CN105439563B - A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and its preparation and application - Google Patents
A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and its preparation and application Download PDFInfo
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Abstract
A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and preparation method thereof, the composite material is first by the way that dispersion is sufficiently stirred in carborundum powder, silicon powder, carbonaceous powder, sintering aid in water, then idiosome is made using ice crystal port-creating method or organic polymer foam template port-creating method, monoblock type silicon carbide nucleome is made after high temperature sintering；One layer is generated on porous SiC nucleome duct by in-situ synthesized or the polymerization carbonizatin method containing carbon matrix precursor again has higher mechanical strength and stable carbon containing shell.This composite material of the invention has the characteristics that high-specific surface area, easily-activated surface, acid-alkali-corrosive-resisting, high temperature resistant, good thermal conductivity and electric conductivity, relatively high and stable mechanical strength, lower gas are cheap by pressure drop, preparation cost, it may be used as the carrier of metal supported catalyst or be directly used as non-metallic catalyst, to solve the easy dusting of existing industrial activited carbon catalytic carrier, easily blocking, difficult molding, the defects of price is high.
Description
Technical field
The present invention relates to a kind of monolithic porous carbon fiber reinforced silicon carbide matrix composites and preparation method thereof, more specifically, this hair
It is bright to be related to a kind of carrier as metal supported catalyst or be directly used as non-metallic catalyst, high mechanical strength and high thermal conductivity
It is conductive, take carbon as shell and porous silicon carbide as the monoblock type composite material and preparation method of core.The carbon-silicon carbide is compound
The surface that material not only possesses the high-specific surface area of hierarchical porous structure and is easily chemically activated or modifies, while possessing stable whole
Body mechanical strength and controllable physicochemical properties.
Background technique
Active carbon is widely used as Industrial Catalysis agent carrier, such as hydrogenation reaction utilizes activated carbon supported noble metal
Pt, Pd etc..Active carbon possesses very high specific surface area (> 1000m2/ g) and very low heap density (0.5-0.9g/cm3), but its
Prepare that raw material sources are different to cause catalytic performance difference very big, the active carbon for causing effect good is expensive.Meanwhile active carbon machine
Tool intensity is very poor, and it is highly difficult to mold the active carbon with stabilizing mechanical intensity, causes to have when its application and is largely lost, not only
Loss catalyst also results in serious environmental pollution.Prepare a kind of cheap, effective, environmental-friendly carbon carrier substitution activity
Charcoal has very great industrial application meaning.
Silicon carbide is cheap as a kind of common industrial abrasive, and has very high mechanical strength and good lead
Electrical conductivity energy, but its specific surface area is low and surface chemistry inertia, is not suitable for being directly used as catalyst carrier.Even if using
SiC powder can greatly weaken as carrier, thermally conductive and conduction property, and only the carbofrax material of monoblock type can just embody it
Good thermally conductive and conduction property can heat direct-electrifying in the application.Europe ceramics of the Fukushima et al. in October, 2010
The micron openings monoblock type silicon carbide (2889- that 88% porosity is up to using ice crystal as template preparation has been delivered in association's will
Page 2896), it is the highest porosity of micron openings monoblock type silicon carbide in hitherto reported, but the monoblock type carbonization prepared by them
Silicon specific surface area is still below 10m2/ g, and it is added to the oxides such as yttrium oxide and aluminium oxide in the preparation, so that silicon carbide material
The further inerting in the surface of material, while the thermally conductive and electric conductivity of monoblock type silicon carbide is also greatly lowered.
Its defect, the packet letter of Dalian Chemical Physics Research Institute and research are solved in order to integrate the property of silicon carbide and active carbon
Team discloses a kind of method in Chinese patent application 201210181890 in 2012, this method be using SiC as substrate,
Enter CCl using He tympanites at 700-1000 DEG C4Steam is reacted with SiC, make surface of SiC generate one layer of high-specific surface area and
The stable carbon-coating of mechanical strength, and by-product SiCl4, while second gas component, including NH being added in reaction atmosphere3、CO2, energy
The physicochemical properties of controllable modulation carbon-coating.But the patent is only limited to be chemically treated SiC powder, although having
Stable mechanical strength and high specific surface area, there is no the structures for forming monoblock type, to cannot embody, SiC is good to be led
Heat and conductive characteristic.Metal Jinsong ZHANG research team, institute, the Chinese Academy of Sciences was mentioned in Chinese patent CN 102814188 disclosed in 2014
A kind of active carbon layer/foam silicon carbon structure catalyst and preparation method thereof is arrived, but this method is only to pass through carbon-coating
The mode of additive coking is applied on porous foam silicon carbide, is not connected closely between silicon carbide and carbon-coating, it is caused
Between heat transmitting be obstructed, while they used in porous foam silicon carbide mainly by oxidesintering, whole electric conductivity
It is all greatly lowered with thermal conductivity compared with silicon carbide.
Summary of the invention
The object of the present invention is to provide a kind of carrier as metal supported catalyst or it is directly used as non-metallic catalyst
High mechanical strength and high heat-conductivity conducting monolithic porous carbon fiber reinforced silicon carbide matrix composite, to solve on of the existing technology
State problem.This monolithic porous carbon fiber reinforced silicon carbide matrix composite of the invention should have excellent thermal conductivity, electric conductivity and stabilization
Good mechanical strength, while composite material integrally has the surface of high-specific surface area and chemically reactive modification, macropore mesoporous micro-
The porous structure and more cheap preparation cost of hole composition, these properties can effectively reduce in specific catalytic applications
Reaction bed pressure drop and the utilization rate and stability for promoting catalyst.
It is a further object to provide a kind of preparation methods of above-mentioned composite material.
Monolithic porous carbon fiber reinforced silicon carbide matrix composite of the invention, characteristic are that the composite material is more by monoblock type
The nucleome of hole silicon carbide-containing (SiC) and carbon containing (C) shell being covered on it composition；The monolithic porous silicon carbide-containing
Nucleome refer to SiC and Si, C, B, Cr, Mn, Fe, Co, Ni simple substance and containing Si, C, B, N, O, S, Cl, Cr, Mn, Fe, Co,
In Ni element one of one or more compound or it is a variety of first pass around pore-creating and form monolithic porous idiosome, then pass through
The porous ceramics of monoblock type made of Overheating Treatment sintering；The carbon containing shell refers to based on C, adulterates other nonmetallic members
One of element or the amorphous carbon containing nanotube or graphene-structured of a variety of formation；The method for covering carbon containing shell includes
In-situ synthesized and containing carbon matrix precursor polymerize carbonizatin method.
It is in terms of 100% by the total weight of SiC nucleome, SiC content is 30~100%, the weight ratio of element is 60~
90% Si, 10~40% C, 0~10% B, 0~10% N, 0~10% O, 0~10% Cr, 0~10%
The Ni of Mn, 0~10% Fe, 0~10% Co and 0~10%；It is C content in terms of 100% by the total weight of carbon containing shell
It is 20~100%, the content of other nonmetalloids is no more than 20%；The weight ratio of SiC nucleome and carbon containing shell is 20:1
~8:1.
Monoblock type idiosome contained substance during the silicon carbide-containing nuclear regime is standby is main are as follows: partial size between 0.02~
20 μm of SiC powder, partial size between 0.02~20 μm Si powder, partial size is between 0.02~20 μm of carbonaceous powder.
The carbonaceous powder can be through high temperature reduction carbonization containing carbon compound or polymer, be preferably but not limited to
Starch, cellulose, polypyrrole, poly- furans, polystyrene, polyethylene, phenolic resin；Be also possible to carbohydrate (preferably but
Be not limited to glucose, fructose, sucrose, starch, cellulose) under hydrothermal conditions (160~220 DEG C) carbonization formed carbonaceous powder
End；It is also possible to carbon containing monomer (being preferably but not limited to glucose, fructose, sucrose, starch, pyrroles, pyridine, furans, styrene)
(concentrated sulfuric acid, hydrogen peroxide, ferric trichloride, ammonium persulfate, azodiisobutyronitrile, diphenyl peroxide are preferably but not limited to through catalyst
Formyl) it polymerize the carbonaceous powder of carbonization；It is also possible in idiosome sintering process logical carbonaceous gas in situ and (is preferably but not limited to first
Alkane, ethylene, acetylene, benzene, pyrroles, pyridine, furans) generate carbonaceous powder.
Can also be added in monoblock type idiosome contained substance during the silicon carbide-containing nuclear regime is standby partial size between
Sintering aid powder described in 0.02~20 μm of sintering aid powder be preferably but not limited to Cr, Mn, Fe, Co, Ni, Cr, B,
B4C, and the compound powder of aforementioned sintering aid can be obtained by high temperature reduction, it is preferably but not limited to iron oxide, nitre
Sour iron, ferric sulfate, iron chloride, iron hydroxide, cobalt oxide, cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt hydroxide, nickel oxide, nitric acid
Nickel, nickel sulfate, nickel chloride, nickel hydroxide, chromium oxide, chromic nitrate, chromium sulfate, chromium chloride, chromium hydroxide, characteristic are not only
Facilitate silicon carbide sintering or Si and C reaction-sintered into the additive of silicon carbide, and its addition will not largely drop
The thermally conductive and conductive characteristic of low SiC.
The pore forming method of the monolithic porous idiosome includes ice crystal port-creating method and organic polymer foam template pore-creating
Method:
The ice crystal port-creating method comprises the steps of:
(a) component for forming monolithic porous idiosome is dispersed in water with the ratio, added component powder
Volume and the volume ratio of water are 0.1~1, preferably 0.1~0.4；In addition or 2~80 DEG C sufficiently under the action of do not add gelling agent
Stirring, gelling agent refer to dissolve by heating in water it is cooling after make the substance of solution gel, be preferably but not limited to agar, agarose,
Gelatin, starch, ethyl orthosilicate, gelling agent additive amount are the 0.5~10%, preferably 0.5~5% of the weight of water used,
(b) by gained slurry inject mold, gel or
It does not freeze and freezes after gel, ice crystal is precipitated from slurry.The preferred gypsum of mold, polytetrafluoroethylene (PTFE), processable ceramic,
The common materials such as steel, size pref. cylindrical, annulus cylindricality, rectangular, spherical, the preferred 1cm~10m of length, cross-sectional maximum dimension
It is preferred that 0.5~50cm, cryogenic temperature -20~-190 DEG C, preferably -30~-70 DEG C, 0.2~20h of cooling time, preferably 0.5~
5h,
(c) gained frozen material is dry, removal ice crystal forms duct, drying means be preferably but not limited to freeze-drying and
Humid control seasoning, the substantially volume contraction generated the purpose is to reduce general drying means；Freeze-drying refers to
Make frozen material without liquid and body phase phase transformation under low-temp low-pressure, the ice on surface is directly sublimed into the fast of gas
Rapid-curing cutback drying method；Humidity control seasoning refer to dried object humidity be 80~95%, temperature be 0~80 DEG C under conditions of at a slow speed
Dry method.
The organic polymer foam template port-creating method comprises the steps of:
(a) agent solution is sticked together in configuration at 20~80 DEG C, the adhesive agent refer to can be dissolved in water after increase solution viscosity
Compound or polymer are preferably but not limited to polyethylene glycol, polyvinyl alcohol, polypyrrole alkanone, will form monolithic porous idiosome
Component be dispersed in stick together with the ratio and form slurry in agent solution, with weight ratio meter, idiosome component powder accounts for 20~50%,
Adhesive agent accounts for 2~10%, and water accounts for 48~78%,
(b) the organic polymer foam block of shear forming is immersed in slurry, is taken out after stirring, take advantage of that slurry is not dry to use weight
Compression foam original volume 40~60% or do not press, three-dimensional stir 1~30min, repeat this step 2~5 time；It is organic poly-
Close the open cell foamed plastic that object foam refers to the connection containing abscess, preferably PU, PE, NBR/PVC, EPDM, more preferable PU.
(c) drying under 20~80 DEG C of temperature, humidity 20~90%, drying time preferably 2~10h.
The heat treatment sintering method of the monolithic porous ceramics comprises the steps of:
(a) by idiosome in air, inert gas (He, Ar), N2、H2Or 300~600 DEG C are warming up under vacuum condition, it heats up
0.1~20 DEG C/min of rate, preferably 0.1~5 DEG C/min switch or do not switch to reducibility gas (preferably H2、H2With indifferent gas
Body (He, Ar), N2Gaseous mixture) heat preservation 0.5~10h, reducibility gas air speed (GHSV) be 500~10000h-1, preferably 2000
~6000h-1,
(b) in inert gas (He, Ar), N2、H2Or 800~1200 DEG C, preferably 900~1050 are warming up under vacuum condition
DEG C, 0.5~50 DEG C/min of heating rate, preferably 2~20 DEG C/min or do not switch to carbonaceous gas and (are preferably but not limited to switching
Methane, ethylene, acetylene, benzene, pyrroles, pyridine, furans or aforementioned substances and inert gas (He, Ar), N2Gaseous mixture) heat preservation
0.5~10h, carbonaceous gas air speed (GHSV) are 500~10000h-1, preferably 2000~6000h-1,
(c) in inert gas (He, Ar), N2、H2Or 1300~2300 DEG C are warming up under vacuum condition, preferably 1500~
It 2050 DEG C, keeps the temperature and 0.2~10h or does not keep the temperature, preferably 0.2~1h of heat preservation or do not keep the temperature, heating rate 0.5~50 DEG C/min is excellent
Select 2~20 DEG C/min, 2~10 DEG C/min of rate of temperature fall.
The carbon containing shell is doped with nonmetalloid, its role is to modulation carbon-coating physicochemical properties, doping
Nonmetalloid include B, N, O, S, P, preferably B, N, O, S, Cl, I.
The in-situ synthesized of the carbon containing shell of covering refers to and will contain under conditions of load or not metal supported catalyst
Silicon carbide nucleome chemically reacts under high temperature (300~1000 DEG C) with the atmosphere that specified chemical forms by one or many, instead
0.1~5h, preferably 0.1~2h between seasonable, consumption or do not consume Portion Core and the carbon containing shell of in-situ preparation, characteristic are to contain
Carbon shell is completely embedded with silicon carbide-containing nucleome, there is relatively high and stable overall mechanical strength.
The described specified chemical composition can be atmosphere containing chlorine, carbon-containing atmosphere, other doping atmosphere, inert gas (He,
Ar)、N2Or H2, it is also possible to the mixture of aforementioned atmosphere.The atmosphere containing chlorine includes CCl4、CHCl3、CH2Cl2、CH3Cl、
HCl, preferably Cl2、CCl4, HCl, more preferable CCl4；Carbon-containing atmosphere includes methane, ethylene, ethane, acetonitrile, benzene, naphthalene, pyrroles, pyrrole
Pyridine, furans, optimization methane, ethylene, acetonitrile, benzene, pyrroles, pyridine；Other doping atmosphere include containing B, N, O, S, P, F, Cl,
The compound of Br, I element, preferably borine, ammonia, ammonia borine, diborane, dimethyamine borane, carbon disulfide, sulfur dioxide,
Carbon dioxide, NOx(x=0.5~2.5), oxygen, ozone, vapor, POx(x=1.5~2.5), phosphorus trichloride, trifluoro oxygen phosphorus,
One of hydrogen bromide, hydrogen iodide are a variety of.
The polymerization carbonizatin method containing carbon matrix precursor of the carbon containing shell of the covering refers in load or not metal supported catalyst
Under the conditions of by specific carbonaceous presoma by polymerization, carbonization, be re-activated and cover carbon-coating in SiC core surface, characteristic exists
It is tightly engaged into silicon carbide-containing core in the carbon containing shell of generation because of the polymerization property of specific carbonaceous presoma.
The specific carbonaceous presoma includes glucose, fructose, sucrose, pyrroles, pyridine, furans, vinyl pyrrole, ethylene
Yl pyridines, vinyl furan, vinyl pyrrole ketone, vinylpyridine ketone, vinyl furan diketone, acrylic acid, acrylamide, benzene
One of ethylene, divinylbenzene are a variety of.
The polymerizing condition can be in air, inert gas (He, Ar) or N2Lower 20~200 DEG C of polymerizations, can also be with
It is hydrothermal condition (160~220 DEG C) polycondensation, polymerization time preferably 0.5~60h.
The Carbonization Conditions are in inert gas (He, Ar) or N2Lower 300~1000 DEG C of heat treatment, processing time are preferred
0.5~10h.
The reactivation instigates other nonmetalloids of sample adulteration or increase specific surface area after aforementioned carbonization
Process.It is described adulterate other nonmetalloids method be by sample after aforementioned carbonization in the case where adulterate atmosphere pass through it is one or many
300~1000 DEG C heat treatment, handle time preferably 0.5~10h.The doping atmosphere include containing H, B, N, O, S, P, F,
The compound of Cl, Br, I element, preferably hydrogen, borine, ammonia, ammonia borine, diborane, dimethyamine borane, carbon disulfide, two
Sulfur oxide, carbon dioxide, NOx(x=0.5~2.5), oxygen, ozone, vapor, POx(x=1.5~2.5), phosphorus trichloride, three
One of fluorine oxygen phosphorus, hydrogen bromide, hydrogen iodide or a variety of and described doped compound and inert gas (He, Ar) or N2's
Gaseous mixture.The method for increasing specific surface area includes common phosphoric acid activation method, potassium hydroxide or sodium hydroxide activation method, two
Carbonoxide activation method.The phosphoric acid activation method, which refers to, mixes sample after aforementioned carbonization with phosphoric acid solution, with mass ratio preferably 1:
1.5~1:6, the concentration of phosphoric acid solution preferably 30~85%, then mixture is in inert gas (He, Ar) or N2Under 300~
600 DEG C of processing 0.5~5h, gas space velocity (GHSV) preferably 2000~6000h-1, heating rate preferably 0.2~20 DEG C/min.Institute
It states potassium hydroxide or sodium hydroxide activation method refers to and mixes sample after aforementioned carbonization with potassium hydroxide solid or sodium hydrate solid
It closes, with the preferred 1:1.5~1:6 of mass ratio, then mixture is in inert gas (He, Ar) or N2Under 600~1000 DEG C handle
0.5~5h, gas space velocity (GHSV) preferably 2000~10000h-1, heating rate preferably 1~20 DEG C/min.The carbon dioxide
Activation method refers to sample after aforementioned carbonization in CO2In 600~1000 DEG C of 2~20h of processing under atmosphere, gas space velocity (GHSV) is excellent
Select 2000~10000h-1, heating rate preferably 1~20 DEG C/min.
The so-called metallic catalyst loaded when covering carbon containing shell refers to urging after high temperature reduction containing metal
Agent, its role is to promote and adjust the generation of carbon containing shell, with modulation carbon-coating physicochemical properties.The metal of the load
Metallic element contained by catalyst includes Cr, Fe, Co, Ni, Cu, Zn, Mo, Ag, Sn, La, Ce, W, Au, preferably Fe, Co, Ni, Mo,
Ag,Ce.The catalyst can be oxidant or radical initiator, be preferably but not limited to iron chloride, sodium peroxydisulfate, dioxygen
One of water, azodiisobutyronitrile, dibenzoyl peroxide are a variety of.
The high temperature reduction refers in inert gas (He, Ar), N2、H2, under CO or vacuum condition, be maintained at high temperature 300~
600 DEG C of 0.5~10h of processing, heating rate preferably 1~20 DEG C/min.
The monolithic porous carbon fiber reinforced silicon carbide matrix composite, conductivity is between 0.01~50S/cm；Its thermal coefficient is situated between
In 1~300W/ (mK)；Its porosity is between 30~95%, preferably 50~90%, more preferable 60~90%；Its average pore size is situated between
In 2 μm~5mm, preferably 20~500 μm, more preferable 20~100 μm；Its specific surface area is between 1~500m2/ g, preferably 10~
300m2/g；More preferable 50~200m2/g。
The present invention is based on the Research foundation of long-term SiC material and carbon material, a kind of monolithic porous carbon-to-carbon is provided
SiClx composite material and preparation method, by the addition of specific sintering aid, in the premise for not influencing thermal conductivity and electric conductivity
Under so that the silicon carbide-containing nucleome of high porosity is provided with high mechanical strength and active surface.By the doping of nonmetalloid and
The variation of synthesis condition, the controllable modulation physicochemical properties of carbon containing shell.Pass through generation or specific polymerization in situ
Carbonization makes the combination of carbon containing shell and silicon carbide-containing nucleome have relatively high and stable mechanical strength.To sum up, of the invention this
Composite material has high-specific surface area, easily-activated surface, acid-alkali-corrosive-resisting, high temperature resistant, good thermal conductivity and electric conductivity, higher
And stable mechanical strength, lower gas by pressure drop, preparation cost is cheap the features such as, may be used as carried metal catalysis
The carrier of agent is directly used as non-metallic catalyst, thus solve the easy dusting of existing industrial activited carbon catalytic carrier, easily blocking,
The defects of hardly possible forms, price is high.
Detailed description of the invention
The scanning electron microscope shape appearance figure of Fig. 1 composite material；Left figure (A) shows the eurypyloue carbon fiber reinforced silicon carbide matrix composite of tool；
Right figure (B) shows the carbon containing shell of silicon carbide nucleome inner bore surface covering.
Specific embodiment
The composite material is first by the way that carborundum powder, silicon powder, carbonaceous powder, sintering aid to be sufficiently stirred point in water
It dissipates, idiosome then is made using ice crystal port-creating method or organic polymer foam template port-creating method, is made whole after high temperature sintering
Body formula silicon carbide nucleome, makes the silicon carbide-containing nucleome of high porosity be provided with height under the premise of not influencing thermal conductivity and electric conductivity
Mechanical strength and active surface；Then it polymerize carbonizatin method in porous SiC nucleome hole by in-situ synthesized or containing carbon matrix precursor
One layer is generated on road has higher mechanical strength and stable carbon containing shell.Pass through the doping of nonmetalloid and synthesis condition
Variation, the controllable modulation physicochemical properties of carbon containing shell.This composite material of the invention have high-specific surface area, easily
Activating surface, acid-alkali-corrosive-resisting, high temperature resistant, good thermal conductivity and electric conductivity, relatively high and stable mechanical strength, lower gas
The features such as body passes through pressure drop, preparation cost is cheap, may be used as the carrier of metal supported catalyst or is directly used as nonmetallic
Catalyst, to solve the easy dusting of existing industrial activited carbon catalytic carrier, easily blocking, difficult molding, the defects of price is high.
Embodiment 1
It weighs 100 mesh SiC powder 10.0g, 100 mesh Si powder 6.5g, acetylene powdered carbon 2.8g, 100 mesh Fe powder 1.5g and pours into 24mL
0.5% agarose solution in, 80 DEG C of stirring 30min.The slurry of formation pours into internal diameter 2cm, the cylindrical polytetrafluoro of long 10cm
In mold, the cooling 2h of room temperature is placed into -30 DEG C of refrigerators and is freezed 2h.Frozen material taking-up, which is put into freeze dryer, is lyophilized the obtained embryo of 48h
Body.By idiosome as in graphite crucible, being warming up to 500 DEG C under the Ar gas of 50mL/min, 1 DEG C/min of heating rate, in 50mL/
It is warming up to 1000 DEG C, 10 DEG C/min of heating rate under the Ar gas of min, 1500 DEG C are warming up under the Ar gas of 50mL/min, heating
2 DEG C/min of rate, heat preservation vacuumize heat preservation 2 hours after 2 hours, monolithic porous SiC nucleome is made in the cold cooling of furnace.
SiC nucleome is encapsulated into quartz ampoule, 800 DEG C are warming up under the Ar gas of 50mL/min, then in 50mL/min
Ar, 1.5mL/min NH3, 4.0mL/min CCl4It is made under gaseous mixture in 800 DEG C of heat preservation 0.5h with 30 DEG C/min cooling
The carbon fiber reinforced silicon carbide matrix composite of N doping.
The scanning electron microscope shape appearance figure of the composite material is as follows, and this pattern is the typical case of carbon fiber reinforced silicon carbide matrix composite.
The composition of composite material SiC nucleome is 91.2% SiC, 3.6% Fe, the carbon of 4.6% Si and 0.6%；
The composition of carbon-coating is 86.7% carbon, 7.2% nitrogen and 6.1% oxygen.
Embodiment 2
Weigh 100 mesh SiC powder 10.0g, 100 mesh Si powder 6.5g, acetylene powdered carbon 2.8g, Cr (NO3)3Powder 1.0g, Ni (NO3)2
Powder 0.5g is poured into 2% gelatin solution of 24mL, 60 DEG C of stirring 30min.The slurry of formation pours into internal diameter 2cm, the circle of long 10cm
In cylindricality polyethylene mold, the cooling 1h of room temperature is placed into -60 DEG C of refrigerators and is freezed 5h.Frozen material taking-up, which is put into freeze dryer, freezes
Idiosome is made in dry 48h.By idiosome as in corundum crucible, 500 DEG C are warming up under the Air gas of 50mL/min, heating rate 0.5
DEG C/min, in the H of 50mL/min21000 DEG C are warming up under gas, 10 DEG C/min of heating rate switches to the CH of 50mL/min4Gas exists
1h is kept the temperature at 1000 DEG C, 1600 DEG C, 2 DEG C/min of heating rate are warming up under the Ar gas of 50mL/min, furnace is cold after heat preservation 2 hours
Cooling, is made monolithic porous SiC nucleome.
SiC nucleome is encapsulated into quartz ampoule, 800 DEG C are warming up under the Ar gas of 50mL/min, then in 10mL/min
Ar, 2mL/min NH3, 3.0mL/min CCl4N is made with 30 DEG C/min cooling in 300 DEG C of heat preservation 0.5h under gaseous mixture
The carbon fiber reinforced silicon carbide matrix composite of doping.
Embodiment 3
Weigh 400 mesh SiC powder 28.9g, acetylene powdered carbon 0.5g, B2O3Powder 0.5g pours into the 5% ethyl orthosilicate (pH of 24mL
1) in solution, 30 DEG C of stirring 2h.The slurry of formation pours into internal diameter 2cm, and in the cylindrical polyethylene mold of long 10cm, room temperature is cooling
5h is placed into and is freezed 0.2h in liquid nitrogen.Frozen material taking-up, which is put into freeze dryer, is lyophilized the obtained idiosome of 48h.By idiosome as graphite
In crucible, 500 DEG C are warming up under the Ar gas of 50mL/min, 1 DEG C/min of heating rate is warming up under the Ar gas of 50mL/min
1000 DEG C, 10 DEG C/min of heating rate, 1600 DEG C, 2 DEG C/min of heating rate are warming up under the Ar gas of 50mL/min, with 3 DEG C/
Min cooling, is made monolithic porous SiC nucleome.
SiC nucleome is encapsulated into quartz ampoule, 800 DEG C are warming up under the Ar gas of 50mL/min, then in 10mL/min
Ar, 4.0mL/min CCl4The carbon-silicon carbide of B doping is made with 30 DEG C/min cooling in 700 DEG C of heat preservation 2h under gaseous mixture
Composite material.
Embodiment 4
200 mesh SiC powder 11.8g are weighed, are poured into 1% agarose solution of 24mL, 60 DEG C of stirring 1h.The slurry of formation falls
Enter internal diameter 2cm, in the cylindrical stainless steel mould of long 10cm, the cooling 2h of room temperature is placed into -50 DEG C of refrigerators and freezed 2h.Freezing
Object taking-up, which is put into freeze dryer, is lyophilized the obtained idiosome of 48h.By idiosome as in graphite crucible, heat up under the Ar gas of 50mL/min
To 500 DEG C, 1 DEG C/min of heating rate, 1000 DEG C, 20 DEG C/min of heating rate are warming up under the Ar gas of 50mL/min,
It is warming up to 2200 DEG C, 10 DEG C/min of heating rate under the Ar gas of 50mL/min, keeps the temperature the cold cooling of furnace after 1h, is made monolithic porous
SiC nucleome.
SiC nucleome is placed in 15% sucrose solution of 70mL and is put into 100mL water heating kettle, is kept the temperature at 180 DEG C for 24 hours, it will
In the NH of 50mL/min after carbon fiber reinforced silicon carbide matrix composite taking-up3N is made with 10 DEG C/min cooling in 700 DEG C of heat preservation 2h under gas
The carbon fiber reinforced silicon carbide matrix composite of doping.
Embodiment 5
Weigh 100 mesh SiC powder 10.0g, 100 mesh Si powder 6.5g, acetylene powdered carbon 2.8g, Fe (NO3)3Powder 1.5g, pours into 24mL
1% agarose solution in, 60 DEG C of stirring 1h.The slurry of formation pours into internal diameter 2cm, the cylindrical polytetrafluoro mold of long 10cm
In, the cooling 2h of room temperature is placed into -50 DEG C of refrigerators and is freezed 2h.Frozen material taking-up, which is put into freeze dryer, is lyophilized the obtained idiosome of 48h.
By idiosome as in graphite crucible, being warming up to 500 DEG C under the Ar gas of 50mL/min, 1 DEG C/min of heating rate, in 50mL/min
H2800 DEG C are warming up under gas, 5 DEG C/min of heating rate is warming up to 1500 DEG C, heating rate 10 under the Ar gas of 50mL/min
DEG C/min, the cold cooling of furnace after 2h is kept the temperature, monolithic porous SiC nucleome is made.
SiC nucleome is placed in 20% glucose solution of 70mL and is put into 100mL water heating kettle, keeps the temperature 20h at 200 DEG C,
In the NH of 50mL/min after carbon fiber reinforced silicon carbide matrix composite is taken out3In 600 DEG C of heat preservation 2h under gas, N doping is made in the cold cooling of furnace
Carbon fiber reinforced silicon carbide matrix composite.
Embodiment 6
It weighs 100 mesh SiC powder 10.0g, 100 mesh Si powder 6.5g, glucose 10.0g and pours into 2% gelatin solution of 24mL
In, it is put into water heating kettle, is kept the temperature at 180 DEG C for 24 hours, Cr (NO is added after cooling3)3Powder 1.5g, 60 DEG C of stirring 1h.The slurry of formation
Material pours into internal diameter 2cm, and in the cylindrical polytetrafluoro mold of long 10cm, the cooling 2h of room temperature is placed into -50 DEG C of refrigerators and freezed 2h,
Place into cooling 0.2h in liquid nitrogen.Frozen material taking-up, which is put into freeze dryer, is lyophilized the obtained idiosome of 48h.By idiosome as graphite crucible
In, 500 DEG C are warming up under the Ar gas of 50mL/min, 1 DEG C/min of heating rate switches to the H of 50mL/min2It is kept the temperature under gas
2h, then 1000 DEG C are warming up under the Ar gas of 50mL/min, 10 DEG C/min of heating rate is warming up under the Ar gas of 50mL/min
1500 DEG C, 5 DEG C/min of heating rate, the cold cooling of furnace after 2h is kept the temperature, monolithic porous SiC nucleome is made.
SiC nucleome incipient impregnation is contained into 0.1%FeCl3Dense hydrogen peroxide, be put into glass tube and be passed through 100mL/min's
Ar and 30mL/min furans steam, keeps the temperature 1h at 60 DEG C, in the Ar gas of 50mL/min after carbon fiber reinforced silicon carbide matrix composite is taken out
Under in 600 DEG C of heat preservation 2h, the carbon fiber reinforced silicon carbide matrix composite of O doping is made in the cold cooling of furnace.
Embodiment 7
It weighs 100 mesh SiC powder 10.0g, 100 mesh Si powder 6.5g, 400 mesh Fe powder 0.6g and pours into 2% gelatin solution of 24mL
In stir 1h at 60 DEG C.The slurry of formation pours into internal diameter 2cm, in the cylindrical polytetrafluoro mold of long 10cm, the cooling 2h of room temperature,
It places into -50 DEG C of refrigerators and freezes 2h, place into cooling 0.2h in liquid nitrogen.Frozen material taking-up is put into freeze-drying 48h system in freeze dryer
Obtain idiosome.By idiosome as in graphite crucible, being warming up to 500 DEG C under the Ar gas of 50mL/min, 1 DEG C/min of heating rate is cut
Shift to the H of 50mL/min22h is kept the temperature under gas, then 1000 DEG C are warming up under the Ar gas of 50mL/min, 10 DEG C/min of heating rate,
Switch to the CH of 100mL/min41h is kept the temperature under gas, then 1500 DEG C are warming up under the Ar gas of 50mL/min, 5 DEG C of heating rate/
Min keeps the temperature the cold cooling of furnace after 2h, monolithic porous SiC nucleome is made.
SiC nucleome incipient impregnation is contained into 0.1%FeCl3Dense hydrogen peroxide, be put into glass tube and be passed through 100mL/min's
Ar and 30mL/min pyrroles's steam, keeps the temperature 1h at 30 DEG C, in the Ar gas of 50mL/min after carbon fiber reinforced silicon carbide matrix composite is taken out
Under in 600 DEG C of heat preservation 2h, the carbon fiber reinforced silicon carbide matrix composite of N doping is made in the cold cooling of furnace.
Embodiment 8
Sucrose 10.0g is weighed, is added in 30mL distilled water, is put into water heating kettle and is kept the temperature at 200 DEG C for 24 hours, cooled and filtered
Carbonaceous powder is obtained to pour into then together with 10 μm of partial size of SiC powder 10.0g, 100 mesh Si powder 6.5g, 100 mesh Fe powder 1.0g
In 2% gelatin solution of 24mL, 60 DEG C of stirring 1h.The slurry of formation pours into internal diameter 2cm, the cylindrical polytetrafluoro mold of long 10cm
In, the cooling 2h of room temperature is placed into -50 DEG C of refrigerators and is freezed 2h.Frozen material taking-up, which is put into freeze dryer, is lyophilized the obtained idiosome of 48h.
By idiosome as in graphite crucible, being warming up to 500 DEG C under the Ar gas of 100mL/min, 1 DEG C/min of heating rate, in 50mL/
It is warming up to 1000 DEG C, 10 DEG C/min of heating rate under the Ar gas of min, 1500 DEG C are warming up under the Ar gas of 50mL/min, heating
5 DEG C/min of rate keeps the temperature the cold cooling of furnace after 2h, monolithic porous SiC nucleome is made.
SiC nucleome is put into the 0.2%w/v dopamine hydrochloride solution of the pH 8.6 newly configured and stirs 20h, it will be made
The carbon fiber reinforced silicon carbide matrix composite obtained impregnates 1h in 60 DEG C of dense HI solution after taking out, and the carbon-silicon carbide of N, I codope is made
Composite material.
Embodiment 9
Sucrose 10.0g is weighed, is added in 30mL distilled water, is put into water heating kettle and is kept the temperature at 200 DEG C for 24 hours, cooled and filtered
Carbonaceous powder is obtained to pour into then together with 10 μm of partial size of SiC powder 10.0g, 100 mesh Si powder 6.5g, 100 mesh Fe powder 1.0g
In the 1%PVA solution of 30mL, slurries are made in 60 DEG C of stirring 1h.By the cubic block of a length of 2cm of porous polyurethane sponge sheared edge,
Cubic block is sufficiently submerged in slurries, cubic block is taken out and compresses the 60% of its volume, agitation is again dipped into slurries in a moment, repeats to soak
Profit, compression step three times, take out cube, and 60 DEG C of dryings are for 24 hours under 80% humidity.By idiosome as in corundum crucible,
500 DEG C are warming up under the Air gas of 100mL/min, 0.5 DEG C/min of heating rate is warming up to 1000 under the Ar gas of 50mL/min
DEG C, 10 DEG C/min of heating rate is warming up to 1500 DEG C, 5 DEG C/min of heating rate under the Ar gas of 50mL/min, keeps the temperature furnace after 2h
Monolithic porous SiC nucleome is made in cold cooling.
SiC nucleome is encapsulated into quartz ampoule, 800 DEG C is heated to 5 DEG C/min heating rate, is passed through 50mL/min's
The Cl of Ar, 5mL/min2, 0.5h is kept the temperature, the Ar furnace for switching to 50mL/min is cold, and monoblock type carbon fiber reinforced silicon carbide matrix composite is made.
Embodiment 10
Weigh 10 μm of partial size of SiC powder 10.0g, 100 mesh Si powder 6.5g, incipient impregnation Fe containing 0.8g (NO) after mixing3
Solution, drying be placed in quartz ampoule, in 50mL/minH2Under be warming up to 500 DEG C of reductase 12 h, risen in 100mL/min Ar
Temperature is passed through 100mL/min Ar and 50mL/min pyridine steam to 800 DEG C again, keeps the temperature 1h, powder is poured into the water of 24mL after cooling
In, it is sufficiently stirred.The slurry of formation pours into internal diameter 2cm, in the cylindrical polytetrafluoro mold of long 10cm, is put into liquid nitrogen and freezes
0.5h.Frozen material taking-up, which is put into freeze dryer, is lyophilized the obtained idiosome of 48h.By idiosome as in graphite crucible, 100mL/min's
500 DEG C are warming up under Ar gas, 1 DEG C/min of heating rate is warming up to 1000 DEG C, heating rate 10 under the Ar gas of 50mL/min
DEG C/min, it is warming up to 1500 DEG C, 5 DEG C/min of heating rate under the Ar gas of 50mL/min, keeps the temperature the cold cooling of furnace after 2h, is made whole
Body formula porous SiC nucleome.
SiC nucleome is put into the 0.2%w/v dopamine hydrochloride solution of the pH 8.6 newly configured and stirs 20h, it will be made
The carbon fiber reinforced silicon carbide matrix composite obtained is warming up to 800 DEG C, 5 DEG C/min of heating rate under the Ar gas of 50mL/min after taking out, heat preservation
The carbon fiber reinforced silicon carbide matrix composite of N doping is made in the cold cooling of furnace after 2h.
The Cl of 5mL/min2, 0.5h is kept the temperature, the Ar furnace for switching to 50mL/min is cold, and it is compound that monoblock type carbon-silicon carbide is made
Material.
Embodiment 11
10 μm of partial size of SiC powder 11.8g is weighed, graphene 0.5g is poured into the water of 24mL, is sufficiently stirred.The slurry of formation
Material pours into internal diameter 2cm, in the cylindrical polytetrafluoro mold of long 10cm, is put into liquid nitrogen and freezes 0.5h.Frozen material taking-up is put into jelly
48h is lyophilized in dry machine, idiosome is made.By idiosome as in graphite crucible, being warming up to 500 DEG C under the Ar gas of 100mL/min, rise
Warm 1 DEG C/min of rate is warming up to 1000 DEG C, 10 DEG C/min of heating rate, in the Ar of 50mL/min under the Ar gas of 50mL/min
It is warming up to 1500 DEG C, 5 DEG C/min of heating rate under gas, keeps the temperature the cold cooling of furnace after 2h, monolithic porous SiC nucleome is made.
SiC nucleome is put into the water heating kettle equipped with 10% starch solution of 30mL, is kept the temperature at 200 DEG C for 24 hours, it will be made
The carbon fiber reinforced silicon carbide matrix composite obtained is warming up to 1000 DEG C, 5 DEG C/min of heating rate under the Ar gas of 50mL/min after taking out, protect
Monoblock type carbon fiber reinforced silicon carbide matrix composite is made in the cold cooling of furnace after warm 2h.
Application examples 1
Catalyst after the Ni metal of carbon fiber reinforced silicon carbide matrix composite load 5% as blast furnace gas methanation, 500 DEG C of air speeds
(GHSV) 20000 lower CO conversions are up to 90%, selectivity 98%, because its high-termal conductivity have in this exothermic reaction it is good
Good stability is stablized in catalyst activity 100 hours when reaction temperature is 550 DEG C.
Application examples 2
Carbon fiber reinforced silicon carbide matrix composite mixes after 6% nitrogen that metal supported catalyst can be directly as acetylene hydrochlorination
Catalyst, in industrial air speed (GHSV) 30h-1Under reach existing mercury catalyst active 90%, laboratory stability is higher than 200 hours.
Claims (5)
1. a kind of monolithic porous carbon-silicon carbide C-SiC composite material, characteristic are: the composite material is more by monoblock type
The nucleome of hole silicon carbide-containing SiC and the carbon containing shell being covered on it composition；
It is described be covered on it refer to shell be covered on nucleome internal channel surfaces or shell be covered on nucleome outer surface and
The internal channel surfaces of nucleome；
Carbon containing shell is based on C, and that adulterates one of other nonmetalloids or a variety of formation contains nanotube or graphite
The amorphous carbon of alkene structure, 1) nucleome of silicon carbide-containing is that the above are originals with one of SiC and following additives or two kinds
Raw material is mixed and forms monolithic porous idiosome by pore-creating by material, monoblock type made of being then sintered through Overheating Treatment it is porous
Ceramics；
Additive include: one of Si, C, B, Cr, Mn, Fe, Co, Ni simple substance or two kinds or more and/or Cr, Mn, Fe,
The borides of one of Co, Ni or two kinds or more, nitride, carbide, silicide, oxide, chloride, hydroxide,
The nitride of the carbide and/or Si of one of carbonate, nitrate, sulfate, silicate or two kinds or more and/or B,
And/or the nitride of B；
2) method for preparing carbon containing shell includes in-situ synthesized or polymerize carbonizatin method containing carbon matrix precursor.
2. composite material described in accordance with the claim 1, characteristic are:
It is in terms of 100% that the nucleome of silicon carbide-containing, which is by its total weight, and SiC content is 30 ~ 100%；Element wt ratio in the nucleome
Example are as follows: 60 ~ 90% Si, 10 ~ 40% C, 0 ~ 10% B, 0 ~ 10% N, 0 ~ 10% O, 0 ~ 10% Cl, 0 ~ 10% Cr, 0 ~
10% Mn, 0 ~ 10% Fe, the Ni of 0 ~ 10% Co and 0 ~ 10%, B, Cr, N, O, Cl, Mn, Fe, Co, Ni are not 0 simultaneously；
Carbon containing shell refers to based on C, adulterates the nanotube or graphene of one of other nonmetalloids or a variety of formation
The amorphous structure carbon of structure is in terms of 100% by the total weight of carbon containing shell, and C content is more than or equal to 20% and less than 100%, other
The content of nonmetalloid is less than 20%；The nonmetalloid of doping includes one of B, N, O, S, P, F, Br, Cl, I or two
Kind or more；
The weight ratio of the nucleome of silicon carbide-containing and carbon containing shell is 20:1 ~ 8:1.
3. composite material described in accordance with the claim 1, characteristic are:
Additive include: Si, C, B, Cr, Mn, Fe, Co, Ni, chromium oxide, chromium chloride, chromium hydroxide, chromium carbonate, chromic nitrate,
Chromium sulfate, manganese oxide, manganese chloride, manganese carbonate, manganese nitrate, manganese sulfate, iron oxide, iron chloride, iron hydroxide, ferric carbonate, nitric acid
Iron, ferric sulfate, ferrosilite, iron suicide, cobalt oxide, cobalt chloride, cobalt hydroxide, cobalt carbonate, cobalt nitrate, cobaltous sulfate, nickel oxide, chlorine
Change one of nickel, nickel hydroxide, nickelous carbonate, nickel nitrate, nickel sulfate, boron nitride, boron carbide or two kinds or more.
4. a kind of preparation method of composite material described in claims 1 or 2, characteristic are:
1) nucleome of silicon carbide-containing with one of SiC and following additives or two kinds the above are raw material, pass through by raw material mixing
Pore-creating forms monolithic porous idiosome, the porous ceramics of monoblock type made of being then sintered through Overheating Treatment；
Additive include: one of Si, C, B, Cr, Mn, Fe, Co, Ni simple substance or two kinds or more and/or Cr, Mn, Fe,
The borides of one of Co, Ni or two kinds or more, nitride, carbide, silicide, oxide, chloride, hydroxide,
The nitride of the carbide and/or Si of one of carbonate, nitrate, sulfate, silicate or two kinds or more and/or B,
And/or the nitride of B；
2) method for preparing carbon containing shell includes in-situ synthesized or polymerize carbonizatin method containing carbon matrix precursor.
5. a kind of application of composite material described in claims 1 or 2, characteristic are: the composite material is used as load
The carrier of metallic catalyst is used in the reaction of acetylene hydrochlorination preparing chloroethylene directly as non-metallic catalyst.
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