CN1496957A - Porous carbon material and porous carbon material product obtained by using it - Google Patents
Porous carbon material and porous carbon material product obtained by using it Download PDFInfo
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- CN1496957A CN1496957A CNA031514863A CN03151486A CN1496957A CN 1496957 A CN1496957 A CN 1496957A CN A031514863 A CNA031514863 A CN A031514863A CN 03151486 A CN03151486 A CN 03151486A CN 1496957 A CN1496957 A CN 1496957A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/0675—Vegetable refuse; Cellulosic materials, e.g. wood chips, cork, peat, paper
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
- C04B35/62213—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse using rice material, e.g. bran or hulls or husks
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
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Abstract
Provided are a porous carbonaceous material using rice hulls as a starting material and a product manufactured by using it. The product of the porous carbonaceous has high availability as an industrial product suitable for mass production. The porous carbonaceous material is obtained by the steps of: mixing and kneading rice hulls with at least one selected from the group consisting of a thermosetting resin, an aqueous solution containing an animal or vegetable adhesive past and water; drying the kneading, followed by granulation to give particulate rice hulls; and baking the particulate rice hulls under inert atmosphere or under vacuum condition, followed by carbonization.
Description
Technical field
The present invention relates to the porous carbon materials that the cavings material by adopting rice bran or wheat bran and so on obtains as raw material and relate to porous carbon material products by using this porous carbon materials to obtain.
Background technology
The byproduct that a large amount of rice husks and rice bran are generally processed as rice, and rice is the staple crops of Japan.And similarly, a large amount of husks and wheat bran are derived from cereal such as wheat, buckwheat and soybean.Many byproducts that are derived from cereal are taken as refuse and burn, and have only a part wherein to obtain actual utilization.For example, Rice pollard oil is produced in the rice bran oil expression, husk (especially rice husk) just part is used for culvert, leaf charcoal etc., and distillatory dry distillation-evaporated material is condensed in leaf charcoal preparation process, and only be used for sterilant, animal expellent, soil redeposition, dermatomycosis medicine or the like.Therefore the great majority that comprise these kind cavings of degreasing cavings can only be used for agricultural material, for example feed, fungi culture medium and fertilizer.So, cavings has been become goal in research as Industrial materials effectively.
Under these circumstances, the technology with the cavings carbonization is known.The carbonization of cavings is feasible, for example in small-scale mode intermittently cavings is carried out vapor baking, or in a continuous manner at rotary kiln, multistage fluidized bed stove burning cavings, or same mode is carried out on a large scale.Yet, when cavings is very thin powder, has poor perviousness and thermal conductivity, and contain oil ﹠ fat, although just a small amount of, cavings is burnt usually, and ashing.Therefore, be difficult to effective and carbonization completely.In addition, the carbide that obtains is tiny, is easy to disperse, and is difficult to handle.Therefore, the cavings carbide is not also positively accomplished industrialization.Although by the carbide that cavings is produced, promptly so-called " charcoal " has been used as the soil redeposition on the agricultural, because its quality and quantity, this carbide also is not used as Industrial materials effectively.
In view of noted earlier, the present inventor studies effectively utilizing the degreasing cavings, on the basis of cooperating with Yamagata University, Faculty of Engineering and Yamagata Prefecture IndustrialEngineering Center, having researched and developed out with the cavings is feedstock production porous carbon material products (for example, referring to JP10-101453A).
Yet disclosed porous carbon material products is satisfactory not enough aspect workability, for example aspect the shrinkage coefficient in baking, stress in bending, compression stress or the wear resistance.And according to the preparation method of described porous carbon material products, this preparation method's a characteristic causes such problem, and the production that is exactly the mould of finished product can only begin after finished product is clear and definite.Therefore, the production of target finished product can only start after the production of mould is finished.As a result, unless finished product is clear and definite (more particularly, unless received relevant finished state and structure the order of clear regulation being arranged), otherwise can not begin the production of finished product.Much less, before receiving order, production line keeps halted state, and this is disadvantageous economically.And, because all product processing must be carried out in proper order by the time of origin of receiving order,, need very many time in the production from receiving the delivery of order to finished product.In other words, can't satisfy the demands of consumers fast.Therefore, in view of the porous carbon that is suitable for scale operation material products is provided, this production method is gratifying inadequately.
As mentioned above, by the porous carbon material products that the cavings that uses as raw material obtains, the raising of its workability and scale operation has become exigence.
Summary of the invention
The purpose of this invention is to provide a kind of porous carbon material products, these goods are by using the cavings as raw material to obtain, have gratifying workability and as the usury of Industrial products with being worth, also be suitable for scale operation.
The result of the broad research of carrying out in order to address the above problem, the present inventor provide a kind of new preparation process of porous carbon material products.The present inventor finds that the porous carbon materials product of producing by this preparation method can address the above problem, and the intermediate that obtains in this preparation method can be used to address the above problem effectively, and has finished the present invention.
Therefore, the invention provides following content:
(1) the particulate porous carbon material that obtains by following manner:
To cavings and be selected from thermosetting resin, contain the aqueous solution of the bonding paste of animal or plant and water at least aly mix and mediate;
The material of mediating is carried out drying and granulation, to obtain granular paddy crack material; With
In inert atmosphere or vacuum, granular cavings material is baked and carbonization.
(2) obtain the powdered porous carbon materials by pulverizing according to the particulate porous carbon material of (1) item.
(3) moulded product that obtains by following manner:
To mixing according to the powdery porous carbon materials of (2) and thermosetting resin or thermoplastic resin and mediating; With
The method of moulding that employing is selected from compression moulding, injection molding, extrusion molding and blowing moulding (inflation molding) carries out molded to the material of mediating.
(4) in inert atmosphere or vacuum,, obtain the porous carbon material products by baking and carbonization according to the moulded product of (3) item.
(5) obtain the porous carbon material products by following manner:
To mix and mediate according to the powdery porous carbon materials of (2) and thermosetting resin;
It is molded to adopt compression moulding that the material of mediating is carried out, to obtain moulded product; With
In inert atmosphere or vacuum, moulded product is baked and carbonization.
(6) obtain the porous carbon material products by following manner:
To mix and mediate according to the powdery porous carbon materials of (2) and thermosetting resin;
It is molded to adopt injection molding that the material of mediating is carried out, to obtain moulded product; With
In inert atmosphere or vacuum, moulded product is baked and carbonization.
(7) obtain moulded product by following manner:
To and be selected from least a in steel fiber, metal powder, carbon fiber, diatomite, tourmalinite and the magneticsubstance powder according to powdery porous carbon materials, thermosetting resin or the thermoplastic resin of (2) mixes and mediates; With
The method of moulding that employing is selected from compression moulding, injection molding, extrusion molding and blowing moulding carries out molded to the material of mediating.
(8) obtain the porous carbon material products by in inert atmosphere or vacuum, the moulded product according to (7) being baked with carbonization.
(9) a kind of preparation method of powdery porous carbon materials may further comprise the steps:
To cavings and be selected from thermosetting resin, contain the aqueous solution of the bonding paste of animal or plant and water at least aly mix and mediate;
The material of mediating is carried out drying and granulation, to obtain granular cavings material;
In inert atmosphere or vacuum, granular cavings material is baked and carbonization, to obtain particulate porous carbon material; With
Particulate porous carbon material is pulverized.
(10) a kind of preparation method of porous carbon material products may further comprise the steps:
To mix and mediate according to the powdery porous carbon materials of (9) item method preparation and thermosetting resin or thermoplastic resin;
The method of moulding that employing is selected from compression moulding, injection molding, extrusion molding and blowing moulding carries out molded to the material of mediating, to obtain moulded product; With
In inert atmosphere or vacuum, moulded product is baked and carbonization.
The embodiment of invention
Below the present invention is described in detail.
＜porous carbon materials 〉
Porous carbon materials according to the present invention contains cavings and is selected from thermosetting resin, contains at least a of the aqueous solution of the bonding paste of animal or plant and water.
Term as used herein " cavings " refers to: the degreasing cavings, and it still keeps a large amount of volumes after being used to produce the oil expression of Rice pollard oil; Wheat bran, flour produces by wheat flour milling is prepared; And husk, it produces in the treating grain process, for example rice husk, Buckwheat shell, soybean peel and gluten raw material (corn husk or plant the benevolence skin, promptly produce the residue of W-Gum).
And, thermosetting resin, the aqueous solution that contains the bonding paste of animal or plant or water, when it mixes with cavings, as with the bonding paste of cavings.In thermosetting resin, the aqueous solution that contains the bonding paste of animal or plant or the water (hereinafter, being called " bonding paste " together) two or more also can be used in combination.
The preferred embodiment of thermosetting resin comprises resol.In the present invention, this thermosetting resin can liquid or powder-form use.At thermosetting resin is under the powdered situation, preferably adds water in cavings and thermosetting resin, with its mixing and kneading, uses so that the mixing of thermosetting resin and cavings is carried out smoothly, and stirs this mixture.
In addition, for the bonding paste of animal or plant, also can use the bonding paste of marine alga.The specific examples of the bonding paste of animal or plant comprises collagen, starch and xylogen.
Porous carbon materials according to the present invention prepares according to following method.＜1〉with above-mentioned cavings and mixing of bonding paste and the cavings of kneading to obtain to mediate.The cavings drying of this kneading is also granulated to obtain granular cavings material.In inert atmosphere or vacuum, should bake and carbonization by granular cavings material, to obtain particulate porous carbon material.
In above-mentioned preparation method, the cavings of use preferably in advance by the process classification, has predetermined particle diameter or littler particle diameter.By carrying out such classification, for example, under the situation of degreasing cavings, macrobead (particle of incendiary or extruding in degreasing process) can be removed.In addition, have the cavings of unified particle diameter, make subsequently molded become easier, and the material that obtains has more uniform structure by use.Specifically, the particle diameter that cavings has passes through 12 mesh sieves, and preferably uses 20 mesh sieves.
When thermosetting resin and cavings mixed, its blending ratio was, based on the cavings of 20 to 95 weight parts, and preferably about 5 to 80 weight parts of thermosetting resin, and more preferably based on the cavings of 40 to 90 weight parts, thermosetting resin is about 10 to 60 weight parts.According to the kind of institute's blended cavings, this ratio can be different.For example, under the situation of using the degreasing cavings, the thermosetting resin of about 5 to 80 weight parts mixes with the cavings of 20 to 95 weight parts; Using under the situation of wheat bran, the thermosetting resin of about 5 to 70 weight parts and 30 to 95 weight parts cavings mix; And under the situation of using the gluten raw material, the thermosetting resin of about 5 to 60 weight parts mixes with the cavings of 40 to 95 weight parts.Yet, it should be noted that under any circumstance, according to the condition difference of the temperature of the raw material of the water-content in the cavings of particle diameter, the kneading of cavings or use for example, preferred blending ratio can be different.In the technology of thermosetting resin and cavings being mixed and mediating, contain the aqueous solution of an amount of tackiness agent (for example, under the situation of using the degreasing cavings, being 5 to 30 weight %) based on the weight of cavings, for example syrup if necessary can add.Perhaps, the aqueous solution and the thermosetting resin that will contain tackiness agent mix, and then blended solution can be mixed with cavings and mediate.
Using under the situation of the bonding paste of animal or plant as bonding paste, can use the aqueous solution of the bonding paste of animal or plant that contains 1.0 to 30 weight %.In addition, under with such solution and cavings blended situation, the blending ratio of solution is that the cavings that for example is preferably based on 90 to 97 weight parts is the solution of about 3 to 10 weight parts.
Under the situation that makes water as bonding paste, the blending ratio of water is that the cavings that for example is preferably based on 80 to 95 weight parts is the water of about 5 to 20 weight parts.
When cavings mixes with bonding paste and mediates, should consider to make bonding paste thoroughly to penetrate into more such conditions of cavings, for example mix and stir environment, and the time of repose after mixing and stirring.
Drying is preferably carried out under about 60 to 80 ℃ heating condition, in order to remove volatile component.
By using known nodulizer, for example board-like nodulizer or tubular type nodulizer are granulated.
In addition, with the granular cavings material of drying and granulating and obtaining, by about 4 orders, and more preferably from about 5 purposes sieve sieves, and screened material is delivered to baking technology and carbonization technique flow process.By sieving, bake with carbonization after, quality inhomogeneous obtained inhibition.
Bake and in rotary kiln or intermittent type Roasting oven, to carry out.Under oxygen free condition, for example bake in rare gas element (for example, the nitrogen) environment, fall so that the granular cavings material that prevents to contain bonding paste is burned.Under the situation of using the intermittent type Roasting oven, also can under vacuum, bake.Preferred baking temperature is selected from about 200 ℃ of scopes to 1 more than thousand Baidu, this is to consider by baking the required character of particulate porous carbon material that obtains with carbonization to determine that these character for example are hardness, purity, porousness, conductivity, workability and structural strength.In addition, the setting that bakes the time should be taken into account multiple factor, and these factors relate to the state that bakes of the intensity that influences particulate porous carbon material, density etc.Specifically, it is 600 ℃ to 1100 ℃ that baking temperature preferably is provided with scope, more preferably from about 700 ℃ or higher, and more preferred 900 ℃ or higher.The time that bakes is preferably at least about 1 hour.
More preferably, bake in the rotary type Roasting oven, the temperature gradient in its stove is 700 ℃ to 900 ℃.For example, the temperature in stove is arranged on 700 ℃, and the intermediate portion is arranged on 800 ℃, and its outlet is set to 900 ℃, and bakes in such stove.It should be noted that heating rate in the process of baking should avoid the rapid increase of temperature, to prevent the damage of granular cavings material.Especially at about 200 ℃ to 400 ℃, be accompanied by the decomposition of material, produced a large amount of gas, so should give one's full attention to heating rate in this temperature range.
To be cooled to normal temperature through baking, preferably use water-cooled condenser with the granular cavings material of the carbonization of carbonization process.
As mentioned above, obtain the particulate porous carbon material of refrigerative.In addition, according to following method, and use the refrigerative porous carbon materials can prepare the powdered porous carbon materials.
＜2〉pass through aforesaid method＜1 the middle particulate porous carbon material pulverizing that obtains, obtain the powdered porous carbon materials.
Can use pulverizer (supper micron mill) to pulverize.
In addition, pulverized the powdery porous carbon materials that obtains, preferably be classified as the grade of pre-determined quantity, each grade has required particle diameter.This is because such classification can be in order to select, and use porous carbon materials with the appropriate particle size that is used to manufacture a finished product, this material is consistent with the various attributes of various high functional products, described high functional product is that the human consumer is needed (specifically, consider the complicacy of shape of product, because the accuracy of such complicacy, structural strength and outward appearance is difficult to product is put in the mould suitably).For example, porous carbon materials is classified as 250 to 100 μ m, 150 to 100 μ m, 150 μ m or littler, 100 μ m or littler, 50 to 10 μ m, 50 μ m or littler, 30 μ m or littler and 10 μ m or littler particle diameter respectively.
By using vibratory screening apparatus to carry out classification.
Will be by aforesaid method＜1〉the particulate porous carbon material that obtains or by aforesaid method＜2 the powdery porous carbon materials of acquisition is used to prepare moulded product or porous carbon material products described later as intermediate.Have those porous carbon materials of outstanding workability (for example, the shrinkage coefficient in baking, stress in bending, compression stress and wear resistance are improved) by method described later and use, obtain the porous carbon material products.In addition, the moulded product that contains porous carbon materials, resin and added ingredients is the porous carbon composite product, and it demonstrates unique physical properties.In addition, moulded product and the porous carbon material products that is adapted to consumer demand can and use previously prepared those porous carbon materials promptly to be produced and to preserve by method described later aptly.
Below, will be to being described by the porous carbon material products that uses the powdery porous carbon materials preparation that obtains as mentioned above.
＜porous carbon material products 〉
Porous carbon material products according to the present invention contains powdery porous carbon materials and thermosetting resin or the thermoplastic resin that obtains as mentioned above.
The thermoplastic resin preferred examples comprises nylon resin and vibrin.In the present invention, thermoplastic resin can liquid or the use of powdered form.
Thermosetting resin as above saves＜porous carbon materials〉described in.
Can be according to porous carbon material products of the present invention according to following method preparation.
＜3〉with method＜2〉in the powdery porous carbon materials that obtains and thermosetting resin or thermoplastic resin mix and mediate, and the molded moulded product that obtains.
＜4〉with method＜3〉in the moulded product that obtains, in inert atmosphere or vacuum, bake and carbonization, to obtain the porous carbon material products.
In above-mentioned preparation method, this resin can be used as tackiness agent and gives moldability.In addition, by baking, this resin is carbonized and becomes a component of powdery porous carbon materials.
Under with thermosetting resin and powdered porous carbon materials blended situation, the blending ratio of thermosetting resin be the powdery porous carbon materials that is preferably based on 40 to 90 weight parts be about 10 to 60 weight parts thermosetting resin (but preferred blending ratio according to the particle diameter of for example powdery porous carbon materials, mediate the water-content in the material or the condition of the temperature of the raw material that adopted and so on can be different.This is equally applicable to following description).Under with thermoplastic resin and powdered porous carbon materials blended situation, the blending ratio of thermoplastic resin is that the powdery porous carbon materials that is preferably based on 5 to 90 weight parts is about 10 to 95 parts by weight of thermoplastic resin.
As for above-mentioned molded, can use any suitable method, for example compression moulding, injection molding, extrusion molding or blowing moulding.
In addition, can in the intermittent type Roasting oven, bake.Bake under oxygen free condition, for example carry out in the inert atmosphere (for example, nitrogen).Under the situation of using the intermittent type Roasting oven, also can under vacuum, bake.Baking temperature preferably is set to about 500 to 1100 ℃, and more preferably 900 ℃ or higher.
With respect to last joint＜porous carbon materials〉described in those, bake with carbonization in heating rate and carbonization after be cooled to normal temperature rate of cooling need control more accurately so that prevent to take place as the disruptive of the porous carbon material products of finished product.
For example, under final baking temperature was 500 ℃ or lower situation, preferred temperature control was as follows.In the scope of room temperature to 500 ℃, heating rate was arranged on 1 ℃/min to 1.2 ℃/min, and then under final baking temperature, with this temperature maintenance 2 to 3 hours.Afterwards, the rate of cooling with 1.5 ℃/min cools the temperature to normal temperature.Surpass under 500 ℃ the situation at final baking temperature, preferred temperature control is as follows.In the scope of room temperature to 500 ℃, heating rate was arranged on 1 ℃/min to 1.2 ℃/min, and then at 500 ℃, with this temperature maintenance 1 hour.Then, temperature is further raise with the heating rate of 2 ℃/min, and under final baking temperature, kept 2 hours.Afterwards, the rate of cooling with 1.2 ℃/min to 1.5 ℃/min cools the temperature to normal temperature.
More preferably, under final baking temperature is 500 ℃ or lower situation, in the scope of room temperature to 250 ℃, heating rate is arranged on 1.2 ℃/min, in 250 ℃ to 350 ℃ scope, heating rate is arranged on 1 ℃/min, and in 350 ℃ to 500 ℃ the scope, heating rate is arranged on 1.2 ℃/min.Under final baking temperature, with this temperature maintenance 2 to 3 hours.Afterwards, the rate of cooling with 1.5 ℃/min cools the temperature to normal temperature.Under final baking temperature surpassed 500 ℃ situation, in the scope of room temperature to 250 ℃, heating rate was arranged on 1.2 ℃/min, in 250 ℃ to 350 ℃ scope, heating rate is arranged on 1 ℃/min, and in 350 ℃ to 500 ℃ the scope, heating rate is arranged on 1.2 ℃/min.Then, at 500 ℃, with this temperature maintenance 1 hour, and rise to the final baking temperature of target from 500 ℃, heating rate is arranged on 2 ℃/min.Next, under final baking temperature, with this temperature maintenance 2 hours.Afterwards, cool the temperature to 600 ℃, and then be cooled to normal temperature with the rate of cooling of 1.5 ℃/min with the rate of cooling of 1.2 ℃/min.
For situation about baking under vacuum, the pressure drop in Roasting oven is low to moderate 4 * 10
3Behind the Pa, adopt said temperature control to bake.When step-down, can use water seal vacuum pump SW-150 (by SHINKOCo., LTD. makes).
In the porous carbon material products that obtains by above-mentioned preparation method, the porous carbon material products demonstrates preferred performance, and these performances can obtain by the qualification to resin and method of moulding kind.Below, with the porous carbon material products of describing according to embodiment preferred.
＜5〉in aforesaid method＜2〉in the powdery porous carbon materials that obtains and thermosetting resin mix and mediate.Then use compression moulding, the material of mediating is carried out molded, to obtain moulded product.This moulded product is baked and carbonization in inert atmosphere or vacuum, in order to obtain the porous carbon material products.
Adopt above-mentioned molded following the carrying out of compression moulding.The material of mediating is put into the mould of heating, and with the internal pressurization and the degassing of mould.Preferably 120 to 170 ℃ of the temperature of mould.The pressure of using in pressurization is preferably 40 to 450kgf/cm
2The per unit area moulded product.
Except the kind that limits resin and method of moulding, with preparation method＜3〉and＜4〉same mode be prepared method＜5 〉.
Next, the porous carbon material products according to another kind of embodiment preferred is described.
＜6〉in aforesaid method＜2〉in the powdery porous carbon materials that obtains and thermosetting resin mix and mediate.Then use injection molding, the material of mediating is carried out molded, to obtain moulded product.This moulded product is baked and carbonization in inert atmosphere or vacuum, in order to obtain the porous carbon material products.
Be injected into the mould of heating by the material that will mediate, and, adopt the above-mentioned molded of injection molding to its pressurization.
Molded temperature is preferably near 180 ℃.Injection is preferably at 120kgf/cm
2Condition under carry out.Apply and keep preferably 40kgf/cm of pressure
2The temperature of injection molding machine is 80 ℃ in the ingress of equipment preferably, be 100 ℃ at the middle portion of equipment, and the temperature at the outlet nozzle place is 120 ℃.
Except the kind that limits resin and method of moulding, with preparation method＜3〉and＜4〉same mode be prepared method＜6 〉.
By aforesaid method＜4〉the porous carbon material products that obtains is applicable to multiple high functionality goods.Especially by aforesaid method＜5〉and＜6〉the porous carbon material products that obtains have excellent workability, for example be improved aspect the shrinkage coefficient in baking, stress in bending, compression stress and the wear resistance, and expectation is applied to the high functionality product.
In addition, by adding following additional added ingredients, can form the porous carbon composite product that demonstrates unique physical character, described interpolation is with aforesaid method＜2〉obtain that powdery porous carbon materials and resin mix and carry out when mediating.Below will be described specific embodiment.
＜7〉in aforesaid method＜2〉in the powdery porous carbon materials, thermosetting resin or the thermoplastic resin that obtain and be selected from least a composition in steel fiber, metal powder, carbon fiber, diatomite, tourmalinite and the magneticsubstance powder (below, be also referred to as " the 3rd composition ") mix and mediate, and molded, to obtain moulded product.
This moulded product can further be baked and carbonization.
＜8〉in inert atmosphere or vacuum, the moulded product that obtains is baked and carbonization, in order to obtain the porous carbon material products.
By the advantage of aspects such as its electricity or mechanical properties, in method＜7〉in the moulded product or method＜8 that obtain in the porous carbon composite product that obtains be applied to each field.
Except further interpolation the 3rd composition, with preparation method＜3〉and＜4〉same mode be prepared method＜7〉and＜8.
According to the present invention, the porous carbon material products that obtains by the cavings that uses as raw material can be provided, its have gratifying workability and as the usury of Industrial products with being worth.In addition, because the method for this porous carbon material products of preparation is suitable for scale operation, therefore can provide the porous carbon material products apace.
Thus obtained porous carbon material products not only can be applicable to material of construction, for example outer wall material, furniture and wrapping material, and can be applicable to mechanical component, for example bearing, and functional article, for example electro-conductive material, heating unit and electronic component.
According to the present invention, cavings can be applied to various high functionality products, described functional product has physical properties, for example structural strength, frictional coefficient and the coefficient of expansion, and functional for example adsorptive power, heat insulation capacity, thermotolerance, chemical resistant properties, weathering resistance, current capacity and electromagnetic shielding ability.In other words, can use cavings effectively exactly as industrial raw material.
Below, the present invention will be explained in more detail according to embodiment.
Embodiment
Embodiment 1
＜blending means 〉
The degreasing cavings that oil has been extracted passes through 50 mesh sieves.Add the resol (by the Honen Corporation Ltd. of Japan, with " Honen Resingul-px-1600 " trade(brand)name manufacturing) of 25 weight parts, and carry out thorough mixing and kneading with the degreasing cavings that sieves of 75 weight parts.
＜method of granulating 〉
In order to remove volatile component,, granulate also by 4 mesh sieves, to obtain granular cavings material with mixture heating up to 80 ℃.
＜bake method 〉
Granular cavings material is baked in exuberant the rotary kiln of nitrogen.Temperature in the rotary kiln is set to, and the temperature of ingress is that 700 ℃, the temperature of middle portion are 800 ℃, and the temperature in exit is 900 ℃, and the formation temperature gradient it should be noted to prevent that material is exposed in the high temperature suddenly.This material by injecting raw material to taking out the time that bakes with the carbonization material, was kept in stove 1 hour at least.By water cooled condenser, the material that bakes with carbonization that will take out from stove is cooled to normal temperature.
＜breaking method 〉
With the granular cavings material of the carbonization that is cooled to normal temperature, pulverize with pulverizer (supper micron mill), and use vibratory screening apparatus to carry out classification, be 100 μ m or littler powdery porous carbon materials in order to obtain particle diameter.
Embodiment 2
The powdery porous carbon materials that obtains by the preparation method who uses embodiment 1 prepares plate shape porous carbon material products.
＜blending means 〉
The powdery porous carbon materials that the embodiment 1 of 75 weight parts is obtained and the resol of 25 weight parts are (by Honen Corporation Ltd., with " Honen Resingul-px-1600 " trade(brand)name manufacturing) mix fully and mediate, in order to obtain to mediate material.
＜metal pattern method of moulding 〉
The kneading material of 10g is put into the metal mold that is used for plate shape goods, and its temperature range is 140-170 ℃.The length of mould is 75mm, and width is 150mm, according to the quantity of material and pressure and variable thickness (mm).The gauge pressure that puts on mould is 50kgf/cm
2, apply 2 minutes, then discharge pressure, and outgas to mould.After the degassing, the gauge pressure that puts on mould again is 50kgf/cm
2, apply 3 minutes, in order to obtain plate shape moulded product.
In addition, be 150 to 250 ℃ well heater by the use temperature scope, moulded product is heat-treated in hot blast, to improve the physical properties of moulded product.
＜bake method 〉
Under oxygen free condition, in exuberant the Roasting oven of nitrogen, mould is baked.During baking, its temperature is brought up to 250 ℃ with the heating rate of 1.2 ℃/min by room temperature, with the heating rate of 1 ℃/min by 250 ℃ to 350 ℃, with the heating rate of 1.2 ℃/min by 350 ℃ to 500 ℃, kept 1 hour at 500 ℃, then bring up to 900 ℃ with the heating rate of 2 ℃/min by 500 ℃ again, and kept 2 hours at 900 ℃, and then being cooled to room temperature, rate of cooling is 1.5 ℃/min.
By aforesaid method, prepare the porous carbon material products.
Embodiment 3
The powdery porous carbon materials that obtains by the preparation method who uses embodiment 1 prepares plate shape porous carbon material products.
＜blending means 〉
The powdery porous carbon materials that the embodiment 1 of 75 weight parts is obtained and the phenolic varnish type powdered phenol-formaldehyde resin of 25 weight parts are (by DAINIPPON INK AND CHEMICALS, INCORPORATED, with " Phenolite 5510 " trade(brand)name manufacturing) mix fully and mediate, in order to obtain to mediate material.
＜metal pattern stamping method 〉
The kneading material of 10g is put into the metal mold that is used for plate shape goods, and its temperature range is 140-170 ℃.The length of mould is 75mm, and width is 150mm, according to the quantity of material and pressure and variable thickness (mm).The gauge pressure that puts on mould is 50kgf/cm
2, apply 2 minutes, then discharge pressure, and outgas to mould.After the degassing, the gauge pressure that puts on mould again is 50kgf/cm
2, apply 3 minutes, in order to obtain plate shape moulded product.
＜bake method 〉
Under oxygen free condition, in exuberant the Roasting oven of nitrogen (outer hot type is made by Tokaikonetsu KogyoCorporation Ltd.), mould is baked.During baking, its temperature is brought up to 250 ℃ with the heating rate of 1.2 ℃/min by room temperature, with the heating rate of 1 ℃/min by 250 ℃ to 350 ℃, with the heating rate of 1.2 ℃/min by 350 ℃ to 500 ℃, kept 1 hour at 500 ℃, then bring up to 900 ℃ with the heating rate of 2 ℃/min by 500 ℃ again, and kept 2 hours at 900 ℃.Then mould is cooled to 600 ℃, rate of cooling is 1.2 ℃/min, and is cooled to room temperature by 600 ℃, and rate of cooling is 1.5 ℃/min.
By aforesaid method, prepare the porous carbon material products.
Embodiment 4
By the powdery porous carbon materials that the preparation method who uses embodiment 1 obtains, preparation plate shape porous carbon material products (60 * 15 * 2mm).
＜blending means 〉
The powdery porous carbon materials that the embodiment 1 of 75 weight parts is obtained and the phenolic varnish type powdered phenol-formaldehyde resin of 25 weight parts are (by DAINIPPON INK AND CHEMICALS, INCORPORATED, with " Phenolite 5510 " trade(brand)name manufacturing) add Hot mixer by drum-type and heat, mix and mediate, in order to obtain to mediate material.The material of mediating is pulverized by the power runner milling, and 4mm is long, 4mm is wide and 4mm thickness or littler granular moulding material to produce.
＜injection molding method 〉
Use screw type injection molding machine 75F-36K type (making) to carry out injection molding by Matsuda Seisakusho Co.Ltd..Inlet injection temperature at this equipment is arranged on 80 ℃, and middle portion is arranged on 100 ℃, and is arranged on 120 ℃ at its outlet nozzle.The temperature of metal pattern is arranged on 180 ℃, when carrying out injection molding, applies 110kgf/cm to mould
2Pressure.
The manufacturing cycle of injection molded article is set to one-period cost 90 seconds.As a result, obtain plate shape moulded product (13 * 64 * 3t).
＜bake method 〉
Use the intermittent type Roasting oven, in nitrogen environment, bake the above-mentioned moulded product that obtains.During baking, its temperature is brought up to 250 ℃ with the heating rate of 1.2 ℃/min by room temperature, with the heating rate of 1 ℃/min by 250 ℃ to 350 ℃, with the heating rate of 1.2 ℃/min by 350 ℃ to 500 ℃, kept 1 hour at 500 ℃, then bring up to 900 ℃ with the heating rate of 2 ℃/min by 500 ℃ again, and kept 2 hours at 900 ℃.Then mould is cooled to 600 ℃, rate of cooling is 1.2 ℃/min, and is cooled to room temperature by 600 ℃, and rate of cooling is 1.5 ℃/mm.
By aforesaid method, prepare the porous carbon material products.
Embodiment 5
＜blending means 〉
The powdery porous carbon materials that the embodiment 1 of 55 weight parts is obtained, the phenolic varnish type powdered phenol-formaldehyde resin of 25 weight parts are (by DAINIPPON INK AND CHEMICALS, INCORPORATED, with " Phenolite 5510 " trade(brand)name manufacturing) and the carbon fiber of 20 weight parts (by DONAC Co.Ltd., with " Donacarbo S-242 " trade(brand)name manufacturing) mix and kneading by mixing machine, to prepare molded material.
＜stamping method 〉
The molding compounds of 100g is put into metal mold, and its temperature is arranged on 150 ℃.The length of mould is 75mm, and width is 150mm and variable thickness (mm).The gauge pressure that puts on mould is 40kgf/cm
2, apply 2 minutes, then discharge pressure, and outgas to mould.After the degassing, the gauge pressure that puts on mould is 40kgf/cm
2, apply 2 minutes and discharged pressure 1 minute.Afterwards, the gauge pressure that puts on mould again is 60kgf/cm
2, apply 2 minutes to obtain moulded product.
By placing 200 ℃ well heater 5 hours, moulded product is heat-treated (after fixing).
Embodiment 6
Except in embodiment 1, using the aqueous solution replacement resol that contains collagen, obtain the powdered porous carbon materials in embodiment 1 same mode, to prepare following granular cavings material.
The aqueous solution that contains 1 weight % collagen of 5 weight parts is spilt cavings to 95 weight parts, and stir this mixture.Then, this mixture is formed particle by desk-top tablets press F-20/12-330 type (DALTON Corporation manufacturing) with 5mm diameter (Φ 5) and 10mm long (L10).
The comparative example 1
The degreasing cavings is sieved with 50 mesh sieves.With the degreasing cavings of 75 weight parts and the resol of 25 weight parts (by Honen Corporation Ltd., with " Honen Resingul-px-1600 " trade(brand)name manufacturing) thorough mixing.
This mixture is granulated, and 80 ℃ of down heating, removing volatile component, and sieve, in order to obtain molding compounds by 12 mesh sieves.
The molding compounds of 15g is put into the metal mold that is equipped with well heater (internal diameter 42mm, and length is 60mm).Using high pressure chuck (the tube internal diameter is 21mm), is 300kgf/cm in gauge pressure
2Under the condition, heating is carried out molded until 180 ℃.During molded, gauge pressure is reduced to about 70kgf/cm
2Be used for for several times the degassing, in order to remove water and the gas that decomposes and produce.
In the Roasting oven of exuberant nitrogen, mould is baked.During baking, its temperature is brought up to 250 ℃ with the heating rate of 1.2 ℃/min by room temperature, with the heating rate of 1 ℃/min by 250 ℃ to 350 ℃, with the heating rate of 1.2 ℃/min by 350 ℃ to 500 ℃, kept 1 hour at 500 ℃, then bring up to 900 ℃ with the heating rate of 2 ℃/min by 500 ℃ again, and kept 2 hours at 900 ℃.Then mould is cooled to 600 ℃, rate of cooling is 1.5 ℃/min, and then naturally cools to room temperature.
By aforesaid method, prepare the porous carbon material products.
EXPERIMENTAL EXAMPLE 1
With embodiment 3 and 4 and comparative example 1 in the porous carbon material products that obtains carry out the evaluation of physical properties.Evaluation results is shown in Table 1.In addition, the moulded product that contains embodiment 5 porous carbon materials carries out the evaluation of physical properties.Evaluation result is shown in table 2.
Every in the table 1 and 2 carries out following evaluation.
With the sample of a certain weight (100g), put into graduated cylinder, the volume of measure sample, and calculate (weight/volume), thus obtain bulk specific gravity.
According to JIS R1620 (specific gravity hydrometer method), measure true specific gravity.
Measure stress in bending according to JIS R1601 (three-point bending resistance test).Under 20 ℃ and 65%RH condition, use Instron type material testing apparatus to measure.
Measure compression stress according to JIS R1608.
Measure thermal expansivity according to JIS P1618.
By with the ruler measurement moulded product before baking and size afterwards, and calculate after baking with bake before magnitude proportion, obtain baking shrinkage coefficient.
Use reciprocating motion type friction testing equipment (by Shin-Toyo Kagaku Co., Ltd. makes, Pin-on-disk HEIDON-22 type) to measure frictional coefficient.
The following wear resistance of carrying out is measured.Use reciprocating motion type friction testing equipment (by Shin-Toyo KagakuCo., Ltd. makes, Pin-on-disk HEIDON-22 type) to measure.Use and follow the trail of the cross-section curve of type surface roughness tester working sample 5 test point.The direction of this cross section is perpendicular to the frictional force direction.Based on cross-section curve, obtain the wear volume of sample.Then, calculate the specific wear amount according to following equation (1), as abrasion resistance index.Here, Ws represents the specific wear amount, and V represents wear volume, and W represents normal load, and L represents sliding distance.
Ws＝V/W·L(1)
The hole area ratio that obtains as described below.Surface by scanned-laser microscope 1LM21 (making) observation sample by LasertecCorporation.Based on to outputing to the observation of the photo on the printer, calculate the hole area ratio according to following equation (2).Here Ap indication window area, and Aa represents the total area.
Hole area than=(Ap/Aa) * 100 (2)
By rely on the expert to sample whether be easy to bore, mill, turning and attrition process judge, measures workability.
By the digital multimeter (CDM-27D) with customization, (1 * 1 * 1t) obtains resistivity to working sample.
By with metering equipment SM-8001 (making) working sample by DKK-TOA Corporation (100 * 100 * 2t), obtain the volume resistivity rate.
Table 1
| Embodiment 3 | Embodiment 4 | The comparative example 1 | |
| Bulk specific gravity (kg/L) | ????1.216 | ????1.280 | ????1.178 |
| True specific gravity (kg/L) | ????1.240 | ????1.490 | ????1.396 |
| Stress in bending (MPa) | ????35.5 | ????61.5 | ????17.1 |
| Compression stress (MPa) | ????121.6 | ????264 | ????44.0 |
| Thermal expansivity | ????4.1×10 -6 | ????2×10 -6 | ????5.1×10 -6 |
| Bake shrinkage coefficient | ????2.5％ | ????2.5％ | ????25％ |
| Frictional coefficient | ????0.14～0.18 | ????0.15～0.2 | ????0.13～0.15 |
| Wear resistance (mm 2/N) | ????10 -9 | ????10 -9 | ????7×10 -8 |
| Hole area is than (%) | ????20 | ????18 | ????40 |
| Workability | Good | Good | Difference |
Table 2
| Embodiment 5 | |
| Bulk specific gravity (kg/L) | ????1.234 |
| True specific gravity (kg/L) | ????1.252 |
| Stress in bending (MPa) | ????49.1 |
| Compression stress (MPa) | ????167.3 |
| Thermal expansivity | ????1.3×10 -6 |
| Resistivity | ????50Ω |
| The volume resistivity rate | ????160Ω |
| Bake shrinkage coefficient | ????2％ |
| Workability | Good |
Show,, to have outstanding workability (for example, baking shrinkage coefficient, stress in bending, compression stress and wear resistance is improved) by test-results by the goods that embodiment 2 grades obtain according to porous carbon material products of the present invention.And the porous carbon materials that embodiment 1 obtains can be effectively as the intermediate for preparing the porous carbon material products.According to the present invention, can select and use the porous carbon materials of optimum grain-diameter be used to manufacture a finished product (high functionality product), described product has the needed multiple character of human consumer (Fu Za shape of product for example is because the accuracy of such complicacy, structural strength and outward appearance is difficult to product is put into mould).In addition, if prepare this intermediate in advance and store, then can be by with powdery porous carbon materials (this intermediate) and mixed with resin and molded and bake the step of this mixture, startup preparation technology.As a result, can produce the porous carbon material products apace.
Claims (10)
1. particulate porous carbon material, it obtains by following manner:
To cavings and be selected from thermosetting resin, contain the aqueous solution of the bonding paste of animal or plant and water at least aly mix and mediate;
The material of mediating is carried out drying and granulation, to obtain granular cavings material; With
In inert atmosphere or vacuum, granular cavings material is baked and carbonization.
2. powdery porous carbon materials, it is to obtain by the particulate porous carbon material of claim 1 is pulverized.
3. moulded product, it obtains by following manner:
To mix and mediate according to the powdery porous carbon materials of claim 2 and thermosetting resin or thermoplastic resin; With
The method of moulding that employing is selected from compression moulding, injection molding, extrusion molding and blowing moulding carries out molded to the material of mediating.
4. porous carbon material products, it is by in inert atmosphere or vacuum, will bake according to the moulded product of claim 3 with carbonization to obtain.
5. porous carbon material products, it obtains by following manner:
To mix and mediate according to the powdery porous carbon materials of claim 2 and thermosetting resin;
It is molded to adopt compression moulding that the material of mediating is carried out, to obtain moulded product; With
In inert atmosphere or vacuum, moulded product is baked and carbonization.
6. porous carbon material products, it obtains by following manner:
To mix and mediate according to the powdery porous carbon materials of claim 2 and thermosetting resin;
It is molded to adopt injection molding that the material of mediating is carried out, to obtain moulded product; With
In inert atmosphere or vacuum, moulded product is baked and carbonization.
7. moulded product, it obtains by following manner:
To and be selected from least a in steel fiber, metal powder, carbon fiber, diatomite, tourmalinite and the magneticsubstance powder according to powdery porous carbon materials, thermosetting resin or the thermoplastic resin of claim 2 mixes and mediates; With
The method of moulding that employing is selected from compression moulding, injection molding, extrusion molding and blowing moulding carries out molded to the material of mediating.
8. porous carbon material products, it is to obtain by in inert atmosphere or vacuum the moulded product according to claim 7 being baked with carbonization.
9. the preparation method of powdery porous carbon materials may further comprise the steps:
To cavings and be selected from thermosetting resin, contain the aqueous solution of the bonding paste of animal or plant and water at least aly mix and mediate;
The material of mediating is carried out drying and granulation, to obtain granular cavings material;
In inert atmosphere or vacuum, granular cavings material is baked and carbonization, to obtain particulate porous carbon material; With
Particulate porous carbon material is pulverized.
10. the preparation method of porous carbon material products may further comprise the steps:
Powdery porous carbon materials that will prepare according to the method for claim 9 and thermosetting resin or thermoplastic resin mix and mediate;
The method of moulding that employing is selected from compression moulding, injection molding, extrusion molding and blowing moulding carries out molded to the material of mediating, to obtain moulded product; With
In inert atmosphere or vacuum, moulded product is baked and carbonization.
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Cited By (6)
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| CN101000955B (en) * | 2006-01-09 | 2010-11-03 | 英耐时有限公司 | Negative electrode carbon material for lithium ion secondary battery and its manufacturing method |
| CN102164851A (en) * | 2008-09-29 | 2011-08-24 | 日清奥利友集团株式会社 | Burned plant material and electromagnetic shielding member |
| CN101454243B (en) * | 2006-05-31 | 2012-04-18 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
| CN103647082A (en) * | 2013-12-24 | 2014-03-19 | 中国船舶重工集团公司第七一二研究所 | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material |
| CN106457214A (en) * | 2014-06-11 | 2017-02-22 | 贺利氏德国有限及两合公司 | Supported catalyst and method for producing a porous graphitized carbon material covered with metal nanoparticles |
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| KR100934386B1 (en) * | 2008-04-17 | 2009-12-30 | 김은경 | Manufacturing method of carbon composite panel |
| KR101123586B1 (en) * | 2010-07-08 | 2012-03-21 | 한서대학교 산학협력단 | A production method of high porosity carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04328591A (en) * | 1991-04-30 | 1992-11-17 | Minolta Camera Co Ltd | Laser printer |
| JP3530329B2 (en) * | 1996-10-01 | 2004-05-24 | 三和油脂株式会社 | Method for manufacturing porous carbon material product |
| JP4550994B2 (en) * | 2000-12-15 | 2010-09-22 | ミネベア株式会社 | Bearing rolling element material |
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2003
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| CN101000955B (en) * | 2006-01-09 | 2010-11-03 | 英耐时有限公司 | Negative electrode carbon material for lithium ion secondary battery and its manufacturing method |
| CN101454243B (en) * | 2006-05-31 | 2012-04-18 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
| CN102164851A (en) * | 2008-09-29 | 2011-08-24 | 日清奥利友集团株式会社 | Burned plant material and electromagnetic shielding member |
| CN103647082A (en) * | 2013-12-24 | 2014-03-19 | 中国船舶重工集团公司第七一二研究所 | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material |
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| CN106457214A (en) * | 2014-06-11 | 2017-02-22 | 贺利氏德国有限及两合公司 | Supported catalyst and method for producing a porous graphitized carbon material covered with metal nanoparticles |
| CN106457214B (en) * | 2014-06-11 | 2020-07-24 | 贺利氏德国有限及两合公司 | Catalyst support and method for producing porous graphitized carbon material covered with metal nanoparticles |
| CN109384454A (en) * | 2018-10-26 | 2019-02-26 | 陕西科技大学 | A kind of environment-friendly type anion porous brick and its preparation method and application |
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| KR20040027447A (en) | 2004-04-01 |
| JP2009173540A (en) | 2009-08-06 |
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