阅读说明：本技术 一种石墨烯改性耐火材料及其制备方法 (Modified refractory material of a kind of graphene and preparation method thereof ) 是由 毕玉保 王慧芳 胡书禾 于仁红 孟庆新 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种石墨烯改性耐火材料的制备方法,以待改性的耐火材料和氧化石墨烯水分散液为原料,将氧化石墨烯水分散液通过真空浸渍到耐火材料的孔隙中得到浸渍有氧化石墨烯的耐火材料,之后将浸渍有氧化石墨烯的耐火材料进行真空干燥,并在干燥后进行还原反应使氧化石墨烯还原为石墨烯,最后进行烘干即得到石墨烯改性的耐火材料。采用该方法所制备的耐火材料在碳含量极低(C<0.1wt%)的条件下即可拥有优异的抗高温熔渣侵蚀性能,且不易对钢水造成污染。本发明的制备方法对耐火材料的材质与成型方法要求低,具有广泛的适用性,且该制备方法工艺简单、生产周期短。(The invention discloses a kind of preparation methods of the modified refractory material of graphene, using refractory material to be modified and graphene oxide aqueous dispersions as raw material, graphene oxide aqueous dispersions are obtained into the refractory material for being impregnated with graphene oxide into the hole of refractory material by vacuum impregnation, the refractory material for being impregnated with graphene oxide is dried in vacuo later, and carrying out reduction reaction after the drying makes graphene oxide be reduced to graphene, finally carries out the refractory material modified to graphene obtained by drying.Excellent slag corrosion performance resistant to high temperatures can be possessed under conditions of carbon content extremely low (C < 0.1wt%) using refractory material prepared by this method, and be not easy to pollute molten steel.Preparation method of the invention requires the material of refractory material with forming method low, has a wide applicability, and the preparation method simple process, with short production cycle.)

1. a kind of preparation method of the modified refractory material of graphene, it is characterised in that: with refractory material to be modified and oxidation stone Black alkene aqueous dispersions are raw material, and graphene oxide aqueous dispersions are impregnated by vacuum impregnation into the hole of refractory material There is the refractory material of graphene oxide, is later dried in vacuo the refractory material for being impregnated with graphene oxide, and in drying Carrying out reduction reaction afterwards makes graphene oxide be reduced to graphene, finally carries out the fire proofed wood modified to graphene obtained by drying Material.

2. a kind of preparation method of the modified refractory material of graphene according to claim 1, it is characterised in that: the oxidation The concentration of graphene aqueous dispersions is 0.5 ~ 5wt%, is graphene oxide and 190 ~ 199 parts of quality using 1 ~ 10 part of quality Water mixing and uniformly obtained through ultrasonic disperse.

3. a kind of preparation method of the modified refractory material of graphene according to claim 1, it is characterised in that: described wait change Property refractory material and graphene oxide aqueous dispersions mass parts ratio be 1:1.

4. a kind of preparation method of the modified refractory material of graphene according to claim 1, it is characterised in that: the reduction Reaction is electronation or thermal reduction.

5. a kind of preparation method of the modified refractory material of graphene according to claim 4, it is characterised in that: electronation Reducing agent used is any one in sodium borohydride, potassium borohydride or hydrazine hydrate；The reaction temperature of electronation is 80 ~ 90 ℃。

6. a kind of preparation method of the modified refractory material of graphene according to claim 4, it is characterised in that: thermal reduction is In Ar or N₂It is heated to 300 ~ 400 DEG C under atmosphere and keeps the temperature 2h.

7. a kind of modified refractory material of graphene, which is characterized in that it is method system according to claim 1-4 Standby.

Technical field

The present invention relates to a kind of technical field of refractory materials, more particularly, to a kind of modified refractory material of graphene and its system Preparation Method.

Background technique

Carbon containing sizing refractory material is due to excellent thermal shock resistance and good resistance to slag corrosion, in steel and iron industry It is widely used, main application range has: 1) blast furnace ironmaking refractory material, such as high temperature furnace bottom, iron tap channel position； 2) liner body of converter, electric furnace and ladle；3) continuous casting critical component, such as the mouth of a river, slide plate, stopper；4) earthenware of smelting metal Crucible.But traditional carbon containing sizing refractory material carbon content is high, and the precipitation of carbon easily occurs in use, increases molten steel Carbon pollutes steel.

Unshape refractory because its convenient construction, without high temperature firing and structural integrity it is good, in refractory material total amount Middle proportion is higher and higher.But due to the non wettability of carbon material and water, so that the preparation of unshape refractory is difficult, and The resistance to slag corrosion of unshape refractory is lower.

Moreover, no matter carbon containing sizing refractory material or unshape refractory, it is high that receiving is removed in use Temperature effect is outer, all can be by the erosion of slag, therefore, and the quality of refractory material slag-resistant erosion performance is to influence refractory material to make With an important quality factor of service life length, and judge a key technical indexes of capabilities of refractory materials superiority and inferiority.Enhancing The slag-resistant erosion performance of refractory material improves the heat of such Thermal Equipment to the service life for extending furnace lining and its masonry Efficiency and production efficiency reduce cost, reduce product because polluting caused by refractory material, it is all meaningful for improving product quality 's.

Therefore, it is badly in need of finding a kind of preparation method of refractory material, refractory material is made to possess good slag-resistant aggressivity Can, while the carbon content of carbon containing sizing refractory material can be made lower, simplify the preparation process of unshape refractory.

Summary of the invention

In view of this, the object of the present invention is to provide modified refractory material of a kind of graphene and preparation method thereof, the preparation Method is suitable for carbon containing sizing refractory material and amorphous refractory simultaneously.The preparation method make preparation refractory material gather around Under the premise of having good slag-resistant erosion performance, the carbon content of carbon containing sizing refractory material can be made lower, made unsetting resistance to The preparation process of fiery material simplifies.

In order to solve the above-mentioned technical problem used technical solution is the present invention: a kind of modified refractory material of graphene Preparation method leads to graphene oxide aqueous dispersions using refractory material to be modified and graphene oxide aqueous dispersions as raw material It crosses vacuum impregnation and obtains the refractory material for being impregnated with graphene oxide into the hole of refractory material, oxidation stone will be impregnated with later The refractory material of black alkene is dried in vacuo, and carrying out reduction reaction after the drying makes graphene oxide be reduced to graphene, most The refractory material modified to graphene obtained by drying is carried out afterwards.

Further, the concentration of the graphene oxide aqueous dispersions is 0.5 ~ 5wt%, is to utilize 1 ~ 10 part of quality Graphene oxide mixes and uniformly obtained through ultrasonic disperse with the water of 190 ~ 199 parts of quality.

Further, the mass parts ratio of the refractory material to be modified and graphene oxide aqueous dispersions is 1:1.

Further, the reduction reaction is electronation or thermal reduction.

Further, reducing agent used in electronation is any one in sodium borohydride, potassium borohydride or hydrazine hydrate； The reaction temperature of electronation is 80 ~ 90 DEG C.

Further, thermal reduction is in Ar or N₂It is heated to 300 ~ 400 DEG C under atmosphere and keeps the temperature 2h.

Using the modified refractory material of the graphene of above method preparation.

The graphene oxide that the present invention selects is crystalline flake graphite gained, technical maturity, raw material after strong oxidation removing It is easy to get.

The utility model has the advantages that

As described above, modified refractory material of a kind of graphene of the invention and preparation method thereof, has the advantages that

1, the present invention is modified refractory material by graphene, coats or fills in refractory surface and internal void There is the graphene not with slag wetting, the channel of slag intrusion refractory material is plugged, so that prepared refractory material is in carbon Excellent slag corrosion performance resistant to high temperatures can be possessed under conditions of content extremely low (C < 0.1wt%), and be not easy to cause dirt to molten steel Dye.

2, the present invention is used electronation (using sodium borohydride, potassium borohydride or hydrazine hydrate as reducing agent) or is gone back using heat Former graphene oxide can be such that the oxygen-containing functional group on graphene oxide removes at a lower temperature and be reduced to graphene and realize also Former effect, does not need high-temperature process, reduces energy consumption.

3, the present invention is immersed in graphene oxide in the hole of refractory material using vacuum impregnation, since graphene has Good spreading property only needs a small amount of graphene oxide that good dipping effect can be realized, saves graphene oxide Dosage, while dip time is shortened, it further reduced production cost.

4, the method that the present invention prepares the modified refractory material of graphene, material and forming method requirement to refractory material It is low, there is wide applicability, and the preparation method simple process, with short production cycle.

Further specific detailed description is done to the present invention below with reference to embodiment the drawings and specific embodiments.

Detailed description of the invention

In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technology to be briefly described, it should be apparent that, the accompanying drawings in the following description is only the present invention Some embodiments for those of ordinary skill in the art without creative efforts, can also basis These attached drawings obtain other attached drawings.

Fig. 1 is the SEM picture of the modified refractory material of graphene prepared by embodiment 1.

Specific embodiment

A kind of preparation method of the modified refractory material of graphene, with refractory material to be modified and graphene oxide water dispersion Liquid is raw material, by graphene oxide aqueous dispersions by vacuum impregnation (vacuum degree be 10par) when vacuum impregnation to be modified Refractory material hole in, the mass parts ratio of refractory material and graphene oxide aqueous dispersions is 1:1, will be impregnated with later The refractory material of graphene oxide is dried in vacuo, and carrying out reduction reaction after the drying makes graphene oxide be reduced to graphite Alkene finally carries out the refractory material modified to graphene obtained by drying.The reduction reaction is electronation or thermal reduction.Using When electronation, reducing agent used in electronation is any one in sodium borohydride, potassium borohydride or hydrazine hydrate；Chemistry is also Former reaction temperature is 80 ~ 90 DEG C.When using thermal reduction, the reaction temperature of thermal reduction is 300 ~ 400 DEG C.

The concentration of the graphene oxide aqueous dispersions is 0.5 ~ 5wt%, is the graphene oxide using 1 ~ 10 part of quality Through made from ultrasonic disperse after being mixed with the water of 190 ~ 199 parts of quality.

It is under conditions of carbon content extremely low (C < 0.1wt%) using the modified refractory material of the graphene of above method preparation Excellent slag corrosion performance resistant to high temperatures can be possessed, and be not easy to pollute molten steel.

Technical scheme in the embodiment of the invention is clearly and completely described combined with specific embodiments below, so that Those skilled in the art can better understand the present invention and can be practiced, but illustrated embodiment is not as to of the invention It limits.

Various raw materials are used in the following example, unless otherwise mentioned, all use conventional commercial product.Below with reference to specific Embodiment does further specific detailed description to the present invention, and embodiments of the present invention are not limited thereto.

It should be noted that this preparation method is suitable for all refractory materials (including carbon containing sizing refractory material and indefinite Type refractory material), part refractory material is only exemplified by embodiment.