPAOH, aluminium source, alkali metal salt, deionized water is 1:0.05～0.50:0.013～0.1:0.02～0.2:100～500;
2) Hydrothermal Synthesis
Carboround is put into mentioned solution, and the weight ratio of Carboround and reaction solution is 1:(5～50); The temperature of Hydrothermal Synthesis is 130～200 ℃, and the reaction time is 3～72 hours, and pressure is the solution self-generated pressure;
3) roasting
First with the cleaning of the sample after Hydrothermal Synthesis, drying; Then, under air atmosphere, at 500～600 ℃, template is removed in roasting 3～12 hours, obtains the ZSM-5 type zeolite coating material of individual layer, b axle orientation at the porous silicon carbide carrier surface.
2. be orientated the preparation method of ZSM-5 zeolite coating material according to porous silicon carbide monolayer surface claimed in claim 1, b axle, it is characterized in that, Carboround has macroporous structure, and Carboround is foaming structure or honeycomb; The muscle surface of foam silicon carbon carrier and the hole wall surface of honeycomb Carboround are the porous layer that the silicon-carbide particle overlap joint forms, and the aperture of porous layer is 3～50 microns, and the thickness of porous layer is 5～200 microns.
3. be orientated the preparation method of ZSM-5 zeolite coating material according to porous silicon carbide monolayer surface claimed in claim 1, b axle, it is characterized in that, zeolite crystal evenly grows in Carboround porous surface layer, and zeolite crystal is adjustable in mass fraction is 8～50% scopes in the load capacity on Carboround surface.
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