CN109734475A

CN109734475A - A kind of preparation method of porous heat-insulating ceramic material

Info

Publication number: CN109734475A
Application number: CN201910124817.2A
Authority: CN
Inventors: 陈倩
Original assignee: Changzhou Haotan Trading Co Ltd
Current assignee: Changzhou Haotan Trading Co Ltd
Priority date: 2019-02-20
Filing date: 2019-02-20
Publication date: 2019-05-10

Abstract

The invention discloses a kind of preparation methods of porous heat-insulating ceramic material, belong to technical field of function materials.The present invention is by sodium alginate, and polyvinyl alcohol, water mixing, after standing swelling, heating stirring dissolution is subsequently added into sodium metaperiodate, and heating stirring mixing obtains mixed slurry；By mixed slurry, organic siliconresin, emulsifier, modified corn starch is newborn, waterglass, and modified additive is stirred, obtains hybrid adhesive；By clay, modification infusorial earth, hybrid adhesive, water, ice crystal, wollastonite, serpentine is stirred, and injection molding, compression moulding demoulds, dry, obtains dry brick；Using the nitrogen treatment adobe containing trimethyl aluminium, pretreatment adobe is obtained；Adobe resistance sintering will be pre-processed, will be cooled down to get porous heat-insulating ceramic material.The porous heat-insulating ceramic material of technical solution of the present invention preparation has the characteristics that excellent in mechanical performance while porosity is high, has broad prospects in the development of functional material technology industry.

Description

A kind of preparation method of porous heat-insulating ceramic material

Technical field

The invention discloses a kind of preparation methods of porous heat-insulating ceramic material, belong to technical field of function materials.

Background technique

Porous ceramics is a kind of new material to grow up the 1970s, since it has porosity height, thermal conductivity The excellent performances such as rate is low, light-weight, hardness is high, anti-thermal shock, high temperature resistant, corrosion-resistant and good mechanical strength, can be used as ideal Building heat preservation heat-barrier material.Porous ceramics can be divided into 2 kinds with regard to microcellular structure form: pore structure of holding one's breath and open pore structure. Pore structure of holding one's breath refers to that ceramic material internal capillary is distributed in continuous ceramic matrix, is separated from each other between Kong Yukong, and opens Implication pore structure includes interconnected and openings at one side between ceramic material internal holes and hole again, and the silent formation in another side is not connected to 2 kinds of stomata.The a large amount of combustible that the pore structure of porous ceramics is usually the cavity formed by particle packing, is added in green body Or decomposable object formed gap, the gap that mechanical foaming is formed in green body forming process and due to blank forming during The organic precursor introduced burns the hole etc. to be formed.It will generally use particles of aggregates method of piling and precursor after-flame method can be with The porous ceramic articles of higher open pore are made, and the stomata for using combustible or decomposition product to be formed inside green body has Major part forms closed pore or half opening stomata, is essentially all closed pore using the stomata that mechanical foaming method is formed. For being used as the porous ceramic film material that filtering, gas distribution etc. use, it is generally intended to apparent porosity with higher, is surrounded This purpose.Currently, the method for preparing foamed ceramic mainly has powder green bodies foaming and slurry foaming.Powder green bodies foaming Method is that green compact are made using foaming agents such as calcium carbonate, calcium hydroxide, aluminum sulfate and hydrogen peroxide, re-sinters and obtains foamed ceramic Preparation process；Slurry foaming is foamed using ceramic suspension liquid, the technique re-sintered through dry demoulding.Above two work Skill is complicated, and higher cost is not easy the large-sized foamed ceramic continuously made, is restricted its purposes.

Coal dust burns in burner hearth in suspended state, and most combustibles in fire coal can be burnt out in furnace, and coal Powder incombustible (predominantly ash content) is largely mingled in high-temperature flue gas.These incombustible partial melting due to by high temperature action, Simultaneously because the effect of its surface tension, forms a large amount of tiny spheric granules.Under the air-extraction function of boiler tail air-introduced machine, Flue gas flow direction furnace tail containing a large amount of ash contents.With the reduction of flue-gas temperature, the particulate of a part melting is because by a certain extent Chilling be in vitreum state, thus potential activity with higher.Before flue gas is discharged into atmosphere by air-introduced machine, it is above-mentioned these Tiny spheric granules is separated, is collected, as flyash by deduster.Porous ceramics keeps the temperature plate exterior wall external heat preservation system In insulation board be inorganic incombustible material, it is nontoxic in use process, will not be generated under high temperature or fire condition any Toxic gas.Fire protecting performance is splendid.In addition, porous ceramics insulation board self-strength is high, the external thermal insulation system pull strength Averagely reach 0.2MPa, and shock resistance is good, system is safe and reliable, is particularly suitable for skyscraper binding face tile.Due to whole A heat-insulation system is inorganic material substantially, and exterior insulation itself does not absorb water, and construction method tradition is easy to worker's palm Hold, system easy to control the quality, this just effectively prevented in terms of material and construction quality two common external thermal insulation system cracking, Hollowing seeps water, falls off, the common faults such as Tile falling.Foamed ceramic have the porosity is high, pyroconductivity is low, anti-thermal shock, high temperature resistant, The performances such as corrosion-resistant, weather-proof, ageing-resistant, non-ignitable, sound-absorbing, sound insulation, have application to aviation, electronics, electric power, environmental protection, building at present Equal fields.

And the problem of porosity of conventional porous thermal insulation ceramics material is low and mechanical property can not also further increase.Cause This, the shortcomings that how improving conventional porous thermal insulation ceramics material is that it is promoted and application to obtain the promotion of more high combination property In broader field, meet industrial production demand urgent problem to be solved.

Summary of the invention

The present invention solves the technical problem of: the low and mechanical property for conventional porous thermal insulation ceramics material porosity The problem of can not further increasing, provides a kind of preparation method of porous heat-insulating ceramic material.

In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:

A kind of preparation method of porous heat-insulating ceramic material, specific preparation process is as follows:

(1) according to parts by weight, by 20~30 parts of diatomite, 10~20 parts of Bacillus pasteurii bacterium solutions, 2~3 portions of nutrient solutions, 2 ~3 parts of urea, 40~60 parts of water mixed fermentations are subsequently added into 0.2~0.3 times of diatomite quality of calcium nitrate solution, and stirring is mixed It closes, filters, wash, dry, high-temperature process obtains modification infusorial earth；

(2) according to parts by weight, by 1~2 part of sodium alginate, 1~2 part of polyvinyl alcohol, 120~200 parts of water mixing, standing swelling Afterwards, heating stirring dissolves, and is subsequently added into 0.02~0.03 times of sodium alginate quality of sodium metaperiodate, and heating stirring mixing obtains mixed Close slurry；

(3) according to parts by weight, by 20~30 parts of mixed slurries, 10~20 parts of organic siliconresins, 3~5 parts of emulsifiers, 10~20 Part modified corn starch cream, 3~5 parts of waterglass, 8~10 parts of modified additives are stirred, obtain hybrid adhesive；

(4) according to parts by weight, 60~80 parts of clays are successively taken, 20~30 parts of modification infusorial earths, 40~60 parts of hybrid adhesives, 20~30 parts of water, 3~5 parts of ice crystals, 8~10 parts of wollastonites, 3~5 parts of serpentines are stirred, injection molding, compression moulding, are taken off Mould, it is dry, obtain dry brick；

(5) the nitrogen treatment adobe containing trimethyl aluminium is utilized, pretreatment adobe is obtained；

(6) adobe resistance sintering will be pre-processed, will be cooled down to get porous heat-insulating ceramic material.

Step (1) the Bacillus pasteurii bacterium solution is made of the raw material of following parts by weight: 1~2 part of Pasteur's gemma Bacillus, 1~2 part of glycerol, 1~2 part of polyethylene glycol, 20~30 parts of water.

Step (1) described nutrient solution is made of the raw material of following parts by weight: 2~3 parts of glucose, 2~3 parts of fructose, 80~100 parts of water.

Step (3) organic siliconresin is poly- methylsiloxane resin, and poly- ethyl organic siliconresin or poly- aryl are organic Any one in silicone resin.

Step (3) emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate, ammonium lauryl sulfate, dodecyl Ammonium sulfate, coconut acyl methyl taurine sodium, any one in ethoxylated dodecyl alcohol carboxylic acid sodium or 1-isobutyl-3,5-dimethylhexylphosphoric acid.

The preparation process of step (3) the modified corn starch cream are as follows: by cornstarch and water 1:50~1 in mass ratio: After 100 mixing swellings, heating stirring mixing obtains corn starch milk；According to parts by weight, by 20~30 parts of octenyl succinic acid anhydrides 30~40 parts of corn starch milks are added dropwise to, are stirred to react, mixed once liquid is obtained, to mixed once drop adding sodium hydroxide solution tune PH is saved, heating stirring reaction obtains secondary mixed liquor, and Xiang Erci mixed liquor is added dropwise hydrochloric acid, adjusts secondary pH of mixed, must be modified jade Rice starch cream.

The preparation process of step (3) the modified additive are as follows: by graphene oxide and water 1:20~1:30 in mass ratio Mixing ultrasound is subsequently added into 0.5~0.8 times of graphene oxide quality of multi-arm carbon nano-tube mixing ultrasound, oxidation is then added The ethylenediamine and 0.03~0.05 times of graphene oxide quality of ammonium hydroxide that 0.1~0.2 times of graphene quality, heating stirring reaction, Filtering, washing are dry to get modified additive.

The volume content of trimethyl aluminium is 3~5% in nitrogen containing trimethyl aluminium described in step (5).

The beneficial effects of the present invention are:

(1) present invention passes through addition modification infusorial earth, mixed slurry and ice crystal, firstly, in modification infusorial earth preparation process, By diatomite, Bacillus pasteurii bacterium solution, nutrient solution, urea, water mixed fermentation, Bacillus pasteurii can be inside diatomite Breeding, and urea can be converted to carbanion in modification liquid under Bacillus pasteurii effect, carbanion can be with Calcium binding in system forms nanometer calcium carbonate in phage surface, and the nanometer calcium carbonate of generation is enriched in Bacillus pasteurii Surface forms nanometer calcium carbonate microballoon, so that the porosity of system gets a promotion, then in hot conditions inside diatomite Under, the organic matter charing in diatomite, meanwhile, the calcium oxide that the calcium carbonate in diatomite is thermally decomposed to generate, in use process In, calcium oxide is reacted with the water in system, calcium hydroxide is generated, so that part calcium ion is dissolved in system, in the work of calcium ion Under, the mixed slurry in system is crosslinked, and the calcium hydroxide microballoon in system is wrapped in organic three-dimensional network, logical In electricity sintering sintering process, the calcium hydroxide dehydration in system increasingly generates calcium oxide, forms calcium oxide microballoon again, then body The pure aluminum that the oxidation reactive aluminum of system generates, pure aluminum melted by heat, the flowing in system, and it is distributed to diatomite and oxidation It between calcium microballoon, and is reacted with the nitrogen in system, aluminium nitride is generated, so that forming chemical bond between calcium oxide microballoon and diatomite It closes, and reacts and generate hard aluminium nitride, so that mechanical property is similarly obtained promotion while system porosity is promoted；

(2) present invention is by addition organic siliconresin and modification infusorial earth, and in use, the silane key of organic siliconresin is disconnected Decomposition is split, the free radical of generation can be dispersed in inside modification infusorial earth, and in conjunction with calcium oxide microballoon, so that calcium oxide microballoon Chemical bonding is formed between diatomite, so that mechanical property is similarly obtained promotion while system porosity is promoted, simultaneously Silicon oxide layer is formed, so that the mechanical property of system is further promoted；

(3) present invention is by adding modified additive, firstly, by multi-walled carbon nanotube and ethylenediamine hybrid reaction, in this process In, since multi-wall carbon nano-tube pipe surface contains a large amount of carboxyl, can be reacted with the amino on ethylenediamine strand, so that amino It is grafted to carbon nano tube surface, then by the way that ammonium hydroxide is added, ammonium hydroxide can make the carboxylic ions on graphene oxide edge, so that Graphene oxide is negatively charged, since like charges are mutually exclusive, enables graphene oxide is good to be dispersed in system, So that modified additive good can be dispersed in system, so that the mechanical property of system gets a promotion.

Specific embodiment

Cornstarch and water 1:50~1:100 in mass ratio are added in No. 1 beaker, 20 are stirred with glass bar~ After 30min, stand 3~4h of swelling, then No. 1 beaker moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 95~100 DEG C, under the conditions of revolving speed is 400~500r/min, heating stirring dissolves 40~50min to get corn starch milk；In parts by weight Meter, 20~30 parts of octenyl succinic acid anhydrides are added dropwise into the four-hole boiling flask for filling 30~40 parts of corn starch milks with dropping funel, And four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, under the conditions of revolving speed is 300~500r/min, it is stirred to react 30~50min obtains mixed once liquid, adjusts pH to 8.3~8.5, Yu Wen then to mixed once drop adding sodium hydroxide solution Degree is 35~50 DEG C, and under the conditions of revolving speed is 200~300r/min, heating stirring reacts 30~50min, obtains secondary mixed liquor, connects To secondary mixed liquor be added dropwise mass fraction be 8~10% hydrochloric acid, adjust secondary pH of mixed to 6.8~7.1, jade must be modified Rice starch cream；Graphene oxide and water 1:20~1:30 in mass ratio are placed in No. 2 beakers, are then placed in No. 2 beakers super In sound separating apparatus, under the conditions of supersonic frequency is 55~75kHz, 40~60min of ultrasound is mixed, is then added into No. 2 beakers The multi-arm carbon nano-tube that 0.5~0.8 times of graphene oxide quality, under the conditions of supersonic frequency is 55~75kHz, mixing ultrasound 40 ~60min, then to ethylenediamine and the graphene oxide quality that 0.1~0.2 times of graphene oxide quality is added in No. 2 beakers No. 2 beakers are then placed in digital display and tested the speed constant temperature blender with magnetic force by the ammonium hydroxide that 0.03~0.05 times of mass fraction is 20~30% In, it is 90~98 DEG C in temperature, under the conditions of revolving speed is 300~500r/min, heating stirring reacts 28~40h, mixed serum is obtained, Mixed serum is filtered again, obtains filter cake, then the filter cake after washing is then placed in Washing of Filter Cake 5~8 times with deionized water It is dry to constant weight under the conditions of temperature is 105~110 DEG C in baking oven, obtain modified additive；According to parts by weight, by 20~30 Part diatomite, 10~20 parts of Bacillus pasteurii bacterium solutions, 2~3 portions of nutrient solutions, 2~3 parts of urea, 40~60 parts of water are placed in fermentation In kettle, it is 30~35 DEG C in temperature, under the conditions of revolving speed is 100~200r/min, fermentation is stirred 3~5 days, then to fermentation In kettle be added 0.2~0.3 times of diatomite quality mass fraction be 10~20% calcium nitrate solution, in revolving speed be 300~ Under the conditions of 500r/min, it is stirred 40~60min, obtains fermentation mixed liquor, then fermentation mixed liquor is filtered, filter residue is obtained, connects With deionized water by residue washing 5~8 times, then the filter residue after washing is placed in baking oven, in temperature be 105~110 DEG C Under the conditions of, it is dry to constant weight, dry filter residue is obtained, then dry filter residue is placed in tube furnace, and with 60~90mL/min rate Nitrogen is filled with into furnace, under the conditions of temperature is 850~950 DEG C, 2~3h of high-temperature process obtains modification infusorial earth；In parts by weight Meter, by 1~2 part of sodium alginate, 1~2 part of polyvinyl alcohol, 120~200 parts of water are placed in No. 3 beakers, and stir 10 with glass bar No. 3 beakers after standing 3~5h of swelling, are placed in digital display and tested the speed in constant temperature blender with magnetic force by~20min, in temperature be 90~95 DEG C, under the conditions of revolving speed is 300~500r/min, heating stirring dissolves 40~60min, and alginic acid then is added into No. 3 beakers The sodium metaperiodate that 0.02~0.03 times of sodium quality is 90~95 DEG C in temperature, under the conditions of revolving speed is 300~500r/min, heats It is stirred 40~60min, obtains mixed slurry；According to parts by weight, by 20~30 parts of mixed slurries, 10~20 parts of organosilicon trees Rouge, 3~5 parts of emulsifiers, 10~20 parts of modified corn starch creams, 3~5 parts of waterglass, 8~10 parts of modified additives are placed in mixing In machine, under the conditions of revolving speed is 600~800r/min, it is stirred 40~60min, obtains hybrid adhesive；According to parts by weight, Successively take 60~80 parts of clays, 20~30 parts of modification infusorial earths, 40~60 parts of hybrid adhesives, 20~30 parts of water, 3~5 parts of ice Spar, 8~10 parts of wollastonites, 3~5 parts of serpentines are placed in blender, under the conditions of revolving speed is 100~200r/min, stirring 40~60min is mixed, homogenate must be mixed, then sprays dimethicone to die surface, mixing is then homogenized injection mold In, then mold is placed in molding machine after compression moulding, is demoulded, is obtained adobe, then adobe is placed in baking oven, be in temperature It is dry to constant weight under the conditions of 105~110 DEG C, obtain dry brick；Then dry brick is placed in fluidized-bed reactor, and with 60~90mL/min rate is passed through the nitrogen containing trimethyl aluminium into reactor, and after being continually fed into 30min, discharging must be pre-processed Adobe；Pretreatment adobe is placed in sintering furnace, and nitrogen is filled with into furnace with 60~90mL/min rate, and with 10~15 DEG C Heating rate in-furnace temperature is risen to 1400~1600 DEG C, and to be passed through the direct current of 200~300kA, 2~3h of resistance sintering Afterwards, room temperature is down to get porous heat-insulating ceramic material with furnace.The Bacillus pasteurii bacterium solution is by the original of following parts by weight Material composition: 1~2 part of Bacillus pasteurii, 1~2 part of glycerol, 1~2 part of polyethylene glycol, 20~30 parts of water.The nutrient solution be by The raw material of following parts by weight forms: 2~3 parts of glucose, 2~3 parts of fructose, 80~100 parts of water.The organic siliconresin is poly- Any one in methylsiloxane resin, poly- ethyl organic siliconresin or poly- aryl organic siliconresin.The emulsifier is 12 Alkyl alcohol ethoxylates sodium sulphate, ammonium lauryl sulfate, ammonium lauryl sulfate, coconut acyl methyl taurine sodium, laurel Any one in alcohol polyoxyethylene ether carboxylic acid sodium or 1-isobutyl-3,5-dimethylhexylphosphoric acid.Trimethyl aluminium in the nitrogen containing trimethyl aluminium Volume content be 3~5%.

Example 1

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, in Temperature is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, diatomite quality is then added into fermentation cauldron The calcium nitrate solution that 0.3 times of mass fraction is 20% is stirred 60min, must ferment under the conditions of revolving speed is 500r/min Fermentation mixed liquor is then filtered, obtains filter residue by mixed liquor, then will be after washing then with deionized water by residue washing 8 times Filter residue is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry filter residue, dry filter residue is then placed in pipe In formula furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified silicon Diatomaceous earth；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and are stirred with glass bar Mix 20min, after standing swelling 5h, No. 3 beakers be placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 95 DEG C, revolving speed Under the conditions of 500r/min, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of height is then added into No. 3 beakers Sodium iodate is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；By weight Number meter, by 30 parts of mixed slurries, 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 parts of modified additives are placed in batch mixer, under the conditions of revolving speed is 800r/min, is stirred 60min, is obtained hybrid adhesive； According to parts by weight, 80 parts of clays are successively taken, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, 10 Part wollastonite, 5 parts of serpentines are placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, must be mixed even Slurry then sprays dimethicone to die surface, and then mixing is homogenized in injection mold, mold is then placed in molding machine After middle compression moulding, demoulding obtains adobe, then adobe is placed in baking oven, under the conditions of temperature is 110 DEG C, drying to constant weight, Obtain dry brick；Then dry brick is placed in fluidized-bed reactor, and is passed through and is contained into reactor with 90mL/min rate The nitrogen of trimethyl aluminium, after being continually fed into 30min, discharging obtains pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and It is filled with nitrogen into furnace with 90mL/min rate, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through The direct current of 300kA after resistance sintering 3h, is down to room temperature with furnace to get porous heat-insulating ceramic material.The Bacillus pasteurii Bacterium solution is made of the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.Institute It states nutrient solution to be made of the raw material of following parts by weight: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organic siliconresin is Poly- methylsiloxane resin.The emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.The nitrogen containing trimethyl aluminium The volume content of middle trimethyl aluminium is 5%.

Example 2

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, in Temperature is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, diatomite quality is then added into fermentation cauldron The calcium nitrate solution that 0.3 times of mass fraction is 20% is stirred 60min, must ferment under the conditions of revolving speed is 500r/min Fermentation mixed liquor is then filtered, obtains filter residue by mixed liquor, then will be after washing then with deionized water by residue washing 8 times Filter residue is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry filter residue, dry filter residue is then placed in pipe In formula furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified silicon Diatomaceous earth；According to parts by weight, by 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 The modified additive of part is placed in batch mixer, under the conditions of revolving speed is 800r/min, is stirred 60min, is obtained hybrid adhesive；It presses Parts by weight meter, successively takes 80 parts of clays, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, and 10 parts Wollastonite, 5 parts of serpentines are placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, must be mixed homogenate, Then dimethicone is sprayed to die surface, then mixing is homogenized in injection mold, then mold is placed in molding machine After compression moulding, demoulding obtains adobe, then adobe is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains Dry brick；Then dry brick is placed in fluidized-bed reactor, and is passed through into reactor containing three with 90mL/min rate The nitrogen of aluminium methyl, after being continually fed into 30min, discharging obtains pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and with 90mL/min rate is filled with nitrogen into furnace, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through The direct current of 300kA after resistance sintering 3h, is down to room temperature with furnace to get porous heat-insulating ceramic material.The Bacillus pasteurii Bacterium solution is made of the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.Institute It states nutrient solution to be made of the raw material of following parts by weight: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organic siliconresin is Poly- methylsiloxane resin.The emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.The nitrogen containing trimethyl aluminium The volume content of middle trimethyl aluminium is 5%.

Example 3

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, in Temperature is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, diatomite quality is then added into fermentation cauldron The calcium nitrate solution that 0.3 times of mass fraction is 20% is stirred 60min, must ferment under the conditions of revolving speed is 500r/min Fermentation mixed liquor is then filtered, obtains filter residue by mixed liquor, then will be after washing then with deionized water by residue washing 8 times Filter residue is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry filter residue, dry filter residue is then placed in pipe In formula furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified silicon Diatomaceous earth；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and are stirred with glass bar Mix 20min, after standing swelling 5h, No. 3 beakers be placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 95 DEG C, revolving speed Under the conditions of 500r/min, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of height is then added into No. 3 beakers Sodium iodate is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；By weight Number meter, by 30 parts of mixed slurries, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 parts of modified additives are set In batch mixer, under the conditions of revolving speed is 800r/min, it is stirred 60min, obtains hybrid adhesive；According to parts by weight, according to It is secondary to take 80 parts of clays, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, 10 parts of wollastonites, 5 portions of snakes Line stone is placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, must be mixed homogenate, then to mold table Dimethicone is sprayed in face, and then mixing is homogenized in injection mold, then mold is placed in molding machine after compression moulding, is taken off Mould obtains adobe, then adobe is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry brick；Then Dry brick is placed in fluidized-bed reactor, and the nitrogen containing trimethyl aluminium is passed through into reactor with 90mL/min rate, After being continually fed into 30min, discharging obtains pretreatment adobe；Will pretreatment adobe be placed in sintering furnace, and with 90mL/min rate to It is filled with nitrogen in furnace, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through the direct current of 300kA, leads to After electricity sintering 3h, room temperature is down to get porous heat-insulating ceramic material with furnace.The Bacillus pasteurii bacterium solution is by following weight The raw material of number forms: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.The nutrient solution is by following The raw material of parts by weight forms: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The emulsifier is Brij 35 Sodium sulphate.The volume content of trimethyl aluminium is 5% in the nitrogen containing trimethyl aluminium.

Example 4

Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, then No. 2 beakers are placed in ultrasonic disperse instrument, Under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, 0.8 times of graphene oxide quality is then added into No. 2 beakers Multi-arm carbon nano-tube, in supersonic frequency be 75kHz under the conditions of, mix ultrasound 60min, then in No. 2 beakers be added oxidation The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene quality is 30% then burns No. 2 Cup is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring reaction 40h obtains mixed serum, then mixed serum is filtered, and obtains filter cake, then will washing then with deionized water by Washing of Filter Cake 8 times Filter cake afterwards is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；According to parts by weight, By 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, Yu Wendu It is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, 0.3 times of diatomite quality is then added into fermentation cauldron Mass fraction be 20% calcium nitrate solution, in revolving speed be 500r/min under the conditions of, be stirred 60min, must ferment mixing Fermentation mixed liquor is then filtered, filter residue is obtained, then with deionized water by residue washing 8 times, then by the filter residue after washing by liquid It is placed in baking oven, it is dry to constant weight under the conditions of temperature is 110 DEG C, dry filter residue is obtained, dry filter residue is then placed in tube furnace In, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified diatom Soil；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and are stirred with glass bar No. 3 beakers after standing swelling 5h, are placed in digital display and tested the speed in constant temperature blender with magnetic force, are 95 DEG C in temperature, revolving speed is by 20min Under the conditions of 500r/min, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of high iodine is then added into No. 3 beakers Sour sodium is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；By weight Number meter, by 30 parts of mixed slurries, 20 parts of organic siliconresins, 5 parts of emulsifiers, 5 parts of waterglass, 10 parts of modified additives are placed in mixing In machine, under the conditions of revolving speed is 800r/min, it is stirred 60min, obtains hybrid adhesive；According to parts by weight, 80 are successively taken Part clay, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, 10 parts of wollastonites, 5 parts of serpentines are set In blender, under the conditions of revolving speed is 200r/min, it is stirred 60min, homogenate must be mixed, then sprayed to die surface Mixing is then homogenized in injection mold, then mold is placed in molding machine after compression moulding, demoulds, obtain by dimethicone Adobe is then placed in baking oven by adobe, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry brick；Then it will do Dry adobe is placed in fluidized-bed reactor, and the nitrogen containing trimethyl aluminium is passed through into reactor with 90mL/min rate, is continued After being passed through 30min, discharging obtains pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and with 90mL/min rate into furnace It is filled with nitrogen, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through the direct current of 300kA, be powered and burn After tying 3h, room temperature is down to get porous heat-insulating ceramic material with furnace.The Bacillus pasteurii bacterium solution is by following parts by weight Raw material composition: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.The nutrient solution is by following weight The raw material of number forms: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organic siliconresin is poly- methylsiloxane resin.Institute Stating emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.The volume content of trimethyl aluminium in the nitrogen containing trimethyl aluminium It is 5%.

Example 5

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；According to parts by weight, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 Part water is placed in fermentation cauldron, is 35 DEG C in temperature, under the conditions of revolving speed is 200r/min, fermentation 5 days is stirred, then to fermentation The calcium nitrate solution that the mass fraction that 0.3 times of diatomite quality is added in kettle is 20% stirs under the conditions of revolving speed is 500r/min Mix mixing 60min, obtain fermentation mixed liquor, then will fermentation mixed liquor filtering, filter residue is obtained, then with deionized water by residue washing 8 times, then the filter residue after washing is placed in baking oven, it is dry to constant weight under the conditions of temperature is 110 DEG C, dry filter residue is obtained, is connect Dry filter residue is placed in tube furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, High-temperature process 3h, obtains modification infusorial earth；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 In beaker, and 20min is stirred with glass bar, after standing swelling 5h, No. 3 beakers is placed in digital display and are tested the speed constant temperature blender with magnetic force In, it is 95 DEG C in temperature, under the conditions of revolving speed is 500r/min, heating stirring dissolves 60min, and sea is then added into No. 3 beakers The sodium metaperiodate that 0.03 times of mosanom quality is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring is mixed 60min obtains mixed slurry；According to parts by weight, by 30 parts of mixed slurries, 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts change Property corn starch milk, 5 parts of waterglass are placed in batch mixer, under the conditions of revolving speed is 800r/min, is stirred 60min, obtains mixed Close binder；According to parts by weight, 80 parts of clays are successively taken, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts Ice crystal, 10 parts of wollastonites, 5 parts of serpentines are placed in blender, under the conditions of revolving speed is 200r/min, are stirred 60min, Homogenate must be mixed, then sprays dimethicone to die surface, then mixing is homogenized in injection mold, then sets mold In molding machine after compression moulding, demoulding obtains adobe, then adobe is placed in baking oven, under the conditions of temperature is 110 DEG C, does It is dry to constant weight, obtain dry brick；Then dry brick is placed in fluidized-bed reactor, and with 90mL/min rate to reactor In be passed through the nitrogen containing trimethyl aluminium, after being continually fed into 30min, discharging, obtain pretreatment adobe；Pretreatment adobe is placed in sintering In furnace, and nitrogen is filled with into furnace with 90mL/min rate, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and To be passed through the direct current of 300kA, after resistance sintering 3h, room temperature is down to get porous heat-insulating ceramic material with furnace.Pasteur's bud Spore bacillus bacterium solution is made of the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, and 30 parts Water.The nutrient solution is made of the raw material of following parts by weight: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organosilicon Resin is poly- methylsiloxane resin.The emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.It is described to contain trimethyl aluminium Nitrogen in trimethyl aluminium volume content be 5%.

Example 6

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and stir 20min with glass bar, are stood molten After swollen 5h, No. 3 beakers are placed in digital display and are tested the speed in constant temperature blender with magnetic force, is 95 DEG C in temperature, revolving speed is 500r/min condition Under, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of sodium metaperiodate is then added into No. 3 beakers, is in temperature 95 DEG C, under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；According to parts by weight, mixed by 30 parts Conjunction slurry, 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 parts of modified additives are set In batch mixer, under the conditions of revolving speed is 800r/min, it is stirred 60min, obtains hybrid adhesive；According to parts by weight, according to It is secondary to take 80 parts of clays, 30 parts of diatomite, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, 10 parts of wollastonites, 5 parts of serpentines It is placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, homogenate must be mixed, then sprayed to die surface Dimethicone is spilt, then mixing is homogenized in injection mold, then mold is placed in molding machine after compression moulding, is demoulded, Adobe is obtained, then adobe is placed in baking oven, it is dry to constant weight under the conditions of temperature is 110 DEG C, obtain dry brick；Then will Dry brick is placed in fluidized-bed reactor, and the nitrogen containing trimethyl aluminium is passed through into reactor with 90mL/min rate, is held Continue after being passed through 30min, discharging obtains pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and with 90mL/min rate to furnace It is inside filled with nitrogen, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through the direct current of 300kA, is powered After being sintered 3h, room temperature is down to get porous heat-insulating ceramic material with furnace.The organic siliconresin is poly- methylsiloxane resin. The emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.The volume of trimethyl aluminium contains in the nitrogen containing trimethyl aluminium Amount is 5%.

Example 7

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, in Temperature is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, diatomite quality is then added into fermentation cauldron The calcium nitrate solution that 0.3 times of mass fraction is 20% is stirred 60min, must ferment under the conditions of revolving speed is 500r/min Fermentation mixed liquor is then filtered, obtains filter residue by mixed liquor, then will be after washing then with deionized water by residue washing 8 times Filter residue is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry filter residue, dry filter residue is then placed in pipe In formula furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified silicon Diatomaceous earth；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and are stirred with glass bar Mix 20min, after standing swelling 5h, No. 3 beakers be placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 95 DEG C, revolving speed Under the conditions of 500r/min, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of height is then added into No. 3 beakers Sodium iodate is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；By weight Number meter, by 30 parts of mixed slurries, 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 parts of modified additives are placed in batch mixer, under the conditions of revolving speed is 800r/min, is stirred 60min, is obtained hybrid adhesive； According to parts by weight, 80 parts of clays are successively taken, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 10 parts of wollastonites, 5 Part serpentine is placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, must be mixed homogenate, then to mould Have surface and spray dimethicone, then mixing is homogenized in injection mold, mold is then placed in compression moulding in molding machine Afterwards, it demoulds, obtains adobe, then adobe is placed in baking oven, it is dry to constant weight under the conditions of temperature is 110 DEG C, obtain dry brick Base；Then dry brick is placed in fluidized-bed reactor, and is passed through into reactor containing trimethyl aluminium with 90mL/min rate Nitrogen, after being continually fed into 30min, discharging, obtain pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and with 90mL/ Min rate is filled with nitrogen into furnace, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through 300kA's Direct current after resistance sintering 3h, is down to room temperature with furnace to get porous heat-insulating ceramic material.The Bacillus pasteurii bacterium solution is It is made of the raw material of following parts by weight: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.The nutrition Liquid is made of the raw material of following parts by weight: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organic siliconresin is poly- methyl Organic siliconresin.The emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.Front three in the nitrogen containing trimethyl aluminium The volume content of base aluminium is 5%.

Example 8

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, in Temperature is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, diatomite quality is then added into fermentation cauldron The calcium nitrate solution that 0.3 times of mass fraction is 20% is stirred 60min, must ferment under the conditions of revolving speed is 500r/min Fermentation mixed liquor is then filtered, obtains filter residue by mixed liquor, then will be after washing then with deionized water by residue washing 8 times Filter residue is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry filter residue, dry filter residue is then placed in pipe In formula furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified silicon Diatomaceous earth；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and are stirred with glass bar Mix 20min, after standing swelling 5h, No. 3 beakers be placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 95 DEG C, revolving speed Under the conditions of 500r/min, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of height is then added into No. 3 beakers Sodium iodate is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；By weight Number meter, by 30 parts of mixed slurries, 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 parts of modified additives are placed in batch mixer, under the conditions of revolving speed is 800r/min, is stirred 60min, is obtained hybrid adhesive； According to parts by weight, 80 parts of clays are successively taken, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, 10 Part wollastonite, 5 parts of serpentines are placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, must be mixed even Slurry then sprays dimethicone to die surface, and then mixing is homogenized in injection mold, mold is then placed in molding machine After middle compression moulding, demoulding obtains adobe, then adobe is placed in baking oven, under the conditions of temperature is 110 DEG C, drying to constant weight, Dry brick is obtained, pretreatment adobe is obtained；Pretreatment adobe is placed in sintering furnace, and nitrogen is filled with into furnace with 90mL/min rate Gas, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, and to be passed through the direct current of 300kA, after resistance sintering 3h, Room temperature is down to furnace to get porous heat-insulating ceramic material.The Bacillus pasteurii bacterium solution is by the raw material of following parts by weight Composition: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.The nutrient solution is by following parts by weight Raw material composition: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organic siliconresin is poly- methylsiloxane resin.The emulsification Agent is dodecyl alcohol polyoxyethylene ether sodium sulfate.

Example 9

Cornstarch and water 1:100 in mass ratio are added in No. 1 beaker, after being stirred 30min with glass bar, stand swelling 4h, then No. 1 beaker is moved into digital display and is tested the speed constant temperature blender with magnetic force, in temperature be 100 DEG C, under the conditions of revolving speed is 500r/min, Heating stirring dissolves 50min to get corn starch milk；According to parts by weight, with dropping funel to filling 40 parts of corn starch milks Four-hole boiling flask in 30 parts of octenyl succinic acid anhydrides are added dropwise, and four-hole boiling flask is moved into digital display and is tested the speed in constant temperature blender with magnetic force, Under the conditions of revolving speed is 500r/min, it is stirred to react 50min, obtains mixed once liquid, adds hydroxide then to mixed once drop Sodium solution adjusts pH to 8.5, is 50 DEG C in temperature, and under the conditions of revolving speed is 300r/min, heating stirring reacts 50min, obtains secondary Mixed liquor is then added dropwise the hydrochloric acid that mass fraction is 10% to secondary mixed liquor, adjusts secondary pH of mixed to 7.1, must be modified jade Rice starch cream；Graphene oxide and water 1:30 in mass ratio are placed in No. 2 beakers, No. 2 beakers are then placed in ultrasonic disperse In instrument, under the conditions of supersonic frequency is 75kHz, ultrasound 60min is mixed, graphene oxide quality is then added into No. 2 beakers 0.8 times of multi-arm carbon nano-tube mixes ultrasound 60min, then to being added in No. 2 beakers under the conditions of supersonic frequency is 75kHz The ammonium hydroxide that 0.05 times of mass fraction of ethylenediamine and graphene oxide quality that 0.2 times of graphene oxide quality is 30%, then by 2 Number beaker is placed in digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 98 DEG C, under the conditions of revolving speed is 500r/min, heating stirring 40h is reacted, mixed serum is obtained, then mixed serum is filtered, obtains filter cake, then with deionized water by Washing of Filter Cake 8 times, then will Filter cake after washing is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains modified additive；In parts by weight Meter, by 30 parts of diatomite, 20 parts of Bacillus pasteurii bacterium solutions, 3 portions of nutrient solutions, 3 parts of urea, 60 parts of water are placed in fermentation cauldron, in Temperature is 35 DEG C, under the conditions of revolving speed is 200r/min, is stirred fermentation 5 days, diatomite quality is then added into fermentation cauldron The calcium nitrate solution that 0.3 times of mass fraction is 20% is stirred 60min, must ferment under the conditions of revolving speed is 500r/min Fermentation mixed liquor is then filtered, obtains filter residue by mixed liquor, then will be after washing then with deionized water by residue washing 8 times Filter residue is placed in baking oven, dry to constant weight under the conditions of temperature is 110 DEG C, obtains dry filter residue, dry filter residue is then placed in pipe In formula furnace, and nitrogen is filled with into furnace with 90mL/min rate, under the conditions of temperature is 950 DEG C, high-temperature process 3h obtains modified silicon Diatomaceous earth；According to parts by weight, by 2 parts of sodium alginates, 2 parts of polyvinyl alcohol, 200 parts of water are placed in No. 3 beakers, and are stirred with glass bar Mix 20min, after standing swelling 5h, No. 3 beakers be placed in digital display and are tested the speed in constant temperature blender with magnetic force, in temperature be 95 DEG C, revolving speed Under the conditions of 500r/min, heating stirring dissolves 60min, and 0.03 times of sodium alginate quality of height is then added into No. 3 beakers Sodium iodate is 95 DEG C in temperature, and under the conditions of revolving speed is 500r/min, heating stirring mixes 60min, obtains mixed slurry；By weight Number meter, by 30 parts of mixed slurries, 20 parts of organic siliconresins, 5 parts of emulsifiers, 20 parts of modified corn starch creams, 5 parts of waterglass, 10 parts of modified additives are placed in batch mixer, under the conditions of revolving speed is 800r/min, is stirred 60min, is obtained hybrid adhesive； According to parts by weight, 80 parts of clays are successively taken, 30 parts of modification infusorial earths, 60 parts of hybrid adhesives, 30 parts of water, 5 parts of ice crystals, 10 Part wollastonite, 5 parts of serpentines are placed in blender, under the conditions of revolving speed is 200r/min, is stirred 60min, must be mixed even Slurry then sprays dimethicone to die surface, and then mixing is homogenized in injection mold, mold is then placed in molding machine After middle compression moulding, demoulding obtains adobe, then adobe is placed in baking oven, under the conditions of temperature is 110 DEG C, drying to constant weight, Obtain dry brick；Then dry brick is placed in fluidized-bed reactor, and is passed through and is contained into reactor with 90mL/min rate The nitrogen of trimethyl aluminium, after being continually fed into 30min, discharging obtains pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and It is filled with nitrogen into furnace with 90mL/min rate, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, after being sintered 3h, Room temperature is down to furnace to get porous heat-insulating ceramic material.The Bacillus pasteurii bacterium solution is by the raw material of following parts by weight Composition: 2 parts of Bacillus pasteuriis, 2 parts of glycerol, 2 parts of polyethylene glycol, 30 parts of water.The nutrient solution is by following parts by weight Raw material composition: 3 parts of glucose, 3 parts of fructose, 100 parts of water.The organic siliconresin is poly- methylsiloxane resin.The emulsification Agent is dodecyl alcohol polyoxyethylene ether sodium sulfate.The volume content of trimethyl aluminium is 5% in the nitrogen containing trimethyl aluminium.

Comparative example:

According to parts by weight, by 5 parts of emulsifiers, 5 parts of waterglass are placed in batch mixer, under the conditions of revolving speed is 800r/min, are stirred Mixing 60min is mixed, hybrid adhesive is obtained；According to parts by weight, 80 parts of clays, 30 parts of diatomite, 60 parts of mixing bondings are successively taken Agent, 30 parts of water, 10 parts of wollastonites, 5 parts of serpentines are placed in blender, under the conditions of revolving speed is 200r/min, are stirred 60min must mix homogenate, then spray dimethicone to die surface, and then mixing is homogenized in injection mold, then will Mold is placed in molding machine after compression moulding, demoulding, obtain adobe, then adobe be placed in baking oven, in temperature be 110 DEG C of conditions Under, it is dry to constant weight, dry brick is obtained, discharges, obtains pretreatment adobe；Pretreatment adobe is placed in sintering furnace, and with 90mL/ Min rate is filled with nitrogen into furnace, and in-furnace temperature is risen to 1600 DEG C with 15 DEG C of heating rate, after being sintered 3h, drops with furnace To room temperature to get porous heat-insulating ceramic material.The emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate.

Example 1 to the resulting porous heat-insulating ceramic material of example 9 and comparative example product are subjected to performance detection, it is specific to detect Method is as follows:

Flexural strength test referring to " inorganic hard insulating product test method " specification is tested, sample dimensions be 40mm × 40mm × 160mm, this test use YDW-20 type microcomputer controlled electro minor Intensity of Breaking Tester, and range selects 20kN to be forced into Test specimen destroys record failing load P, is accurate to 1N, measures specimen width b and thickness h.Formula used is R=3PL ÷ 2bh2, examination Test being accurate to of result 0.1MPa；Porosity is measured using mercury injection apparatus (Autopore9500).

Specific testing result is as shown in table 1:

The 1 specific testing result of porous heat-insulating ceramic material of table

By 1 testing result of table it is found that while the porous heat-insulating ceramic material of technical solution of the present invention preparation is high with porosity The characteristics of excellent in mechanical performance, has broad prospects in the development of functional material technology industry.

Claims

1. a kind of preparation method of porous heat-insulating ceramic material, it is characterised in that specific preparation process is as follows:

2. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (1) is described Bacillus pasteurii bacterium solution is made of the raw material of following parts by weight: 1~2 part of Bacillus pasteurii, 1~2 part of glycerol, and 1~2 Part polyethylene glycol, 20~30 parts of water.

3. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (1) is described Nutrient solution is made of the raw material of following parts by weight: 2~3 parts of glucose, 2~3 parts of fructose, 80~100 parts of water.

4. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (3) is described Organic siliconresin is poly- methylsiloxane resin, any one in poly- ethyl organic siliconresin or poly- aryl organic siliconresin.

5. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (3) is described Emulsifier is dodecyl alcohol polyoxyethylene ether sodium sulfate, ammonium lauryl sulfate, ammonium lauryl sulfate, coconut acyl methyl ox Sodium sulfonate, any one in ethoxylated dodecyl alcohol carboxylic acid sodium or 1-isobutyl-3,5-dimethylhexylphosphoric acid.

6. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (3) is described The preparation process of modified corn starch cream are as follows: after cornstarch is mixed swelling with water 1:50~1:100 in mass ratio, heating is stirred Mixing is mixed, corn starch milk is obtained；According to parts by weight, 20~30 parts of octenyl succinic acid anhydrides 30~40 parts of corns are added dropwise to form sediment Powder cream, is stirred to react, obtains mixed once liquid, adjusts pH to mixed once drop adding sodium hydroxide solution, heating stirring reaction obtains Secondary mixed liquor, Xiang Erci mixed liquor are added dropwise hydrochloric acid, adjust secondary pH of mixed, obtain modified corn starch cream.

7. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (3) is described The preparation process of modified additive are as follows: graphene oxide is mixed into ultrasound with water 1:20~1:30 in mass ratio, is subsequently added into oxygen The multi-arm carbon nano-tube of 0.5~0.8 times of graphite alkene quality mixes ultrasound, is then added 0.1~0.2 times of graphene oxide quality Ethylenediamine and 0.03~0.05 times of graphene oxide quality of ammonium hydroxide, heating stirring reaction filters, and washing is dry to get changing Property additive.

8. a kind of preparation method of porous heat-insulating ceramic material according to claim 1, it is characterised in that: step (5) is described The volume content of trimethyl aluminium is 3~5% in nitrogen containing trimethyl aluminium.