CN105439563A - Integral porous carbon-silicon carbide composite material, and preparation method and application thereof - Google Patents
Integral porous carbon-silicon carbide composite material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105439563A CN105439563A CN201410432919.8A CN201410432919A CN105439563A CN 105439563 A CN105439563 A CN 105439563A CN 201410432919 A CN201410432919 A CN 201410432919A CN 105439563 A CN105439563 A CN 105439563A
- Authority
- CN
- China
- Prior art keywords
- kinds
- carbon
- powder
- silicon carbide
- nucleome
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses an integral porous carbon-silicon carbide composite material, and a preparation method and an application thereof. The preparation method comprises the following steps: fully stirring and dispersing silicon carbide powder, silicon powder, carbon-containing powder and a sintering aid in water, preparing a green body by using an ice crystal pore formation technology or an organic polymer foam template pore formation technology, and carrying out high temperature sintering to prepare an integral silicon carbide core; and generating a stable carbon-containing shell with high mechanical strength in the pore channels of the porous SiC core through an in-situ generation technology or a carbon-containing precursor polymerization carborization technology. The composite material has the characteristics of high specific surface area, easy activation surface, acid and alkali corrosion resistance, good heat and electricity conduction property, high and stable mechanical strength, low gas passing pressure drop and low preparation cost, can be used as a metal catalyst loading carrier, or can be directly used as a nonmetal catalyst, so the defects of easiness in pulverization, easiness in obstruction, difficulty in molding and high price of present industrial active carbon catalysis carriers are avoided.
Description
Technical field
The present invention relates to a kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and preparation method thereof, more particularly, the present invention relates to a kind of be used as metal supported catalyst carrier or be directly used as non-metallic catalyst, high mechanical strength and high heat-conductivity conducting, be shell with carbon and monoblock type matrix material that porous silicon carbide is core and preparation method thereof.The surface that the high-ratio surface sum that this carbon fiber reinforced silicon carbide matrix composite not only has hierarchical porous structure is easily chemically activated or modifies, has stable overall mechanical strength and controlled physicochemical property simultaneously.
Background technology
Gac is widely used as Industrial Catalysis agent carrier, and such as hydrogenation reaction utilizes activated carbon supported precious metals pt, Pd etc.Gac has very high specific surface area (>1000m
2/ g) and very low bulk density (0.5-0.9g/cm
3), but differing and cause catalytic performance difference very large in its raw materials source, causes effective gac expensive.Meanwhile, gac physical strength is very poor, molds the gac with stabilizing mechanical intensity very difficult, has a large amount of loss when causing it to apply, and not only loses catalyzer and also causes serious environmental pollution.Prepare a kind of cheapness, effective, eco-friendly carbon support substitutes gac very great industrial application meaning.
Silicon carbide is cheap as a kind of common industrial abrasive, and has very high physical strength and good heat-conductivity conducting performance, but the low and surface chemistry inertia of its specific surface area, be not suitable for directly being used as support of the catalyst.Even if use SiC powder as carrier, its heat conduction and conduction property can greatly weaken, and only have all-in-one-piece carbofrax material just can embody its good heat conduction and conduction property, can direct-electrifying heating in the application.The people such as Fukushima have delivered and have utilized ice crystal as the micron openings monoblock type silicon carbide (2889-2896 page) of Template preparation up to 88% porosity in European Ceramic Society's will in October, 2010, be the porosity that in hitherto reported, micron openings monoblock type silicon carbide is the highest, but the monoblock type silicon carbide specific surface area prepared by them is still lower than 10m
2/ g, and with the addition of the oxide compound such as yttrium oxide and aluminum oxide in the preparation, makes the further inerting in the surface of carbofrax material, and the heat conduction of monoblock type silicon carbide simultaneously and conductivity also greatly reduce.
In order to the character of comprehensive silicon carbide and gac solves its defect, the bag letter of Dalian Chemical Physics Research Institute and research team disclose a kind of method in the Chinese patent application 201210181890 of 2012, the method is using SiC as substrate, utilizes He tympanites to enter CCl at 700-1000 DEG C
4steam and SiC react, and make surface of SiC generate one deck high-specific surface area and the stable carbon-coating of physical strength, and by-product SiCl
4, in reaction atmosphere, add the second gaseous fraction simultaneously, comprise NH
3, CO
2, the physicochemical property of modulation carbon-coating that can be controlled.But this patent is only limited to carries out chemical treatment to SiC powder, although have stable physical strength and high specific surface area, do not form all-in-one-piece structure, thus the good heat conduction of SiC and conductive characteristic can not be embodied.Jinsong ZHANG research team of metal institute of the Chinese Academy of Sciences refer to a kind of active carbon layer/foam silicon carbon structure catalyst and preparation method thereof in Chinese patent CN102814188 disclosed in 2014, but this method is only spread upon on porous foam silicon carbide by carbon-coating by the mode of additive coking, do not connect closely between silicon carbide and carbon-coating, the heat trnasfer between it is caused to be obstructed, simultaneously their porous foam silicon carbide of using is primarily of oxidesintering, and overall electroconductibility and thermal conductivity comparatively silicon carbide all greatly reduce.
Summary of the invention
The object of this invention is to provide a kind of carrier or direct as the high mechanical strength of non-metallic catalyst and the monolithic porous carbon fiber reinforced silicon carbide matrix composite of high heat-conductivity conducting being used as metal supported catalyst, to solve the problems referred to above that prior art exists.This monolithic porous carbon fiber reinforced silicon carbide matrix composite of the present invention should have excellent thermal conductivity, electroconductibility and stablize good physical strength, composites has the surface of high-specific surface area and easily chemically modified, the vesicular structure of macropore mesoporous micropore composition and comparatively cheap preparation cost simultaneously, and these character can effectively reduce reaction bed Pressure Drop and promote utilization ratio and the stability of catalyzer in concrete catalytic applications.
Another object of the present invention is to provide a kind of preparation method of above-mentioned matrix material.
Monolithic porous carbon fiber reinforced silicon carbide matrix composite of the present invention, its characteristic is that described matrix material is made up of the nucleome of monolithic porous silicon carbide-containing (SiC) and carbon containing (C) shell covered thereon; The nucleome of described monolithic porous silicon carbide-containing refers to SiC and Si, C, B, Cr, Mn, Fe, Co, Ni simple substance and first forms monolithic porous idiosome through pore-creating, then through the all-in-one-piece porous ceramics of Overheating Treatment sintering containing one or more in one or more compound in Si, C, B, N, O, S, Cl, Cr, Mn, Fe, Co, Ni element; Described carbon containing shell refers to based on C, one or more decolorizing carbon containing nanotube or graphene-structured formed adulterated in other non-metallic elements; The method covering carbon containing shell comprises in-situ synthesized and is polymerized carborization containing carbon matrix precursor.
In the gross weight of SiC nucleome for 100%, SiC content is 30 ~ 100%, the part by weight of element is the Si of 60 ~ 90%, the C of 10 ~ 40%, the B of 0 ~ 10%, the N of 0 ~ 10%, the O of 0 ~ 10%, 0 ~ 10% Cr, Mn, the Fe of 0 ~ 10% of 0 ~ 10%, the Ni of the Co of 0 ~ 10% and 0 ~ 10%; In the gross weight of carbon containing shell for 100%, C content is 20 ~ 100%, and the content of other non-metallic elements is no more than 20%; The part by weight of SiC nucleome and carbon containing shell is 20:1 ~ 8:1.
Contained by monoblock type idiosome in described silicon carbide-containing nucleome preparation process, material is mainly: particle diameter between 0.02 ~ 20 μm SiC powder, particle diameter between 0.02 ~ 20 μm Si powder, particle diameter is between the carbonaceous powder of 0.02 ~ 20 μm.
Described carbonaceous powder can be through high temperature reduction carbonization containing carbon compound or polymkeric substance, preferably but be not limited to starch, Mierocrystalline cellulose, polypyrrole, poly-furans, polystyrene, polyethylene, resol; Also can be carbohydrate (preferably but be not limited to glucose, fructose, sucrose, starch, the Mierocrystalline cellulose) carbonaceous powder that formed of (160 ~ 220 DEG C) carbonization under hydrothermal conditions; The carbonaceous powder of carbonization that also can be carbon containing monomer (preferably but be not limited to glucose, fructose, sucrose, starch, pyrroles, pyridine, furans, vinylbenzene) through catalyzer (preferably but be not limited to the vitriol oil, hydrogen peroxide, iron trichloride, ammonium persulphate, Diisopropyl azodicarboxylate, dibenzoyl peroxide) be polymerized; Also can be lead at idiosome sintering process situ the carbonaceous powder that carbonaceous gas (preferably but be not limited to methane, ethene, acetylene, benzene, pyrroles, pyridine, furans) generates.
Particle diameter can also be added between the sintering aid powder described in the sintering aid powder of 0.02 ~ 20 μm preferably but be not limited to Cr, Mn, Fe, Co, Ni, Cr, B, B in material contained by monoblock type idiosome in described silicon carbide-containing nucleome preparation process
4c, and the compound powder of aforementioned sintering aid can be obtained through high temperature reduction, preferably but be not limited to ferric oxide, iron nitrate, ferric sulfate, iron(ic) chloride, ironic hydroxide, cobalt oxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, cobaltous hydroxide, nickel oxide, nickelous nitrate, single nickel salt, nickelous chloride, nickel hydroxide, chromic oxide, chromium nitrate, chromium sulphate, chromium chloride, chromium hydroxide, its characteristic is not only to contribute to the additive that silicon carbide sintering or Si and C reaction sintering become silicon carbide, and its interpolation can not reduce heat conduction and the conductive characteristic of SiC to a great extent.
The pore forming method of described monolithic porous idiosome comprises ice crystal port-creating method and organic polymer foam template port-creating method:
Described ice crystal port-creating method is made up of following steps:
A the component of the monolithic porous idiosome of composition is dispersed in water with described ratio by (), the volume of the component powder added and the volume ratio of water are 0.1 ~ 1, and preferably 0.1 ~ 0.4; Under the effect added or do not add gelifying agent, 2 ~ 80 DEG C are fully stirred, gelifying agent refers to the material making solution gel in heating for dissolving after water cooling, preferably but be not limited to agar, agarose, gelatin, starch, tetraethoxy, gelifying agent addition is 0.5 ~ 10% of the weight of water used, preferably 0.5 ~ 5%
(b) by gained slurry inject mould, gel or
Not freezing icing after gel, ice crystal is separated out from slurry.The common materials such as the preferred gypsum of mould, tetrafluoroethylene, processable ceramic, steel, gravel size decision is cylindrical, annulus cylindricality, square, spherical, preferred 1cm ~ the 10m of length, cross-sectional maximum dimension is 0.5 ~ 50cm preferably, freezing temp-20 ~-190 DEG C, preferably-30 ~-70 DEG C, freezing time 0.2 ~ 20h, preferably 0.5 ~ 5h
C () is dry by gained frozen material, remove ice crystal and form duct, and drying means preferably but be not limited to freeze-drying and humid control desiccating method, its objective is and reduces general drying means and the significantly volumetric shrinkage that produces; Freeze-drying refers under low-temp low-pressure, to make frozen material when without liquid and body phase phase transformation, and the ice on its surface is directly sublimed into the quickly drying method of gas; Humidity control desiccating method refers to that dried object is 80 ~ 95% in humidity, and temperature is method dry at a slow speed under the condition of 0 ~ 80 DEG C.
Described organic polymer foam template port-creating method is made up of following steps:
A () configures sticking agent solution at 20 ~ 80 DEG C, described sticking agent refers to compound or the polymkeric substance of the water-soluble rear increase solution viscosity of energy, preferably but be not limited to polyoxyethylene glycol, polyvinyl alcohol, polypyrrole alkane ketone, the component of the monolithic porous idiosome of composition is dispersed in sticking agent solution with described ratio and forms slurry, with mass ratio range, idiosome component powder accounts for 20 ~ 50%, and sticking agent accounts for 2 ~ 10%, water accounts for 48 ~ 78%
B the organic polymer foam block of shear forming immerses in slurry by (), take out, take advantage of 40 ~ 60% of slurry not dry weight compression foam original volume or do not press after stirring, and three-dimensional stirs 1 ~ 30min, repeats this step 2 ~ 5 time; Organic polymer foam refers to the open-cell foamed plastics be communicated with containing abscess, preferred PU, PE, NBR/PVC, EPDM, more preferably PU.
C (), temperature 20 ~ 80 DEG C, humidity 20 ~ 90% times dryings, time of drying is 2 ~ 10h preferably.
The thermal treatment sintering method of described monolithic porous pottery is made up of following steps:
(a) by idiosome at air, rare gas element (He, Ar), N
2, H
2or be warming up to 300 ~ 600 DEG C under vacuum condition, temperature rise rate 0.1 ~ 20 DEG C/min, preferably 0.1 ~ 5 DEG C/min, switch or do not switch to reducing gas (preferred H
2, H
2with rare gas element (He, Ar), N
2gas mixture) be incubated 0.5 ~ 10h, reducing gas air speed (GHSV) is 500 ~ 10000h
-1, preferably 2000 ~ 6000h
-1,
B () is at rare gas element (He, Ar), N
2, H
2or be warming up to 800 ~ 1200 DEG C under vacuum condition, preferably 900 ~ 1050 DEG C, temperature rise rate 0.5 ~ 50 DEG C/min, preferably 2 ~ 20 DEG C/min, switches or does not switch to carbonaceous gas (preferably but be not limited to methane, ethene, acetylene, benzene, pyrroles, pyridine, furans or aforementioned substances and rare gas element (He, Ar), N
2gas mixture) be incubated 0.5 ~ 10h, carbonaceous gas air speed (GHSV) is 500 ~ 10000h
-1, preferably 2000 ~ 6000h
-1,
C () is at rare gas element (He, Ar), N
2, H
2or be warming up to 1300 ~ 2300 DEG C under vacuum condition, preferably 1500 ~ 2050 DEG C, be incubated 0.2 ~ 10h or be not incubated, be preferably incubated 0.2 ~ 1h or be not incubated, temperature rise rate 0.5 ~ 50 DEG C/min, preferably 2 ~ 20 DEG C/min, rate of temperature fall 2 ~ 10 DEG C/min.
Described carbon containing shell is doped with non-metallic element, its role is to modulation carbon-coating physicochemical property, the non-metallic element of doping comprise B, N, O, S, P, preferred B, N, O, S, Cl, I.
The in-situ synthesized of described covering carbon containing shell refers to that atmosphere silicon carbide-containing nucleome and specified chemical formed under the condition of load or not metal supported catalyst is through one or many chemical reaction under high temperature (300 ~ 1000 DEG C), reaction times 0.1 ~ 5h, preferably 0.1 ~ 2h, consume or do not consume Portion Core and in-situ preparation carbon containing shell, its characteristic is that carbon containing shell is connected closely with silicon carbide-containing nucleome, has higher and stable overall mechanical strength.
Described specified chemical composition can be atmosphere containing chlorine, carbon-containing atmosphere, other adulterate atmosphere, rare gas element (He, Ar), N
2or H
2, also can be the mixture of aforementioned atmosphere.Described atmosphere containing chlorine comprises CCl
4, CHCl
3, CH
2cl
2, CH
3cl, HCl, preferred Cl
2, CCl
4, HCl, more preferably CCl
4; Carbon-containing atmosphere comprises methane, ethene, ethane, acetonitrile, benzene, naphthalene, pyrroles, pyridine, furans, optimization methane, ethene, acetonitrile, benzene, pyrroles, pyridine; Other doping atmosphere comprise the compound containing B, N, O, S, P, F, Cl, Br, I element, preferred borine, ammonia, ammonia borine, diborane, dimethyamine borane, dithiocarbonic anhydride, sulfurous gas, carbonic acid gas, NO
x(x=0.5 ~ 2.5), oxygen, ozone, water vapour, PO
xone or more in (x=1.5 ~ 2.5), phosphorus trichloride, trifluoro oxygen phosphorus, hydrogen bromide, hydrogen iodide.
Described covering carbon containing shell to refer under the condition of load or not metal supported catalyst by specific carbonaceous presoma through polymerization, carbonization, reactivate and cover carbon-coating at SiC core surface containing carbon matrix precursor polymerization carborization, its characteristic is that the carbon containing shell of generation is because of the polymerization property of specific carbonaceous presoma and silicon carbide-containing core tight joint.
Described specific carbonaceous presoma comprise in glucose, fructose, sucrose, pyrroles, pyridine, furans, vinyl pyrrole, vinyl pyridine, vinyl furans, vinyl pyrrole ketone, vinyl pyridine ketone, vinyl furandione, vinylformic acid, acrylamide, vinylbenzene, Vinylstyrene one or more.
Described polymerizing condition can be at air, rare gas element (He, Ar) or N
2lower 20 ~ 200 DEG C of polymerizations, also can be hydrothermal condition (160 ~ 220 DEG C) polycondensation, polymerization time is 0.5 ~ 60h preferably.
Described Carbonization Conditions is at rare gas element (He, Ar) or N
2lower 300 ~ 1000 DEG C of thermal treatments, the treatment time is 0.5 ~ 10h preferably.
Described reactivate is the process of instigating other non-metallic elements of sample adulteration after aforementioned carbonization or increasing specific surface area.The method of described other non-metallic elements of doping is that the treatment time is 0.5 ~ 10h preferably by 300 ~ 1000 DEG C of thermal treatments through one or many under doping atmosphere of sample after aforementioned carbonization.Described doping atmosphere comprises the compound containing H, B, N, O, S, P, F, Cl, Br, I element, preferred hydrogen, borine, ammonia, ammonia borine, diborane, dimethyamine borane, dithiocarbonic anhydride, sulfurous gas, carbonic acid gas, NO
x(x=0.5 ~ 2.5), oxygen, ozone, water vapour, PO
xone or more in (x=1.5 ~ 2.5), phosphorus trichloride, trifluoro oxygen phosphorus, hydrogen bromide, hydrogen iodide, and described doped compound and rare gas element (He, Ar) or N
2gas mixture.The method of described increase specific surface area comprises common phosphoric acid activation method, potassium hydroxide or sodium hydroxide activation method, carbon dioxide activation method.Described phosphoric acid activation method refers to and is mixed with phosphoric acid solution by sample after aforementioned carbonization, and with the preferred 1:1.5 ~ 1:6 of mass ratio, the concentration of phosphoric acid solution preferably 30 ~ 85%, then mixture is at rare gas element (He, Ar) or N
2under 300 ~ 600 DEG C process 0.5 ~ 5h, gas space velocity (GHSV) preferably 2000 ~ 6000h
-1, temperature rise rate is 0.2 ~ 20 DEG C/min preferably.Described potassium hydroxide or sodium hydroxide activation method refer to and are mixed with potassium hydroxide solid or sodium hydrate solid by sample after aforementioned carbonization, and with the preferred 1:1.5 ~ 1:6 of mass ratio, then mixture is at rare gas element (He, Ar) or N
2under 600 ~ 1000 DEG C process 0.5 ~ 5h, gas space velocity (GHSV) preferably 2000 ~ 10000h
-1, temperature rise rate is 1 ~ 20 DEG C/min preferably.Described carbon dioxide activation method refers to sample after aforementioned carbonization at CO
2at 600 ~ 1000 DEG C of process 2 ~ 20h, gas space velocity (GHSV) preferably 2000 ~ 10000h under atmosphere
-1, temperature rise rate is 1 ~ 20 DEG C/min preferably.
The so-called metal catalyst of the described load when covering carbon containing shell refers to the containing metal catalyzer after high temperature reduction, its role is to the generation promoting and regulate carbon containing shell, with modulation carbon-coating physicochemical property.Contained by the metal catalyst of described load, metallic element comprises Cr, Fe, Co, Ni, Cu, Zn, Mo, Ag, Sn, La, Ce, W, Au, preferred Fe, Co, Ni, Mo, Ag, Ce.Described catalyzer can be oxygenant or radical initiator, preferably but be not limited in iron(ic) chloride, Sodium Persulfate, hydrogen peroxide, Diisopropyl azodicarboxylate, dibenzoyl peroxide one or more.
Described high temperature reduction refers at rare gas element (He, Ar), N
2, H
2, under CO or vacuum condition, remain on high temperature 300 ~ 600 DEG C process 0.5 ~ 10h, temperature rise rate is 1 ~ 20 DEG C/min preferably.
Described monolithic porous carbon fiber reinforced silicon carbide matrix composite, its specific conductivity is between 0.01 ~ 50S/cm; Its thermal conductivity is between 1 ~ 300W/ (mK); Its porosity between 30 ~ 95%, preferably 50 ~ 90%, more preferably 60 ~ 90%; Its mean pore size between 2 μm ~ 5mm, preferably 20 ~ 500 μm, more preferably 20 ~ 100 μm; Its specific surface area is between 1 ~ 500m
2/ g, preferably 10 ~ 300m
2/ g; More preferably 50 ~ 200m
2/ g.
The present invention is based on the Research foundation of long-term SiC material and carbon material, provide a kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and preparation method thereof, by the interpolation of specific sintering aid, under the prerequisite not affecting thermal conductivity and electroconductibility, the silicon carbide-containing nucleome of high porosity is made to be provided with high mechanical strength and active surface.By the doping of non-metallic element and the change of synthesis condition, the controlled modulation physicochemical property of carbon containing shell.By the generation of original position or be specifically polymerized carbonization, the combination of carbon containing shell and silicon carbide-containing nucleome is made to have higher and stable physical strength.To sum up, this matrix material of the present invention has high-specific surface area, easily-activated surface, acid-alkali-corrosive-resisting, high temperature resistant, good thermal conductivity and electroconductibility, higher and stable physical strength, lower gas by the feature such as Pressure Drop, preparation cost be cheap, the carrier of metal supported catalyst can be used as or directly be used as non-metallic catalyst, thus solving easy efflorescence, the easily blocking of existing industrial activited carbon catalytic carrier, the defect such as difficulty is shaping, price is high.
Accompanying drawing explanation
The scanning electron microscope shape appearance figure of Fig. 1 matrix material; Left figure (A) demonstrates the eurypyloue carbon fiber reinforced silicon carbide matrix composite of tool; Right figure (B) demonstrates the carbon containing shell that silicon carbide nucleome inner bore surface covers.
Embodiment
This matrix material first passes through carborundum powder, silica flour, carbonaceous powder, sintering aid abundant dispersed with stirring in water, then ice crystal port-creating method or organic polymer foam template port-creating method is utilized to make idiosome, obtained monoblock type silicon carbide nucleome after high temperature sintering, makes the silicon carbide-containing nucleome of high porosity be provided with high mechanical strength and active surface under the prerequisite not affecting thermal conductivity and electroconductibility; Then on porous SiC nucleome duct, generate one deck there is higher mechanical strength and stable carbon containing shell by in-situ synthesized or containing carbon matrix precursor polymerization carborization.By the doping of non-metallic element and the change of synthesis condition, the controlled modulation physicochemical property of carbon containing shell.This matrix material of the present invention has high-specific surface area, easily-activated surface, acid-alkali-corrosive-resisting, high temperature resistant, good thermal conductivity and electroconductibility, higher and stable physical strength, lower gas by the feature such as Pressure Drop, preparation cost be cheap, the carrier of metal supported catalyst can be used as or directly be used as non-metallic catalyst, thus solving easy efflorescence, the easily blocking of existing industrial activited carbon catalytic carrier, the defect such as difficulty is shaping, price is high.
Embodiment 1
Take 100 order SiC powder 10.0g, 100 order Si powder 6.5g, acetylene powdered carbon 2.8g, 100 order Fe powder 1.5g, pour in 0.5% agarose solution of 24mL, and 80 DEG C are stirred 30min.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polytetrafluoro mould of long 10cm, and room temperature cooling 2h, then put into-30 DEG C of refrigerator and cooled and freeze 2h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, 500 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 1 DEG C/min, under the Ar gas of 50mL/min, be warming up to 1000 DEG C, temperature rise rate 10 DEG C/min, under the Ar gas of 50mL/min, be warming up to 1500 DEG C, temperature rise rate 2 DEG C/min, be incubated and vacuumize insulation 2 hours after 2 hours, the cold cooling of stove, obtained monolithic porous SiC nucleome.
SiC nucleome is encapsulated in silica tube, under the Ar gas of 50mL/min, is warming up to 800 DEG C, then at the NH of Ar, 1.5mL/min of 50mL/min
3, 4.0mL/min CCl
4at 800 DEG C of insulation 0.5h under gas mixture, lower the temperature with 30 DEG C/min, the carbon fiber reinforced silicon carbide matrix composite of obtained N doping.
The scanning electron microscope shape appearance figure of this matrix material is as follows, and this pattern is the typical case of carbon fiber reinforced silicon carbide matrix composite.
The composition of this matrix material SiC nucleome is the SiC of 91.2%, the Fe of 3.6%, the Si of 4.6% and the carbon of 0.6%; The composition of carbon-coating is the carbon of 86.7%, the nitrogen of 7.2% and the oxygen of 6.1%.
Embodiment 2
Take 100 order SiC powder 10.0g, 100 order Si powder 6.5g, acetylene powdered carbon 2.8g, Cr (NO
3)
3powder 1.0g, Ni (NO
3)
2powder 0.5g, pours in 2% gelatin solution of 24mL, and 60 DEG C are stirred 30min.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polyethylene mould of long 10cm, and room temperature cooling 1h, then put into-60 DEG C of refrigerator and cooled and freeze 5h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in corundum crucible, under the Air gas of 50mL/min, be warming up to 500 DEG C, temperature rise rate 0.5 DEG C/min, at the H of 50mL/min
2be warming up to 1000 DEG C under gas, temperature rise rate 10 DEG C/min, switches to the CH of 50mL/min
4gas is incubated 1h at 1000 DEG C, under the Ar gas of 50mL/min, be warming up to 1600 DEG C, temperature rise rate 2 DEG C/min, is incubated the cold cooling of stove after 2 hours, obtained monolithic porous SiC nucleome.
SiC nucleome is encapsulated in silica tube, under the Ar gas of 50mL/min, is warming up to 800 DEG C, then at the NH of Ar, 2mL/min of 10mL/min
3, 3.0mL/min CCl
4at 300 DEG C of insulation 0.5h under gas mixture, lower the temperature with 30 DEG C/min, the carbon fiber reinforced silicon carbide matrix composite of obtained N doping.
Embodiment 3
Take 400 order SiC powder 28.9g, acetylene powdered carbon 0.5g, B
2o
3powder 0.5g, pours in 5% tetraethoxy (pH1) solution of 24mL, and 30 DEG C are stirred 2h.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polyethylene mould of long 10cm, and room temperature cooling 5h, then put into the freezing 0.2h of liquid nitrogen.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, 500 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 1 DEG C/min, 1000 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, is warming up to 1600 DEG C under the Ar gas of 50mL/min, temperature rise rate 2 DEG C/min, lower the temperature with 3 DEG C/min, obtained monolithic porous SiC nucleome.
SiC nucleome is encapsulated in silica tube, under the Ar gas of 50mL/min, is warming up to 800 DEG C, then at the CCl of Ar, 4.0mL/min of 10mL/min
4at 700 DEG C of insulation 2h under gas mixture, lower the temperature with 30 DEG C/min, the carbon fiber reinforced silicon carbide matrix composite of obtained B doping.
Embodiment 4
Take 200 order SiC powder 11.8g, pour in 1% agarose solution of 24mL, 60 DEG C are stirred 1h.Internal diameter 2cm poured into by the slurry formed, in the cylindrical stainless steel mould of long 10cm, and room temperature cooling 2h, then put into-50 DEG C of refrigerator and cooled and freeze 2h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, 500 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 1 DEG C/min, 1000 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 20 DEG C/min, is warming up to 2200 DEG C under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, the cold cooling of stove after insulation 1h, obtained monolithic porous SiC nucleome.
SiC nucleome is placed in 70mL15% sucrose solution and puts into 100mL water heating kettle, at 180 DEG C, be incubated 24h, at the NH of 50mL/min after carbon fiber reinforced silicon carbide matrix composite is taken out
3at 700 DEG C of insulation 2h under gas, lower the temperature with 10 DEG C/min, the carbon fiber reinforced silicon carbide matrix composite of obtained N doping.
Embodiment 5
Take 100 order SiC powder 10.0g, 100 order Si powder 6.5g, acetylene powdered carbon 2.8g, Fe (NO
3)
3powder 1.5g, pours in 1% agarose solution of 24mL, and 60 DEG C are stirred 1h.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polytetrafluoro mould of long 10cm, and room temperature cooling 2h, then put into-50 DEG C of refrigerator and cooled and freeze 2h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, under the Ar gas of 50mL/min, be warming up to 500 DEG C, temperature rise rate 1 DEG C/min, at the H of 50mL/min
2be warming up to 800 DEG C under gas, temperature rise rate 5 DEG C/min, under the Ar gas of 50mL/min, be warming up to 1500 DEG C, temperature rise rate 10 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
SiC nucleome is placed in 70mL20% glucose solution and puts into 100mL water heating kettle, at 200 DEG C, be incubated 20h, at the NH of 50mL/min after carbon fiber reinforced silicon carbide matrix composite is taken out
3at 600 DEG C of insulation 2h under gas, the cold cooling of stove, the carbon fiber reinforced silicon carbide matrix composite of obtained N doping.
Embodiment 6
Take 100 order SiC powder 10.0g, 100 order Si powder 6.5g, glucose 10.0g, pours in 2% gelatin solution of 24mL, puts into water heating kettle, at 180 DEG C, be incubated 24h, adds Cr (NO after cooling
3)
3powder 1.5g, 60 DEG C are stirred 1h.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polytetrafluoro mould of long 10cm, and room temperature cooling 2h, then put into-50 DEG C of refrigerator and cooled and freeze 2h, then put into liquid nitrogen and cool 0.2h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, under the Ar gas of 50mL/min, be warming up to 500 DEG C, temperature rise rate 1 DEG C/min, switches to the H of 50mL/min
2be incubated 2h under gas, then be warming up to 1000 DEG C under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, under the Ar gas of 50mL/min, be warming up to 1500 DEG C, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
By SiC nucleome incipient impregnation containing 0.1%FeCl
3dense hydrogen peroxide, put into Ar and the 30mL/min furans steam that Glass tubing passes into 100mL/min, at 60 DEG C, be incubated 1h, after being taken out by carbon fiber reinforced silicon carbide matrix composite, under the Ar gas of 50mL/min, be incubated 2h at 600 DEG C, the cold cooling of stove, the carbon fiber reinforced silicon carbide matrix composite of obtained O doping.
Embodiment 7
Take 100 order SiC powder 10.0g, 100 order Si powder 6.5g, 400 order Fe powder 0.6g, pour in 2% gelatin solution of 24mL and stir 1h at 60 DEG C.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polytetrafluoro mould of long 10cm, and room temperature cooling 2h, then put into-50 DEG C of refrigerator and cooled and freeze 2h, then put into liquid nitrogen and cool 0.2h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, under the Ar gas of 50mL/min, be warming up to 500 DEG C, temperature rise rate 1 DEG C/min, switches to the H of 50mL/min
2be incubated 2h under gas, then be warming up to 1000 DEG C under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, switches to the CH of 100mL/min
4be incubated 1h under gas, then be warming up to 1500 DEG C under the Ar gas of 50mL/min, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
By SiC nucleome incipient impregnation containing 0.1%FeCl
3dense hydrogen peroxide, put into Ar and the 30mL/min pyrroles steam that Glass tubing passes into 100mL/min, at 30 DEG C, be incubated 1h, after being taken out by carbon fiber reinforced silicon carbide matrix composite, under the Ar gas of 50mL/min, be incubated 2h at 600 DEG C, the cold cooling of stove, the carbon fiber reinforced silicon carbide matrix composite of obtained N doping.
Embodiment 8
Take sucrose 10.0g, add in 30mL distilled water, put into water heating kettle and be incubated 24h at 200 DEG C, cooled and filtered obtains carbonaceous powder, then together with SiC powder 10.0g, the 100 order Si powder 6.5g of particle diameter 10 μm, 100 order Fe powder 1.0g, pour in 2% gelatin solution of 24mL, 60 DEG C are stirred 1h.Internal diameter 2cm poured into by the slurry formed, in the cylindrical polytetrafluoro mould of long 10cm, and room temperature cooling 2h, then put into-50 DEG C of refrigerator and cooled and freeze 2h.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, 500 DEG C are warming up under the Ar gas of 100mL/min, temperature rise rate 1 DEG C/min, 1000 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, is warming up to 1500 DEG C under the Ar gas of 50mL/min, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
0.2%w/v dopamine hydrochloride solution SiC nucleome being put into the pH8.6 of new configuration stirs 20h, soaks 1h after being taken out by obtained carbon fiber reinforced silicon carbide matrix composite in the dense HI solution of 60 DEG C, the carbon fiber reinforced silicon carbide matrix composite of obtained N, I codoped.
Embodiment 9
Take sucrose 10.0g, add in 30mL distilled water, put into water heating kettle and be incubated 24h at 200 DEG C, cooled and filtered obtains carbonaceous powder, then together with SiC powder 10.0g, the 100 order Si powder 6.5g of particle diameter 10 μm, 100 order Fe powder 1.0g, pour in the 1%PVA solution of 30mL, 60 DEG C are stirred 1h and obtain slurries.Porous polyurethane sponge is sheared the cubic block that the length of side is 2cm, cubic block is fully immersed slurries, take out cubic block and compress 60% of its volume, stir and again immerse slurries in a moment, repeat infiltration, compression step three times, take out cubes, 60 DEG C of dry 24h under 80% humidity.By idiosome as in corundum crucible, 500 DEG C are warming up under the Air gas of 100mL/min, temperature rise rate 0.5 DEG C/min, 1000 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, is warming up to 1500 DEG C under the Ar gas of 50mL/min, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
SiC nucleome is encapsulated in silica tube, is heated to 800 DEG C with 5 DEG C/min temperature rise rate, passes into the Cl of Ar, 5mL/min of 50mL/min
2, insulation 0.5h, the Ar stove switching to 50mL/min is cold, obtained monoblock type carbon fiber reinforced silicon carbide matrix composite.
Embodiment 10
Take the SiC powder 10.0g of particle diameter 10 μm, 100 order Si powder 6.5g, after mixing, incipient impregnation is containing 0.8gFe (NO)
3solution, drying is placed in silica tube, at 50mL/minH
2under be warming up to 500 DEG C of reductase 12 h, in 100mL/minAr, be warming up to 800 DEG C pass into 100mL/minAr and 50mL/min pyridine steam again, insulation 1h, after cooling, powder is poured in the water of 24mL, fully stirs.Internal diameter 2cm poured into by the slurry formed, and in the cylindrical polytetrafluoro mould of long 10cm, puts into the freezing 0.5h of liquid nitrogen.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, 500 DEG C are warming up under the Ar gas of 100mL/min, temperature rise rate 1 DEG C/min, 1000 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, is warming up to 1500 DEG C under the Ar gas of 50mL/min, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
0.2%w/v dopamine hydrochloride solution SiC nucleome being put into the pH8.6 of new configuration stirs 20h, under the Ar gas of 50mL/min, 800 DEG C are warming up to after being taken out by obtained carbon fiber reinforced silicon carbide matrix composite, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, the carbon fiber reinforced silicon carbide matrix composite of obtained N doping.
The Cl of 5mL/min
2, insulation 0.5h, the Ar stove switching to 50mL/min is cold, obtained monoblock type carbon fiber reinforced silicon carbide matrix composite.
Embodiment 11
Take the SiC powder 11.8g of particle diameter 10 μm, Graphene 0.5g, pours in the water of 24mL, fully stirs.Internal diameter 2cm poured into by the slurry formed, and in the cylindrical polytetrafluoro mould of long 10cm, puts into the freezing 0.5h of liquid nitrogen.Frozen material taking-up is put into Freeze Drying Equipment freeze-drying 48h and is obtained idiosome.By idiosome as in plumbago crucible, 500 DEG C are warming up under the Ar gas of 100mL/min, temperature rise rate 1 DEG C/min, 1000 DEG C are warming up under the Ar gas of 50mL/min, temperature rise rate 10 DEG C/min, is warming up to 1500 DEG C under the Ar gas of 50mL/min, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monolithic porous SiC nucleome.
SiC nucleome is put into the water heating kettle that 30mL10% starch solution is housed, 24h is incubated at 200 DEG C, under the Ar gas of 50mL/min, 1000 DEG C are warming up to after being taken out by obtained carbon fiber reinforced silicon carbide matrix composite, temperature rise rate 5 DEG C/min, the cold cooling of stove after insulation 2h, obtained monoblock type carbon fiber reinforced silicon carbide matrix composite.
Application examples 1
As the catalyzer of blast furnace gas methanation after the Ni metal of carbon fiber reinforced silicon carbide matrix composite load 5%, 500 DEG C of air speeds (GHSV), 20000 times CO conversion can reach 90%, selectivity 98%, because its high thermal conductivity has satisfactory stability in this thermopositive reaction, when temperature of reaction is 550 DEG C, catalyst activity was stablized in 100 hours.
Application examples 2
After mixing the nitrogen of 6%, metal supported catalyst can directly as the catalyzer of acetylene hydrochlorination, at industrial air speed (GHSV) 30h for carbon fiber reinforced silicon carbide matrix composite
-1be issued to 90% of existing mercury catalyst activity, laboratory stability was higher than 200 hours.
Claims (10)
1. monolithic porous carbon-silicon carbide (C-SiC) matrix material, its characteristic is: described matrix material by monolithic porous silicon carbide-containing (SiC) nucleome and cover carbon containing (C) shell thereon and form.
2., according to matrix material according to claim 1, its characteristic is:
Described covering refers to that shell covers the internal channel surfaces of nucleome thereon, or shell covers the outside surface of nucleome and the internal channel surfaces of nucleome;
Carbon containing shell refers to based on C, one or two or more kinds in one or two or more kinds nanotube formed adulterated in other non-metallic elements or Graphene or amorphous structure carbon.
3., according to the matrix material described in claim 1 or 2, its characteristic is:
The nucleome of silicon carbide-containing is for 100% in the gross weight containing SiC nucleome, SiC content is 30 ~ 100%, the part by weight of nucleome element is the Si of 60 ~ 90%, the C of 10 ~ 40%, the B of 0 ~ 10%, the N of 0 ~ 10%, the O of 0 ~ 10%, 0 ~ 10% Cl, the Cr of 0 ~ 10%, the Mn of 0 ~ 10%, the Fe of 0 ~ 10%, the Co of 0 ~ 10%, and the Ni of 0 ~ 10%;
Carbon containing shell comprises the carbon shell of carbon shell or the doping of other nonmetallic heteroatoms, and in the gross weight of carbon containing shell for 100%, C content is 20 ~ 100%, and the content of other non-metallic elements is no more than 20%; Carbon containing shell is doped with other non-metallic element, its role is to modulation carbon-coating physicochemical property, the non-metallic element of doping comprise in B, N, O, S, P, F, Br, Cl, I one or two or more kinds, one or two or more kinds in preferred B, N, O, S, Cl, I;
The part by weight of SiC nucleome and carbon containing shell is 20:1 ~ 8:1.
4. a preparation method for the matrix material described in claim 1,2 or 3, its characteristic is:
1) nucleome of silicon carbide-containing is with one or two or more kinds in SiC and following substance for raw material, and first raw material mixing forms monolithic porous idiosome through pore-creating, then through the all-in-one-piece porous ceramics of Overheating Treatment sintering;
Substance comprises: one or two or more kinds in Si, C, B, Cr, Mn, Fe, Co, Ni simple substance, one or two or more kinds in the boride of one or two or more kinds in Cr, Mn, Fe, Co, Ni, nitride, carbide, silicide, oxide compound, muriate, oxyhydroxide, carbonate, nitrate, vitriol, silicate, the carbide of B, the nitride of Si, the nitride of B;
2) method covering carbon containing shell comprises in-situ synthesized or is polymerized carborization containing carbon matrix precursor.
5. according to preparation method according to claim 4, its characteristic is: contained by the monoblock type idiosome in silicon carbide-containing nucleome preparation process, material is mainly: particle diameter between 0.02 ~ 20 μm SiC powder, particle diameter between 0.02 ~ 20 μm Si powder, particle diameter is between the carbonaceous powder of 0.02 ~ 20 μm; Wherein do not add and maybe can also add particle diameter between the sintering aid powder of 0.02 ~ 20 μm;
The SiC powder of the part by weight 20 ~ 90% between SiC powder, Si powder, carbonaceous powder, sintering aid powder, the Si powder of 5 ~ 75%, the carbonaceous powder of 0.1 ~ 25%, the sintering aid powder of 0 ~ 10%;
This sintering aid powder preferably but be not limited to Cr, Mn, Fe, Co, Ni, B, the carbide of B, and the compound powder of aforementioned sintering aid can be obtained through high temperature reduction, preferably but be not limited to ferric oxide, iron nitrate, ferric sulfate, iron(ic) chloride, ironic hydroxide, cobalt oxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt chloride, cobaltous hydroxide, nickel oxide, nickelous nitrate, single nickel salt, nickelous chloride, nickel hydroxide, chromic oxide, chromium nitrate, chromium sulphate, chromium chloride, chromium hydroxide, sintering aid powder not only contributes to silicon carbide sintering or Si and C reaction sintering becomes the additive of silicon carbide, and its interpolation can not reduce heat conduction and the conductive characteristic of SiC to a great extent.
6., according to preparation method according to claim 5, its characteristic is:
Carbonaceous powder be following in one or two or more kinds;
Carbonaceous powder can be through high temperature reduction carbonization containing carbon compound or polymkeric substance, containing carbon compound or polymkeric substance preferably but be not limited in starch, Mierocrystalline cellulose, polypyrrole, poly-furans, polystyrene, polyethylene, resol one or two or more kinds;
Or, also can be carbohydrate (preferably but be not limited in glucose, fructose, sucrose, starch, Mierocrystalline cellulose the one or two or more kinds) carbonaceous powder that formed of (160 ~ 220 DEG C) carbonization under hydrothermal conditions;
Or, also can be carbon containing monomer (preferably but be not limited in glucose, fructose, sucrose, starch, pyrroles, pyridine, furans, vinylbenzene one or two or more kinds) through the carbonaceous powder of catalyzer (preferably but be not limited in the vitriol oil, hydrogen peroxide, iron trichloride, ammonium persulphate, Diisopropyl azodicarboxylate, dibenzoyl peroxide one or two or more kinds) polymerization carbonization;
Or, also can be lead at idiosome sintering process situ the carbonaceous powder that carbonaceous gas (preferably but be not limited in methane, ethene, acetylene, benzene, pyrroles, pyridine, furans one or two or more kinds) generates.
7. according to preparation method according to claim 4, its characteristic is: the pore forming method of monolithic porous idiosome comprises ice crystal port-creating method or organic polymer foam template port-creating method;
Described ice crystal port-creating method is made up of following steps:
A the component of the monolithic porous idiosome of composition is dispersed in water with required ratio by (), the volume of the component powder added and the volume ratio of water are 0.1-1, preferred 0.1-0.4; Under the effect added or do not add gelifying agent, 2 ~ 80 DEG C are fully stirred, gelifying agent refers to the material making solution gel in heating for dissolving after water cooling, preferably but be not limited to agar, agarose, gelatin, starch, tetraethoxy, gelifying agent addition is 0.5 ~ 10% of the weight of water used, preferably 0.5 ~ 5%;
B gained slurry is injected mould by (), freezing icing after gel or not gel, ice crystal is separated out from slurry; The common materials such as the preferred gypsum of mould, tetrafluoroethylene, processable ceramic or steel, cylindrical (preferred 1cm ~ the 10m of length of gravel size decision, diameter is 0.5 ~ 50cm preferably), the annulus cylindricality (preferred 1cm ~ 10m of length, outside diameter is 0.5 ~ 50cm preferably, wall thickness 0.1 ~ 10cm), the square column type (preferred 1cm ~ 10m of length, cut cross-sectional maximum dimension preferably 0.5 ~ 50cm) or spherical (diameter is 0.5 ~ 50cm preferably), freezing temp-20 ~-190 DEG C, preferably-30 ~-70 DEG C, freezing time 0.2 ~ 20h, preferably 0.5 ~ 5h
C () is dry by gained frozen material, remove ice crystal and form duct, and drying means preferably but be not limited to freeze-drying or humid control desiccating method, its objective is and reduces general drying means and the significantly volumetric shrinkage that produces; Freeze-drying refers under low-temp low-pressure (-80 ~-20 DEG C, 1mbar ~ 10
-4mbar) make frozen material when without liquid state and the phase transformation of body phase, the ice on its surface is directly sublimed into the quickly drying method of gas; Humidity control desiccating method refers to that dried object is 80 ~ 95% in humidity, and temperature is method dry at a slow speed under the condition of 0 ~ 80 DEG C;
Or described organic polymer foam template port-creating method is made up of following steps:
A () configures sticking agent solution at 20 ~ 80 DEG C, described sticking agent refers to compound or the polymkeric substance of the water-soluble rear increase solution viscosity of energy, preferably but be not limited in polyoxyethylene glycol, polyvinyl alcohol, polypyrrole alkane ketone one or two or more kinds, the component of the monolithic porous idiosome of composition is dispersed in sticking agent solution with described ratio and forms slurry, with mass ratio range, idiosome component powder accounts for 20 ~ 50%, and sticking agent accounts for 2 ~ 10%, and water accounts for 48 ~ 78%;
B the organic polymer foam block of shear forming immerses in slurry by (), take out, take advantage of the not dry weight of slurry and be compressed to 40 ~ 60% of foam original volume or do not press slurry after stirring, and three-dimensional stirs 1 ~ 30min, repeats this step 2 ~ 5 time; Organic polymer foam refers to the open-cell foamed plastics be communicated with containing abscess, one or two or more kinds in preferred PU, PE, NBR/PVC, EPDM, more preferably PU;
(c) temperature 20 ~ 80 DEG C, humidity 20 ~ 90% times dryings, time of drying is 2 ~ 10h preferably;
The thermal treatment sintering method of described monolithic porous pottery is made up of following steps:
(a) by idiosome at air, rare gas element (in He, Ar one or two or more kinds), N
2, H
2in one or two or more kinds or vacuum condition under be warming up to 300 ~ 600 DEG C, temperature rise rate 0.1 ~ 20 DEG C/min, preferably 0.1 ~ 5 DEG C/min, switch or do not switch to reducing gas (preferred H
2, 10 ~ 50% H
2with rare gas element (in He, Ar one or two or more kinds) and/or N
2gas mixture) be incubated 0.5 ~ 10h, reducing gas air speed (GHSV) is 500 ~ 10000h
-1, preferably 2000 ~ 6000h
-1;
B () is at rare gas element (in He, Ar one or two or more kinds), N
2, H
2or be warming up to 800 ~ 1200 DEG C under vacuum condition, preferably 900 ~ 1050 DEG C, temperature rise rate 0.5 ~ 50 DEG C/min, preferably 2 ~ 20 DEG C/min, switch or do not switch to carbonaceous gas (preferably but be not limited in methane, ethene, acetylene, benzene, pyrroles, pyridine, furans carbonaceous material one or two or more kinds, or one or two or more kinds and rare gas element in the aforementioned carbonaceous material of content 0.1 ~ 50% (in He, Ar one or two or more kinds) and/or N
2gas mixture) be incubated 0.5 ~ 10h, carbonaceous gas air speed (GHSV) is 500 ~ 10000h
-1, preferably 2000 ~ 6000h
-1;
C () is at rare gas element (in He, Ar one or two or more kinds), N
2, H
2in one or two or more kinds or vacuum condition under be warming up to 1300 ~ 2300 DEG C, preferably 1500 ~ 2050 DEG C, insulation 0.2 ~ 10h or be not incubated, preferred insulation 0.2 ~ 1h or be not incubated, temperature rise rate 0.5 ~ 50 DEG C/min, preferably 2 ~ 20 DEG C/min, rate of temperature fall 2 ~ 10 DEG C/min.
8., according to preparation method according to claim 4, its characteristic is:
The in-situ synthesized of A, described covering carbon containing shell refer to the atmosphere that under the condition of load or not metal supported catalyst, silicon carbide-containing nucleome and specified chemical formed through once or more than secondary under high temperature (300 ~ 1000 DEG C) chemical reaction, reaction times 0.1 ~ 5h, preferably 0.1 ~ 2h, consume or do not consume Portion Core and in-situ preparation carbon containing shell, carbon containing shell is connected closely with silicon carbide-containing nucleome, has higher and stable overall mechanical strength;
Described metal catalyst refers to one or two or more kinds in Cr, Mn, Fe, Co, Ni simple substance, and can obtain one or two or more kinds in the oxide compound of one or two or more kinds in the Compound C r of aforementioned metal, Mn, Fe, Co, Ni, muriate, oxyhydroxide, carbonate, nitrate, vitriol, silicate through high temperature reduction; Charge capacity is 0 ~ 10% of nucleome weight;
Described specified chemical composition can be atmosphere containing chlorine, carbon-containing atmosphere, other adulterate atmosphere, rare gas element (He, Ar), N
2or H
2in the mixture of one or two or more kinds;
Described atmosphere containing chlorine comprises CCl
4, CHCl
3, CH
2cl
2, CH
3one or two or more kinds in Cl, HCl, preferred Cl
2, CCl
4, one or two or more kinds in HCl, more preferably CCl
4;
Described carbon-containing atmosphere comprises one or two or more kinds in methane, ethene, ethane, acetonitrile, benzene, naphthalene, pyrroles, pyridine, furans, one or two or more kinds in optimization methane, ethene, acetonitrile, benzene, pyrroles, pyridine;
Other described doping atmosphere comprise one or two or more kinds in the compound containing B, N, O, S, P, F, Cl, Br, I element, preferred borine, ammonia, ammonia borine, diborane, dimethyamine borane, dithiocarbonic anhydride, sulfurous gas, carbonic acid gas, NO
x(x=0.5 ~ 2.5), oxygen, ozone, water vapour, PO
xone or two or more kinds in (x=1.5 ~ 2.5), phosphorus trichloride, trifluoro oxygen phosphorus, hydrogen bromide, hydrogen iodide;
Or B, described covering carbon containing shell to refer under the condition of adding or do not add catalyzer on the nucleome of silicon carbide-containing by specific carbonaceous presoma through polymerization, carbonization, reactivate and at SiC core surface covering carbon-coating containing carbon matrix precursor polymerization carborization, the carbon containing shell of generation is because of the polymerization property of specific carbonaceous presoma and silicon carbide-containing core tight joint;
Described catalyzer can be oxygenant or radical initiator, preferably but be not limited in iron(ic) chloride, Sodium Persulfate, hydrogen peroxide, Diisopropyl azodicarboxylate, dibenzoyl peroxide one or more; Addition is containing carbon matrix precursor weight 0 ~ 20%;
Described specific carbonaceous presoma comprises one or two or more kinds in glucose, fructose, sucrose, pyrroles, pyridine, furans, vinyl pyrrole, vinyl pyridine, vinyl furans, vinyl pyrrole ketone, vinyl pyridine ketone, vinyl furandione, vinylformic acid, acrylamide, vinylbenzene, Vinylstyrene;
Described polymerizing condition can be at air, rare gas element (He, Ar) or N
2in one or two or more kinds condition under 20 ~ 200 DEG C of polymerizations, or also can be hydrothermal condition (160 ~ 220 DEG C) polycondensation, polymerization time is 0.5 ~ 60h preferably;
Described Carbonization Conditions is at rare gas element (in He, Ar one or two or more kinds) or N
2in one or two or more kinds condition under 300 ~ 1300 DEG C of thermal treatments, the treatment time is 0.5 ~ 10h preferably;
Described reactivate is the process of instigating other non-metallic elements of sample adulteration after aforementioned carbonization or increasing specific surface area;
The method of described other non-metallic elements of doping is adulterating sample after aforementioned carbonization through DEG C thermal treatment of 300 ~ 1000 once or more than secondary under atmosphere, and the treatment time is 0.5 ~ 10h preferably;
Described doping atmosphere comprises one or two or more kinds in the compound containing H, B, N, O, S, P, F, Cl, Br, I element, preferred hydrogen, borine, ammonia, ammonia borine, diborane, dimethyamine borane, dithiocarbonic anhydride, sulfurous gas, carbonic acid gas, NO
x(x=0.5 ~ 2.5), oxygen, ozone, water vapour, PO
xone or two or more kinds in (x=1.5 ~ 2.5), phosphorus trichloride, trifluoro oxygen phosphorus, hydrogen bromide, hydrogen iodide, and the above-mentioned doped compound of 0.1 ~ 50% and rare gas element (in He, Ar one or two or more kinds) or N
2in the gas mixture of one or two or more kinds;
The method of described increase specific surface area comprises phosphoric acid activation method, potassium hydroxide or sodium hydroxide activation method or carbon dioxide activation method;
Described phosphoric acid activation method refers to and is mixed with phosphoric acid solution by sample after aforementioned carbonization, and with the preferred 1:1.5 ~ 1:6 of mass ratio, the concentration of phosphoric acid solution preferably 30 ~ 85%, then mixture is at rare gas element (He, Ar) or N
2under 300 ~ 600 DEG C process 0.5 ~ 5h, gas space velocity (GHSV) preferably 2000 ~ 6000h
-1, temperature rise rate is 0.2 ~ 20 DEG C/min preferably;
Described potassium hydroxide or sodium hydroxide activation method refer to and are mixed with potassium hydroxide solid and/or sodium hydrate solid by sample after aforementioned carbonization, and with the preferred 1:1.5 ~ 1:6 of mass ratio, then mixture is at rare gas element (He, Ar) or N
2under 600 ~ 1000 DEG C process 0.5 ~ 5h, gas space velocity (GHSV) preferably 2000 ~ 10000h
-1, temperature rise rate is 1 ~ 20 DEG C/min preferably
Described carbon dioxide activation method refers to sample after aforementioned carbonization at CO
2at 600 ~ 1000 DEG C of process 2 ~ 20h, gas space velocity (GHSV) preferably 2000 ~ 10000h under atmosphere
-1, temperature rise rate is 1 ~ 20 DEG C/min preferably.
9. according to preparation method according to claim 8, its characteristic is: the so-called metal catalyst of the described load on the nucleome of silicon carbide-containing when covering carbon containing shell or catalyzer, its role is to the generation promoting and regulate carbon containing shell, with modulation carbon-coating physicochemical property;
Described high temperature reduction refers at rare gas element (He, Ar), N
2, H
2, under one or two or more kinds or vacuum condition in CO, remain on high temperature 300 ~ 600 DEG C process 0.5 ~ 10h, temperature rise rate is 1 ~ 20 DEG C/min preferably.
10. an application for the matrix material described in claim 1,2 or 3, its characteristic is: described matrix material is used as the carrier of metal supported catalyst or is directly used as non-metallic catalyst in the reaction of acetylene hydrochlorination preparing chloroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410432919.8A CN105439563B (en) | 2014-08-28 | 2014-08-28 | A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410432919.8A CN105439563B (en) | 2014-08-28 | 2014-08-28 | A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105439563A true CN105439563A (en) | 2016-03-30 |
| CN105439563B CN105439563B (en) | 2019-08-27 |
Family
ID=55550271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410432919.8A Active CN105439563B (en) | 2014-08-28 | 2014-08-28 | A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105439563B (en) |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531487A (en) * | 2015-04-13 | 2018-01-02 | 科廷大学 | Produce the method and system of solid carbonaceous material |
| CN107740266A (en) * | 2017-10-30 | 2018-02-27 | 厦门大学 | Continuous SiC fiber surface in situ C SiO2Preparation method of composite coating |
| CN107790136A (en) * | 2017-11-08 | 2018-03-13 | 西安向阳航天材料股份有限公司 | A kind of preparation method of high temperature resistant methanation catalyst |
| CN108097307A (en) * | 2018-01-10 | 2018-06-01 | 南开大学 | The preparation method and its application method of a kind of non-metal catalyst for fixed bed acetylene preparing chloroethylene |
| CN108126659A (en) * | 2018-01-10 | 2018-06-08 | 中国科学院过程工程研究所 | A kind of not fire-hazardous absorbent charcoal composite material and its preparation method and application |
| CN108187712A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | A kind of nonmetallic nitridation B catalyst and preparation and application and regeneration method |
| CN109415267A (en) * | 2016-06-22 | 2019-03-01 | 拜罗伊特大学 | Ceramic composite and its manufacturing method |
| CN109534816A (en) * | 2017-09-21 | 2019-03-29 | 中南大学 | A method of preparing porous silicon carbide ceramic with high strength |
| CN109928759A (en) * | 2019-03-14 | 2019-06-25 | 武汉工程大学 | A kind of SiC ceramic membrane electrochemical reaction electrode and preparation method thereof |
| CN110079996A (en) * | 2019-05-24 | 2019-08-02 | 中国人民解放军国防科技大学 | Method for repairing surface defects of silicon carbide fibers and silicon carbide fibers repaired by same |
| CN110341014A (en) * | 2019-06-12 | 2019-10-18 | 李辉 | A kind of preparation method of mildew preventing agent for wood |
| CN111099917A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Porous composite material for generating electric arc in microwave and preparation method thereof |
| CN111138200A (en) * | 2020-01-11 | 2020-05-12 | 浙江东新新材料科技有限公司 | Multiphase composite reinforced low-friction silicon carbide ceramic sealing material and preparation method thereof |
| CN111495410A (en) * | 2020-04-29 | 2020-08-07 | 浙江师范大学 | Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof |
| CN111760581A (en) * | 2019-08-30 | 2020-10-13 | 万华化学（宁波）有限公司 | Catalyst for preparing phosgene, preparation method thereof and method for preparing phosgene and comprehensively utilizing energy |
| CN112264081A (en) * | 2020-11-23 | 2021-01-26 | 大连理工大学 | Electrochemical reduction of CO2Bimetallic-nitrogen-doped integral carbon-based electrocatalyst for preparing ethanol and preparation method thereof |
| CN112499612A (en) * | 2020-12-23 | 2021-03-16 | 北京林业大学 | Silicon carbide ceramic derived carbon material with wood hierarchical pore structure and preparation method thereof |
| CN112823441A (en) * | 2018-10-29 | 2021-05-18 | 中国石油化工股份有限公司 | Porous composite material capable of generating electric arc in microwave field and preparation method and application thereof |
| CN112851394A (en) * | 2021-02-03 | 2021-05-28 | 潍坊工商职业学院 | Preparation method of porous silicon carbide ceramic |
| CN113000057A (en) * | 2021-02-02 | 2021-06-22 | 湖南大学 | Loaded with Cu/ZnO/CeO2Preparation method and application of porous material of catalyst |
| CN113060735A (en) * | 2021-05-14 | 2021-07-02 | 辽宁科技大学 | Ordered porous material constructed by silicon carbide and carbon material and preparation method thereof |
| CN113104860A (en) * | 2020-05-14 | 2021-07-13 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore channel structure |
| CN113135813A (en) * | 2020-01-20 | 2021-07-20 | 中国石油大学(华东) | Method for producing vinyl chloride by one-step method ethylene |
| CN113479888A (en) * | 2021-06-01 | 2021-10-08 | 中科汇通(内蒙古)投资控股有限公司 | Core-shell structure powder for SiC single crystal growth and preparation process thereof |
| CN113582197A (en) * | 2021-08-31 | 2021-11-02 | 青岛大学 | MOR molecular sieve with high silica-alumina ratio and preparation method thereof |
| CN113754454A (en) * | 2021-09-24 | 2021-12-07 | 中国矿业大学 | Preparation method and application of carbon fiber/silicon carbide directional porous framework |
| CN114100623A (en) * | 2020-08-26 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof |
| CN114349519A (en) * | 2022-01-19 | 2022-04-15 | 江苏宝利金材科技有限公司 | Slurry formula and production process of gel-casting ceramic filter |
| CN114870876A (en) * | 2022-06-14 | 2022-08-09 | 北京碧水源膜科技有限公司 | Catalyst and preparation method and application thereof |
| CN114939427A (en) * | 2022-06-11 | 2022-08-26 | 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) | High-efficiency silicon carbide catalyst and preparation method and application thereof |
| CN116060033A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method and application thereof |
| CN116120069A (en) * | 2022-12-28 | 2023-05-16 | 大莲电瓷（福建）有限公司 | Silicon carbide honeycomb ceramic and preparation method thereof |
| CN116161985A (en) * | 2023-01-12 | 2023-05-26 | 哈尔滨工业大学 | Surface treatment method before welding silicon carbide and welding method of silicon carbide and high-temperature alloy |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716533A (en) * | 2009-11-13 | 2010-06-02 | 北京化工大学 | Integrated catalyst carriers and method thereof for preparing catalyst |
| CN101966471A (en) * | 2010-04-23 | 2011-02-09 | 周江林 | High-efficiency environmental-friendly catalyst carrier |
| CN103301864A (en) * | 2012-03-12 | 2013-09-18 | 中国科学院大连化学物理研究所 | Pd/TiO2-C-SiC catalyst as well as preparation and application 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 |
| CN103706407A (en) * | 2014-01-02 | 2014-04-09 | 哈尔滨商业大学 | Method for preparing silicon carbide/porous carbon composite material with high specific surface area |
| CN103846101A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | C-SiC catalyst, its preparation and its application thereof |
-
2014
- 2014-08-28 CN CN201410432919.8A patent/CN105439563B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716533A (en) * | 2009-11-13 | 2010-06-02 | 北京化工大学 | Integrated catalyst carriers and method thereof for preparing catalyst |
| CN101966471A (en) * | 2010-04-23 | 2011-02-09 | 周江林 | High-efficiency environmental-friendly catalyst carrier |
| CN103301864A (en) * | 2012-03-12 | 2013-09-18 | 中国科学院大连化学物理研究所 | Pd/TiO2-C-SiC catalyst as well as preparation and application 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 |
| CN103846101A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | C-SiC catalyst, its preparation and its application thereof |
| CN103706407A (en) * | 2014-01-02 | 2014-04-09 | 哈尔滨商业大学 | Method for preparing silicon carbide/porous carbon composite material with high specific surface area |
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531487A (en) * | 2015-04-13 | 2018-01-02 | 科廷大学 | Produce the method and system of solid carbonaceous material |
| CN107531487B (en) * | 2015-04-13 | 2020-11-06 | 科廷大学 | Method and system for producing solid carbon material |
| CN109415267A (en) * | 2016-06-22 | 2019-03-01 | 拜罗伊特大学 | Ceramic composite and its manufacturing method |
| CN109415267B (en) * | 2016-06-22 | 2022-04-15 | 拜罗伊特大学 | Ceramic composite material and method for producing same |
| CN108187712A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | A kind of nonmetallic nitridation B catalyst and preparation and application and regeneration method |
| CN109534816A (en) * | 2017-09-21 | 2019-03-29 | 中南大学 | A method of preparing porous silicon carbide ceramic with high strength |
| CN107740266B (en) * | 2017-10-30 | 2019-05-17 | 厦门大学 | Continuous SiC fiber surface in situ C-SiO2Preparation method of composite coating |
| CN107740266A (en) * | 2017-10-30 | 2018-02-27 | 厦门大学 | Continuous SiC fiber surface in situ C SiO2Preparation method of composite coating |
| CN107790136A (en) * | 2017-11-08 | 2018-03-13 | 西安向阳航天材料股份有限公司 | A kind of preparation method of high temperature resistant methanation catalyst |
| CN107790136B (en) * | 2017-11-08 | 2020-01-21 | 西安向阳航天材料股份有限公司 | Preparation method of high-temperature-resistant methanation catalyst |
| CN108126659A (en) * | 2018-01-10 | 2018-06-08 | 中国科学院过程工程研究所 | A kind of not fire-hazardous absorbent charcoal composite material and its preparation method and application |
| CN108097307A (en) * | 2018-01-10 | 2018-06-01 | 南开大学 | The preparation method and its application method of a kind of non-metal catalyst for fixed bed acetylene preparing chloroethylene |
| CN108097307B (en) * | 2018-01-10 | 2020-08-21 | 南开大学 | Preparation method and use method of metal-free catalyst for preparing vinyl chloride from fixed bed acetylene |
| CN111099917A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Porous composite material for generating electric arc in microwave and preparation method thereof |
| CN112823441A (en) * | 2018-10-29 | 2021-05-18 | 中国石油化工股份有限公司 | Porous composite material capable of generating electric arc in microwave field and preparation method and application thereof |
| CN109928759A (en) * | 2019-03-14 | 2019-06-25 | 武汉工程大学 | A kind of SiC ceramic membrane electrochemical reaction electrode and preparation method thereof |
| CN110079996B (en) * | 2019-05-24 | 2021-08-13 | 中国人民解放军国防科技大学 | Method for repairing surface defects of silicon carbide fibers and silicon carbide fibers repaired by same |
| CN110079996A (en) * | 2019-05-24 | 2019-08-02 | 中国人民解放军国防科技大学 | Method for repairing surface defects of silicon carbide fibers and silicon carbide fibers repaired by same |
| CN110341014A (en) * | 2019-06-12 | 2019-10-18 | 李辉 | A kind of preparation method of mildew preventing agent for wood |
| CN111760581A (en) * | 2019-08-30 | 2020-10-13 | 万华化学（宁波）有限公司 | Catalyst for preparing phosgene, preparation method thereof and method for preparing phosgene and comprehensively utilizing energy |
| CN111138200A (en) * | 2020-01-11 | 2020-05-12 | 浙江东新新材料科技有限公司 | Multiphase composite reinforced low-friction silicon carbide ceramic sealing material and preparation method thereof |
| CN113135813A (en) * | 2020-01-20 | 2021-07-20 | 中国石油大学(华东) | Method for producing vinyl chloride by one-step method ethylene |
| CN111495410B (en) * | 2020-04-29 | 2022-12-20 | 浙江师范大学 | Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof |
| CN111495410A (en) * | 2020-04-29 | 2020-08-07 | 浙江师范大学 | Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof |
| CN113104860A (en) * | 2020-05-14 | 2021-07-13 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore channel structure |
| CN113104860B (en) * | 2020-05-14 | 2024-01-30 | 青岛大学威海创新研究院 | Preparation method of SAPO-34 molecular sieve with bionic pore structure |
| CN114100623B (en) * | 2020-08-26 | 2023-12-08 | 中国石油化工股份有限公司 | Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof |
| CN114100623A (en) * | 2020-08-26 | 2022-03-01 | 中国石油化工股份有限公司 | Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof |
| CN112264081A (en) * | 2020-11-23 | 2021-01-26 | 大连理工大学 | Electrochemical reduction of CO2Bimetallic-nitrogen-doped integral carbon-based electrocatalyst for preparing ethanol and preparation method thereof |
| CN112264081B (en) * | 2020-11-23 | 2022-01-07 | 大连理工大学 | Electrochemical reduction of CO2Bimetallic-nitrogen-doped integral carbon-based electrocatalyst for preparing ethanol and preparation method thereof |
| CN112499612A (en) * | 2020-12-23 | 2021-03-16 | 北京林业大学 | Silicon carbide ceramic derived carbon material with wood hierarchical pore structure and preparation method thereof |
| CN113000057A (en) * | 2021-02-02 | 2021-06-22 | 湖南大学 | Loaded with Cu/ZnO/CeO2Preparation method and application of porous material of catalyst |
| CN113000057B (en) * | 2021-02-02 | 2022-01-28 | 湖南大学 | Loaded with Cu/ZnO/CeO2Preparation method and application of porous material of catalyst |
| CN112851394A (en) * | 2021-02-03 | 2021-05-28 | 潍坊工商职业学院 | Preparation method of porous silicon carbide ceramic |
| CN112851394B (en) * | 2021-02-03 | 2022-04-12 | 潍坊工商职业学院 | Preparation method of porous silicon carbide ceramic |
| CN113060735A (en) * | 2021-05-14 | 2021-07-02 | 辽宁科技大学 | Ordered porous material constructed by silicon carbide and carbon material and preparation method thereof |
| CN113479888A (en) * | 2021-06-01 | 2021-10-08 | 中科汇通(内蒙古)投资控股有限公司 | Core-shell structure powder for SiC single crystal growth and preparation process thereof |
| CN113582197A (en) * | 2021-08-31 | 2021-11-02 | 青岛大学 | MOR molecular sieve with high silica-alumina ratio and preparation method thereof |
| CN113754454A (en) * | 2021-09-24 | 2021-12-07 | 中国矿业大学 | Preparation method and application of carbon fiber/silicon carbide directional porous framework |
| CN116060033A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method and application thereof |
| CN116060033B (en) * | 2021-10-29 | 2024-05-10 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method and application thereof |
| CN114349519A (en) * | 2022-01-19 | 2022-04-15 | 江苏宝利金材科技有限公司 | Slurry formula and production process of gel-casting ceramic filter |
| CN114939427A (en) * | 2022-06-11 | 2022-08-26 | 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) | High-efficiency silicon carbide catalyst and preparation method and application thereof |
| CN114870876A (en) * | 2022-06-14 | 2022-08-09 | 北京碧水源膜科技有限公司 | Catalyst and preparation method and application thereof |
| CN114870876B (en) * | 2022-06-14 | 2024-01-19 | 北京碧水源膜科技有限公司 | Catalyst and preparation method and application thereof |
| CN116120069A (en) * | 2022-12-28 | 2023-05-16 | 大莲电瓷（福建）有限公司 | Silicon carbide honeycomb ceramic and preparation method thereof |
| CN116120069B (en) * | 2022-12-28 | 2024-04-26 | 大莲电瓷（福建）有限公司 | Silicon carbide honeycomb ceramic and preparation method thereof |
| CN116161985A (en) * | 2023-01-12 | 2023-05-26 | 哈尔滨工业大学 | Surface treatment method before welding silicon carbide and welding method of silicon carbide and high-temperature alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105439563B (en) | 2019-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105439563A (en) | Integral porous carbon-silicon carbide composite material, and preparation method and application thereof | |
| Qian et al. | Octadecane/C-decorated diatomite composite phase change material with enhanced thermal conductivity as aggregate for developing structural–functional integrated cement for thermal energy storage | |
| Diez et al. | Synthesis strategies of templated porous carbons beyond the silica nanocasting technique | |
| Liu et al. | Carbon foams: 3D porous carbon materials holding immense potential | |
| Lee et al. | Recent advances in preparations and applications of carbon aerogels: A review | |
| Yuan et al. | Preparation and properties of mullite-bonded porous fibrous mullite ceramics by an epoxy resin gel-casting process | |
| Shcherban | Review on synthesis, structure, physical and chemical properties and functional characteristics of porous silicon carbide | |
| EP2909134B1 (en) | Process for the preparation of hierarchically meso and macroporous structured materials | |
| Zhang et al. | Enhanced thermal performance of phase-change material supported by nano-Ag coated eggplant-based biological porous carbon | |
| Mao et al. | Gelcasting of alumina foams consolidated by epoxy resin | |
| CN104925787A (en) | Method for preparing graphene aerogel through constant pressure drying | |
| Zhao et al. | Hierarchical porous carbon with graphitic structure synthesized by a water soluble template method | |
| Yuan et al. | Effect of mullite phase formed in situ on pore structure and properties of high-purity mullite fibrous ceramics | |
| Liu et al. | Development of cost-effective PCM-carbon foam composites for thermal energy storage | |
| Ma et al. | Direct ink writing of porous SiC ceramics with geopolymer as binder | |
| CN110289424A (en) | A kind of preparation method of MOF derived carbon and cellular porous carbon composite | |
| CN101293783A (en) | Method for preparing inorganic porous composite material by freeze-drying method | |
| CN111072318B (en) | Graphene aerogel phase-change composite material with oriented heat conduction characteristic and preparation method thereof | |
| CN103924172B (en) | A kind of preparation method of reinforced aluminum matrix composites | |
| Yang et al. | High-temperature CO2 adsorption by one-step fabricated Nd-doped Li4SiO4 pellets | |
| CN104945005A (en) | Porous material with central symmetry structure and method for preparing the same | |
| CN101759178A (en) | Preparation method for hollow carbon hemisphere | |
| CN105036798A (en) | Method for preparing porous ceramic by impregnation combining freeze-drying technology | |
| Zhao et al. | 3D hierarchical porous expanded perlite-based composite phase-change material with superior latent heat storage capability for thermal management | |
| CN109020469A (en) | A kind of SiO2Aeroge/SiC foam composite insulation material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |