CN102274743A - High intercrystal poriness zeolite coating material on surface of porous silicon carbide carrier and preparation method thereof - Google Patents
High intercrystal poriness zeolite coating material on surface of porous silicon carbide carrier and preparation method thereof Download PDFInfo
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Abstract
The invention which belongs to the technical field of structured catalysts and application technologies thereof concretely relates to a high intercrystal poriness zeolite coating material on the surface of a porous silicon carbide carrier and a preparation method thereof. The porous silicon carbide carrier involved by the material has a macroscopic porous structure, for example a foamy structure, and a honeycomb structure. The zeolite coating has a high intercrystal poriness. According to the preparation method, the surface of the porous silicon carbide carrier is modified by a colloidal zeolite guiding agent to realize the preferred growth of zeolite crystal on the surface of the porous silicon carbide carrier; and the alkalinity of a secondary growth solution, the concentration of nutrients, and the addition of alkali metal ions are controlled to control the intercrystal poriness of zeolite. The coating material has the advantages of high intercrystal poriness, small zeolite crystal dimension, good molecular diffusion ability, large zeolite load capacity, adjustable silica-alumina ratio of the zeolite crystal and zeolite coating thickness, and good binding ability of the zeolite crystal with the surface of the porous silicon carbide carrier. The structured catalyst which is in favor of mass and heat transfer reinforcement has wide application prospects in fields of catalysis, adsorption, separation and the like.
Description
Technical field
The invention belongs to structure catalyst and applied technical field thereof, the concrete high intercrystalline pore of a kind of porous silicon carbide carrier surface rate zeolite coating material and preparation method thereof that relates 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.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 molecular sieve molecular sieve and adhesive oxides, thereby makes carrier table load one deck zeolite molecular sieve.The outstanding advantage of this method is simple to operate, applicable to the carrier of different shape.But its shortcoming is a course of reaction firm inadequately in conjunction with getting, therefore violent in some variations in temperature, that air velocity is fast and mechanical shock is big between zeolite coating and the carrier, and is not ideal enough by the load zeolite 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 coating combines with carrier surface and must compare firmly.It is very fine and close that but the shortcoming of this method is a coating, and intracrystalline pore is considerably less.For obtaining bigger load capacity, the method for taking usually is to prepare zeolite megacryst or thicker zeolite membrane at carrier surface.Like this, reactant and product are spread in zeolite crystal and zeolite coating be restricted, consequently, have only the zeolite inner surface of close catalyst granules outside to be utilized, and the inner surface of micropore core and the inside can not utilize, and has reduced the utilization rate of catalyst.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.
Summary of the invention
The object of the present invention is to provide the high intercrystalline pore of a kind of porous silicon carbide carrier surface rate zeolite coating material and preparation method thereof, solve in the prior art problems such as load zeolite coating is not ideal enough.The porous silicon carbide carrier that this material relates to has macroporous structure, as foaming structure, honeycomb.The zeolite coating has high intercrystalline pore rate, and intracrystalline pore is formed by 0.5～10 micron ZSM-5 or Silicalite-1 type zeolite crystal overlap joint.This method is by the colloidal state guiding agent for zeolite of growing at the Carboround surface in situ, and basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution, the realization zeolite crystal is at Carboround surface preferential growth and control the intercrystalline pore rate.This coating material has high intercrystalline pore rate, and the zeolite crystal size is little, and the molecular diffusion performance is good; Zeolite-loaded amount is bigger, and the zeolite crystal silica alumina ratio, the zeolite coating layer thickness is adjustable; Zeolite crystal and Carboround interfacial combined function are good.
Technical scheme of the present invention is:
The high intercrystalline pore of a kind of porous silicon carbide carrier surface rate zeolite coating material and preparation method thereof, this method adopt the carborundum of foaming structure or honeycomb as carrier, at the zeolite crystal of the high intercrystalline pore of its superficial growth rate.The hole that has 2～3000 nanometers between the zeolite crystal helps improving reactant and the mass transfer ability of product in the zeolite coating.Adopt colloidal state crystal seed directed agents to the porous silicon carbide support modification, realize that zeolite crystal is at the preferential forming core of carrier surface, preferential growth.Basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution, the realization zeolite crystal is at Carboround surface preferential growth and control the intercrystalline pore rate.By adjusting the method for aluminium ion addition, regulation and control zeolite coating silica alumina ratio.By ratio that changes solution and porous silicon carbide carrier and the method for synthesizing number of times, the load capacity of regulation and control zeolite crystal.
Among the present invention, this coating material has high intercrystalline pore rate, intracrystalline pore is of a size of 2～3000 nanometers, and zeolite crystal is big in the load capacity of porous silicon carbide carrier surface, and the load capacity of zeolite crystal is adjustable in mass fraction 0～60% (being preferably 10～30%) scope.Carboround has macroporous structure, and Carboround is foaming structure or honeycomb.
Among the present invention, described zeolite crystal is ZSM-5 or silicalite-1 type zeolite, and zeolite crystal is of a size of 0.5～10 micron.
Among the present invention, the preparation method of the high intercrystalline pore of porous silicon carbide carrier surface rate zeolite coating material carries out modification by the colloidal state guiding agent for zeolite to Carboround, and the control zeolite crystal is at the preferential forming core in Carboround surface, preferential growth; Basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution, regulation and control coating intercrystalline pore rate and load capacity.
The preparation of colloidal state guiding agent for zeolite 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; 100～170 ℃ of the synthetic temperature of hydro-thermal, reaction time 0～12 (being preferably 1～6) hour, 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: 0.1～0.35: 100～500; Preferred mol ratio is 1: 0.085～0.38: 0～0.08: 0.15～0.30: 150～380;
2) hydro-thermal is synthetic
Carboround is put into above-mentioned solution, and the weight ratio of silicon carbide ceramics 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 high intercrystalline pore rate zeolite coating material 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 present invention's pottery muscle density height, microscopic structure uniform strength height.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.
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 (2～10) * (1.0～5.0) * (0.5～3.0) micron, load capacity is 0～60wt%, coating layer thickness is 2～100 microns, and the specific area of gained zeolite coating and porous silicon carbide ceramic composite that carrier is formed is 2～200m
2/ g, sial atomic ratio are 11～∞.
Among the present invention, the main component scope and the technical parameter of silicalite-1 type zeolite coating are as follows: molecular sieve crystal is of a size of (2～10) * (1.5～6.0) * (0.5～4.0) micron, load capacity is 0～60wt%, coating layer thickness is 2～120 microns, and the specific area of gained molecular sieve coating and porous silicon carbide ceramic composite that carrier is formed is 2～240m
2/ g.
The present invention has following beneficial effect:
The first, the zeolite crystal size is little.The zeolite of little crystal grain has that external surface area is big, the surface can be high, the sour bit quantity of outer surface increases, high adsorption capacity, also is that conventional zeolite institute is inaccessible to macromolecular suction-operated particularly.These character all will help to macromolecular activation and for the modulation modification of outer surface of zeolite.After the zeolite particle diameter diminished, its duct was short and regular, helped the diffusion of molecule and reduce carbon distribution taking place.In addition, zeolite crystal diminishes, and helps improving carried metal component dispersiveness and load capacity.
The second, zeolite-loaded amount is big, and the zeolite coating has high intercrystalline pore rate, and interfacial combined function is good between zeolite coating and the carrier, helps improving mass transfer, the heat-transfer capability of zeolite coating, thereby improves reaction efficiency and improve selectivity to target product.
Three, zeolite coating layer thickness, silica alumina ratio, thickness is adjustable, satisfies the needs of differential responses.
For strengthening zeolite coating inner transmission matter and improving zeolite coating load capacity, adopt among the present invention at Carboround surface in situ growth colloidal state guiding agent for zeolite, and the method for basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution, the realization zeolite crystal is at Carboround surface preferential growth and control the intercrystalline pore rate.This coating material has high intercrystalline pore rate, and the zeolite crystal size is little, and the molecular diffusion performance is good; Zeolite-loaded amount is bigger, and the zeolite crystal silica alumina ratio, the zeolite coating layer thickness is adjustable; Zeolite crystal and Carboround interfacial combined function are good.This structure catalyst helps strengthening mass transfer, heat transfer, will have wide practical use in fields such as catalysis, absorption, separation.
Description of drawings
Fig. 1 is the surface and the fracture apperance of ZSM-5 type zeolite/foam silicon carbon composite.Wherein, (a) figure is a surface topography; (b) figure is the cross section pattern.
Fig. 2 is the graph of pore diameter distribution of ZSM-5 type zeolite/foam silicon carbon composite.The specific area (BET) of ZSM-5/ foam SiC composite is 82.47m
2g
-1, micropore surface is long-pending to be 42.75m
2g
-1, the external surface area that the t-plot method records composite is 39.72m
2g
-1, micro pore volume is 0.022cm
3g
-1Adopt the method for Barrett-Joyner-Halenda (BJH) to estimate the pore size distribution of aperture in 1.7～300nm scope, and to calculate the aperture be 0.027cm at the volume of 1.7～300nm part
3g
-1
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
In the present embodiment, the preparation method of the high intercrystalline pore of foam silicon carbon carrier surface rate zeolite coating material:
At first, utilize colloidal state zeolite seed crystal directed agents that the foam silicon carbon carrier is carried out surface modification.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 4h.Preparation diauxic growth solution, ethyl orthosilicate, TPAOH, aluminum nitrate, sodium chloride, deionized water 1: 0.15: 0.013 in molar ratio: mix at 0.22: 150.The weight ratio of foam silicon carbon carrier and reaction solution is 1: 30, and the foam silicon carbon carrier 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 load capacity that obtains the high intercrystalline pore of ZSM-5/ foam silicon carbon carrier surface rate zeolite coating material is 13wt%, and coating layer thickness is 10 microns, and the sial atomic ratio is 75, and specific area (BET) is 82.47m
2g
-1, micropore surface is long-pending to be 42.75m
2g
-1, the external surface area that the t-plot method records composite is 39.72m
2g
-1, micro pore volume is 0.022cm
3g
-1Adopt the method for Barrett-Joyner-Halenda (BJH) to estimate the pore size distribution of aperture in 1.7～300nm scope, and to calculate the aperture be 0.027cm at the volume of 1.7～300nm part
3g
-1(see Fig. 1-Fig. 2).
Embodiment 2
In the present embodiment, the preparation method of the high intercrystalline pore of foam silicon carbon carrier surface rate zeolite coating material:
Colloidal state zeolite seed crystal directed agents is carried out the method for surface modification with embodiment 1 to the foam silicon carbon carrier.Preparation diauxic growth solution, ethyl orthosilicate, TPAOH, deionized water mixed in 1: 0.15: 150 in molar ratio.The weight ratio of foam silicon carbon carrier and reaction solution is 1: 30, and the foam silicon carbon carrier 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 load capacity that obtains the high intercrystalline pore of silicalite-1/ foam silicon carbon carrier surface rate zeolite coating material is 19wt%, and coating layer thickness is 18 microns, and specific area (BET) is 120.35m
2g
-1, micropore surface is long-pending to be 62.75m
2g
-1, the external surface area that the t-plot method records composite is 57.60m
2g
-1, micro pore volume is 0.034cm
3g
-1Adopt the method for Barrett-Joyner-Halenda (BJH) to estimate the pore size distribution of aperture in 1.7～300nm scope, and to calculate the aperture be 0.033cm at the volume of 1.7～300nm part
3g
-1
Embodiment 3
In the present embodiment, the preparation method of high intercrystalline pore, honeycomb Carboround surface rate zeolite coating material:
Colloidal state zeolite seed crystal directed agents is carried out the method for surface modification with embodiment 1 to the honeycomb Carboround.Preparation diauxic growth solution, ethyl orthosilicate, TPAOH, aluminum nitrate, sodium chloride, deionized water 1: 0.15: 0.0065 in molar ratio: mix at 0.15: 190.The weight ratio of honeycomb Carboround 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 load capacity that obtains high intercrystalline pore, ZSM-5/ honeycomb Carboround surface rate zeolite coating material is 23wt%, and coating layer thickness is 15 microns, and the sial atomic ratio is 150, and specific area (BET) is 150.23m
2g
-1, micropore surface is long-pending to be 80.75m
2g
-1, the external surface area that the t-plot method records composite is 69.48m
2g
-1, micro pore volume is 0.040cm
3g
-1Adopt the method for Barrett-Joyner-Halenda (BJH) to estimate the pore size distribution of aperture in 1.7～300nm scope, and to calculate the aperture be 0.038cm at the volume of 1.7～300nm part
3g
-1
Embodiment result shows, adopts colloidal state crystal seed directed agents to the porous silicon carbide support modification, realizes that zeolite crystal is at the preferential forming core of carrier surface, preferential growth.Basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution, the realization zeolite crystal is at Carboround surface preferential growth and control the intercrystalline pore rate.By adjusting the method for aluminium ion addition, regulation and control zeolite coating silica alumina ratio.
Among the present invention, this structure catalyst is a carrier with foam silicon carbon or honeycomb carborundum, and the zeolite coating with high intercrystalline pore rate evenly grows in the Carboround surface.Institute's coating material has high intercrystalline pore rate, and the zeolite crystal size is little, and the molecular diffusion performance is good; Zeolite-loaded amount is bigger, and the zeolite crystal silica alumina ratio, the zeolite coating layer thickness is adjustable; Zeolite crystal and Carboround interfacial combined function are good.This structure catalyst helps strengthening mass transfer, heat transfer, will have wide practical use in fields such as catalysis, absorption, separation.
Claims (7)
1. the high intercrystalline pore of a porous silicon carbide carrier surface rate zeolite coating material is characterized in that this coating material has high intercrystalline pore rate, and intracrystalline pore is of a size of 2～3000 nanometers.
2. according to the high intercrystalline pore of the described porous silicon carbide carrier surface of claim 1 rate zeolite coating material, it is characterized in that zeolite crystal is big in the load capacity of porous silicon carbide carrier surface, the load capacity of zeolite crystal is adjustable in mass fraction 0～60% scope.
3. according to the high intercrystalline pore of the described porous silicon carbide carrier surface of claim 1 rate zeolite coating material, it is characterized in that described zeolite crystal is ZSM-5 or silicalite-1 type zeolite, zeolite crystal is of a size of 0.5～10 micron.
4. according to the high intercrystalline pore of the described porous silicon carbide carrier surface of claim 1 rate zeolite coating material, it is characterized in that Carboround has macroporous structure, Carboround is foaming structure or honeycomb.
5. according to the preparation method of the high intercrystalline pore of the described porous silicon carbide carrier surface of claim 1 rate zeolite coating material, it is characterized in that, by the colloidal state guiding agent for zeolite Carboround is carried out modification, the control zeolite crystal is at the preferential forming core in Carboround surface, preferential growth; Basicity, nutriment concentration and the alkali metal ion addition of control diauxic growth solution, regulation and control coating intercrystalline pore rate and load capacity.
6. according to the preparation method of the high intercrystalline pore of the described porous silicon carbide carrier surface of claim 5 rate zeolite coating material, it is characterized in that, the preparation of colloidal state guiding agent for zeolite 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; 100～170 ℃ of the temperature that hydro-thermal is synthesized, in 0～12 hour reaction time, pressure is the solution self-generated pressure.
7. according to the preparation method of the high intercrystalline pore of the described porous silicon carbide carrier surface of claim 5 rate zeolite coating material, 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: 0.1～0.35: 100～500.
2) hydro-thermal is synthetic
Carboround is put into above-mentioned solution, and the weight ratio of silicon carbide ceramics 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 high intercrystalline pore rate zeolite coating material at the porous silicon carbide carrier surface.
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| CN103252253A (en) * | 2013-05-07 | 2013-08-21 | 中国科学院金属研究所 | Porous silicon-carbide carrier surface gradient pore molecular sieve coating and preparation method thereof |
| CN103357443A (en) * | 2012-04-10 | 2013-10-23 | 中国科学院金属研究所 | Titanium oxide coating/foam silicon carbide structure catalytic carrier and preparation method thereof |
| CN108430628A (en) * | 2015-12-04 | 2018-08-21 | 庄信万丰催化剂(德国)有限公司 | Catalyst and the method for being used to prepare catalyst |
| CN111068619A (en) * | 2019-12-31 | 2020-04-28 | 欧梯恩智能科技(苏州)有限公司 | Composite material for adsorbing volatile organic compounds and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103357443A (en) * | 2012-04-10 | 2013-10-23 | 中国科学院金属研究所 | Titanium oxide coating/foam silicon carbide structure catalytic carrier and preparation method thereof |
| CN103357443B (en) * | 2012-04-10 | 2015-06-03 | 中国科学院金属研究所 | Titanium oxide coating/foam silicon carbide structure catalytic carrier and preparation method thereof |
| CN103252253A (en) * | 2013-05-07 | 2013-08-21 | 中国科学院金属研究所 | Porous silicon-carbide carrier surface gradient pore molecular sieve coating and preparation method thereof |
| CN108430628A (en) * | 2015-12-04 | 2018-08-21 | 庄信万丰催化剂(德国)有限公司 | Catalyst and the method for being used to prepare catalyst |
| CN111068619A (en) * | 2019-12-31 | 2020-04-28 | 欧梯恩智能科技(苏州)有限公司 | Composite material for adsorbing volatile organic compounds and preparation method thereof |
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