CN102274744A - 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 crystal is 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, concrete a kind of porous silicon carbide carrier surface individual layer, b axle orientation ZSM-5 type zeolite coating material and preparation method thereof of relating to.
Background technology
Zeolite crystal has particular structure and performance, has obtained in fields such as petrochemical industry, environmental protection using widely as catalyst, catalyst carrier or adsorbent.Traditional zeolite crystal catalyst all is that the form with particle is applied in the fixed bed, not only causes bed pressure drop to raise and causes the waste of the energy, and also produce bigger concentration and thermograde in process of production, has reduced the catalytic efficiency of catalyst.Simultaneously, the separation and the recovery difficult of zeolite crystal catalyst are big, 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.Ceramic materials such as 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; Though ceramic material such as aluminium oxide, cordierite oxidation resistance is strong, its mechanical strength and thermal conductivity are poor.Silicon carbide ceramics has high thermal conductivity and mechanical strength, anti-oxidant, chemical inertness, advantage that density is 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 advantage of this method is simple to operate, applicable to the carrier of different shape.But its shortcoming is to be difficult for forming fine and close zeolite membrane, and it is firm inadequately between zeolite coating and the carrier in conjunction with getting, therefore the course of reaction violent in some variations in temperature, that air velocity is fast and mechanical shock is big, 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 this method is that the zeolite molecular sieve layer combines with carrier surface and must compare firmly.But the zeolite coating of this method preparation is very fine and close, and intracrystalline pore is considerably less.For obtaining bigger load capacity, the method for taking usually 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, have only the active sites of close zeolite catalyst outer surface to be utilized, and zeolite crystal or zeolite coating inside can not be utilized, and have reduced the utilization rate of catalyst.Simultaneously, because the zeolite crystal size is big 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 the selectivity to target product.Simultaneously,, make the heat transfer between zeolite coating and the carrier limited, cause the hot-spot in the zeolite coating easily, make catalysqt deactivation because the zeolite crystal size is big or the zeolite coating is thicker.
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 the hydrocracking and refining.Catalytic field in petrochemical industry, fine chemistry industry and environmental protection etc. also has numerous important use.ZSM-5 has two kinds of intersection ducts, and a kind of is circular straight hole road, and another kind is the oval duct of sinusoidal.People such as Ivanova are applied to ZSM-5/ foam SiC composite to find in methanol-to-olefins (MTO) reaction, the zeolite coating is thin more, help shortening the diffusion length of reactant and product more, prevent the generation of secondary response, improve selectivity 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 conversion of methanol 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 the prior art because problem such as ZSM-5 type zeolite crystal layer is thinner, and zeolite crystal is lower in the load capacity of foam silicon carbon carrier surface growth, conversion of methanol is lower.At silicon carbide ceramics surface in situ growth one deck crystal seed colloid, basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution realize the controllable growth of zeolite crystal on the Carboround surface to this method in advance.This structure catalyst is a carrier with foam silicon carbon or honeycomb carborundum, 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 the porous layer.The zeolite coating is a 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, this 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 the porous layer perpendicular to the zeolite crystal on silicon-carbide particle surface.ZSM-5 type zeolite crystal b axle so just makes most reactants and product spread in the straight hole road of zeolite crystal perpendicular to the silicon-carbide particle superficial growth, has improved diffuser efficiency.Change the 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 bigger, when having improved the zeolite crystal load capacity, can not make reactant and product diffusion limited in structure catalyst.The support type structure catalyst of Xing Chenging like this, the duct is open, specific area is bigger, the molecular diffusion performance is good, zeolite crystal and Carboround contact area are big, help strengthening mass transfer, heat transfer, shorten the time of contact of reactant and product and catalyst, reduce the probability of happening of secondary response, improve selectivity target product.The crystal seed colloid because the silicon carbide ceramics surface in situ has been grown, can realize the preferential growth of zeolite crystal on the Carboround surface, basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution can realize the control of the zeolite crystal orientation of growth.Zhi Bei zeolite coating like this, growth property, crystal orientation according to qualifications are controlled, and load capacity, silica alumina ratio is adjustable.
Among the present invention, the zeolite coating is a 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 porous layer thickness is 5～200 microns.Zeolite crystal evenly grows in the 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.
Among the present invention, zeolite crystal is a ZSM-5 type zeolite.
Among 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, basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution realize the controllable growth of zeolite crystal on the Carboround surface.
Growth in situ crystal seed colloid adopts ethyl orthosilicate as the silicon source, and TPAOH is as the template agent, and original position is synthetic in deionized water, and 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, the deionized water is 1: 0.1～1.0: 10～100; Preferred mol ratio is 1: 0.2～0.4: 20～50;
2) hydro-thermal is synthetic
After treating the ethyl orthosilicate complete hydrolysis, it is synthetic that above-mentioned solution and porous silicon carbide carrier are placed in the reactor hydro-thermal; The synthetic temperature of hydro-thermal 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 the template agent, 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, original position is synthetic in deionized water, and 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, the 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) hydro-thermal is synthetic
Carboround is put into above-mentioned solution, and the weight ratio of Carboround and reaction solution is 1: (5～50); The synthetic temperature of hydro-thermal is 130～200 ℃, and the reaction time is 3～72 hours, and pressure is the solution self-generated pressure;
3) roasting
Sample after earlier hydro-thermal being synthesized cleans, drying; Then, under air atmosphere, at 500～600 ℃, the template agent 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.
Among 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 an amount of silica flour or silica powder as pore creating material.
Among the present invention, the foam silicon carbon ceramic material can use Chinese invention patent application (publication number: foam silicon carbon ceramic material of a kind of high strength dense of mentioning CN1600742A) and preparation method thereof.After foamed plastics cut out, immerse in the slip, after the taking-up, remove unnecessary slip, semi-solid preparation, high temperature, high pressure solidify then; With the foams pyrolysis after solidifying, obtain the same with the original foam shape foam-like carbon skeleton of forming by carborundum and RESEARCH OF PYROCARBON; The carbon skeleton centre bore left by mill, with the pressure injection method with carborundum slip pressure injection in the carbon skeleton centre bore and add full centre bore, pyrolysis then; Through the siliconising process, the carbon in the carbon skeleton and gas phase or liquid-phase silicone reaction generation carborundum, and combine with original silicon-carbide particle in the foam framework, thus 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 the moulding, through the siliconising process, the reaction of carbon and gas phase or liquid-phase silicone generates carborundum, and combines with original silicon-carbide particle in the foam framework, thereby obtains the foam silicon carbide ceramics of high strength dense.Handle through taking out silicon again, can remove the remaining silicon that the siliconising process stays in the silicon carbide ceramics.Thereby, stayed 3～50 microns hole on the Carboround surface.
Among the present invention, the 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～∞.
Among the present invention, b axle orientation is meant 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 big molecular product such as alkane, aromatic hydrocarbon.As in methanol to olefins reaction, improve the selectivity of ZSM-5 type zeolite to low-carbon alkene.In addition, thin zeolite coating can prevent the generation of carbon distribution phenomenon, prolongs catalyst life.
The second, ZSM-5 type zeolite molecular sieve has two kinds of intersection ducts, and a kind of is circular straight hole road, and another kind is the oval duct of sinusoidal.As ZSM-5 type zeolite crystal along b axle oriented growth in carrier surface, gas infiltration will be undertaken by the straight hole road of crystal, diffusion length is the shortest, is the direction that helps mass transfer most.Can make product hightail zeolite, improve the selectivity of zeolite product.
Three, do not influencing on the intensity based,, adjusting the load capacity of ZSM-5 type zeolite molecular sieve by adjusting the aperture and the porous layer thickness of Carboround porous surface layer.
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, the gas infiltration will be undertaken by the straight hole road of crystal, and diffusion length is the shortest, is the direction that helps mass transfer most.Adopt the surface to have the carborundum of the foaming structure of the porous layer that forms by the silicon-carbide particle overlap joint or honeycomb among the present invention as carrier.In its porous layer, the zeolite coating of growth individual layer, b axle orientation.The support type structure catalyst of Xing Chenging like this, the zeolite coating is extremely thin, and the duct that mass-transfer efficiency is the highest in the zeolite crystal is perpendicular to carrier surface, and the molecular diffusion performance is good.Zeolite crystal grows in the Carboround porous surface layer, and the load capacity of zeolite crystal is bigger, and the ZSM-5/ foam silicon carbon structure catalyst specific area that obtains is bigger.Zeolite crystal b axle is grown perpendicular to carrier surface, zeolite crystal and Carboround contact area are big, help strengthening 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, improve selectivity 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 the surface and the fracture apperance of ZSM-5 type zeolite molecular sieve/foam silicon carbon composite.Wherein, (a) figure is a surface topography; (b) figure is a 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 porous layer that the muscle surface of foam silicon carbon carrier forms for the silicon-carbide particle overlap joint, the aperture of porous layer is 10～20 microns, porous layer thickness 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 treating the ethyl orthosilicate complete hydrolysis, foam silicon carbon carrier and above-mentioned solution are placed reactor, at 130 ℃, hydro-thermal is synthesized 3.5h.Behind the 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 foam silicon carbon pottery is 1: 25 with the weight ratio of reaction solution, and the foam silicon carbon pottery is fixed on apart from reactor bottom 2 centimeters with poly-tetrafluoro bracing frame; Liquor capacity is 55 milliliters, and reactor volume is 100 milliliters.The used temperature of hydro-thermal reaction is 170 ℃, and the time is 48 hours, and pressure is the self-generated pressure that the solution vaporization produces.After reaction was finished, sample cleaned for several times in 100 ℃ deionized water repeatedly, is the 40Hz supersonic wave cleaning machine with frequency again, cleaned 20 minutes, with remove residual solution with matrix a little less than the zeolite crystal that is connected.To clean the back sample and put into drying baker, drying is 12 hours under 100 ℃ of conditions.Dry the back sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, with the stove cooling).The specific area of the ZSM-5/ foam silicon carbon structure catalyst that obtains is 30m
2/ g, the load capacity of zeolite is 8%, and the sial atomic ratio of ZSM-5 type zeolite crystal is 130, and 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, the load in foam silicon carbon carrier surface porous layer of ZSM-5 type zeolite crystal is even, and zeolite crystal b axle is perpendicular to silicon-carbide particle superficial growth (see figure 2).
Embodiment 2
The foam silicon carbon carrier is (in the present embodiment, the porous layer that the muscle surface of foam silicon carbon carrier forms for the silicon-carbide particle overlap joint, the aperture of porous layer is 30～40 microns, porous layer thickness 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 foam silicon carbon pottery is 1: 25 with the weight ratio of reaction solution, and the foam silicon carbon pottery is fixed on apart from reactor bottom 1 centimeters with poly-tetrafluoro bracing frame; Liquor capacity is 55 milliliters, and reactor volume is 100 milliliters.The used temperature of hydro-thermal reaction is 170 ℃, and the time is 48 hours, and pressure is the self-generated pressure that the solution vaporization produces.After reaction was finished, sample cleaned for several times in 100 ℃ deionized water repeatedly, is the 40Hz supersonic wave cleaning machine with frequency again, cleaned 20 minutes, with remove residual solution with matrix a little less than the molecular sieve crystal that is connected.To clean the back sample and put into drying baker, drying is 12 hours under 100 ℃ of conditions.Dry the back sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, with the stove cooling).The specific area of the ZSM-5/ foam silicon carbon structure catalyst that obtains is 75m
2/ g, the load capacity of zeolite is 20%, and the sial atomic ratio of ZSM-5 type zeolite crystal is 200, and 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, the load in foam silicon carbon carrier surface porous layer of ZSM-5 type zeolite crystal is even, 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, porous layer thickness 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 poly-tetrafluoro bracing frame; Liquor capacity is 55 milliliters, and reactor volume is 100 milliliters.The used temperature of hydro-thermal reaction is 170 ℃, and the time is 48 hours, and pressure is the self-generated pressure that the solution vaporization produces.After reaction was finished, sample cleaned for several times in 100 ℃ deionized water repeatedly, is the 40Hz supersonic wave cleaning machine with frequency again, cleaned 20 minutes, with remove residual solution with matrix a little less than the molecular sieve crystal that is connected.To clean the back sample and put into drying baker, drying is 12 hours under 100 ℃ of conditions.Dry the back sample in Muffle furnace, 550 ℃ of roastings 6 hours (programming rate is 2 ℃/min, with the stove cooling).The specific area of the ZSM-5/ honeycomb silicon carbide structure catalyst that obtains is 156m
2/ g, the load capacity of zeolite is 40%, and the sial atomic ratio of ZSM-5 type zeolite crystal is 195, and 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, the load in honeycomb Carboround porous surface layer of ZSM-5 type zeolite crystal is even, and zeolite crystal b axle is perpendicular to the silicon-carbide particle superficial growth.
Embodiment result shows that at porous silicon carbide surface in situ growth one deck crystal seed colloid, basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution realize the controllable growth of zeolite crystal on the Carboround surface in advance.Regulation and control porous silicon carbide carrier surface porosity can be adjusted the zeolite crystal load capacity.
Among the present invention, this structure catalyst is a carrier with foam silicon carbon or honeycomb carborundum, 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 the porous layer.The zeolite coating is a single layer structure, and zeolite crystal b axle is perpendicular to the Carboround superficial growth.At silicon carbide ceramics surface in situ growth one deck crystal seed colloid, basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution realize the controllable growth of zeolite crystal on the Carboround surface to this method in advance.This structure catalyst duct is open, the molecular diffusion performance is good, specific area and load capacity are bigger, zeolite crystal and Carboround contact area are big, help strengthening 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, improve selectivity to target product.
Claims (7)
1. a porous silicon carbide monolayer surface, b axle orientation ZSM-5 zeolite coating material is characterized in that the zeolite coating is a single layer structure, zeolite crystal along the b axle perpendicular to the Carboround superficial growth.
2. be orientated ZSM-5 zeolite coating material according to the described porous silicon carbide monolayer surface of claim 1, b axle, it is characterized in that Carboround has macroporous structure, 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 porous layer thickness is 5～200 microns.
3. be orientated ZSM-5 zeolite coating material according to the described porous silicon carbide monolayer surface of claim 1, b axle, it is characterized in that, zeolite crystal evenly grows in the Carboround porous surface layer, and zeolite crystal is adjustable in mass fraction is 0～50% scope in the load capacity on Carboround surface.
4. be orientated ZSM-5 zeolite coating material according to the described porous silicon carbide monolayer surface of claim 1, b axle, it is characterized in that, zeolite crystal is a ZSM-5 type zeolite.
5. be orientated the preparation method of ZSM-5 zeolite coating material according to the described porous silicon carbide monolayer surface of claim 1, b axle, it is characterized in that, in advance at Carboround surface in situ growth one deck crystal seed colloid, basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution realize the controllable growth of zeolite crystal on the Carboround surface.
6. be orientated the preparation method of ZSM-5 zeolite coating material according to the described porous silicon carbide monolayer surface of claim 5, b axle, it is characterized in that, growth in situ crystal seed colloid adopts ethyl orthosilicate as the silicon source, TPAOH is as the template agent, original position is synthetic in deionized water, and 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, the deionized water is 1: 0.1～1.0: 10～100;
2) hydro-thermal is synthetic
After treating the ethyl orthosilicate complete hydrolysis, it is synthetic that above-mentioned solution and porous silicon carbide carrier are placed in the reactor hydro-thermal; The synthetic temperature of hydro-thermal is 100～170 ℃, and the reaction time is 0～12 hour, and pressure is the solution self-generated pressure.
7. be orientated the preparation method of ZSM-5 zeolite coating material according to the described porous silicon carbide monolayer surface of claim 5, b axle, it is characterized in that, the preparation of diauxic growth solution adopts ethyl orthosilicate as the silicon source, TPAOH is as the template agent, sodium metaaluminate, aluminum nitrate, aluminum sulfate or aluminium isopropoxide are as the aluminium source, add alkali metal ion balance skeleton electric charge, original position is synthetic in deionized water, and 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, the deionized water is 1: 0.05～0.50: 0～0.1: 0～0.2: 100～500;
2) hydro-thermal is synthetic
Carboround is put into above-mentioned solution, and the weight ratio of Carboround and reaction solution is 1: (5～50); The synthetic temperature of hydro-thermal is 130～200 ℃, and the reaction time is 3～72 hours, and pressure is the solution self-generated pressure;
3) roasting
Sample after earlier hydro-thermal being synthesized cleans, drying; Then, under air atmosphere, at 500～600 ℃, the template agent 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.
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| CN108587576A (en) * | 2018-07-23 | 2018-09-28 | 淄博职业学院 | A kind of computer heat transmission heat-conducting silicone grease and preparation method thereof |
| CN115397777A (en) * | 2020-02-12 | 2022-11-25 | 休斯敦大学系统 | Synthesis of Fin-shaped zeolite crystals |
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| 《无机材料学报》 20090331 罗民等 "ＺＳＭ-５分子筛膜／多孔ＳｉＳｉＣ陶瓷复合孔结构微反应器的制备" 第334页第3节结论、第300页摘要、第333页图4 1-4 第24卷, 第2期 * |
| 罗民等: ""ＺＳＭ-５分子筛膜／多孔ＳｉＳｉＣ陶瓷复合孔结构微反应器的制备"", 《无机材料学报》, vol. 24, no. 2, 31 March 2009 (2009-03-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587576A (en) * | 2018-07-23 | 2018-09-28 | 淄博职业学院 | A kind of computer heat transmission heat-conducting silicone grease and preparation method thereof |
| CN115397777A (en) * | 2020-02-12 | 2022-11-25 | 休斯敦大学系统 | Synthesis of Fin-shaped zeolite crystals |
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