JP2005516883A5 - - Google Patents

Description

Microwave-assisted treatment of carbon foam

(Field of Invention)
The present invention relates to the treatment (ie, carbonization and / or graphitization) of carbon foam materials, and more particularly to the use of microwave and induction heating devices to facilitate such heating.

(Background of the Invention)
Traditionally, the treatment of carbon foams called carbonization and graphitization is well known in the art and at elevated temperatures on the order of about 1000 ° C. or higher to remove all remaining volatiles from them. Including the treatment of such foams. Such treatments can and will generally affect the properties of such materials, such as by making them more thermally and / or electrically insulating, more wear resistant, and the like.

  Such treatments are highly desirable in order to control the above and similar properties of carbon foam, but they are not limited to the specific carbon foam being treated, as well as its physical shape and conventional radiation or convection. Depending on the thickness of the sample being processed in the base heating device, it tends to include an extension of the heating period on the order of hours to days. Such extended processing can significantly affect and actually affect the economics of the manufacturing process for such carbon foams, both in terms of required energy and equipment use. Yes.

  Part of the required heating time is due to the need to note that the carbon foam is not subjected to excessive stress during the heating period (and also the cooling period), which is The inherent thermal insulation properties of the convection and radiant heating devices expose only the outer surface of the carbon foam under treatment to thermal energy, and the interior of the shape being processed via the thermal insulation of the carbon foam It takes a lot of time due to the fact that it must be implemented. Thus, the inert thermal insulation properties of the carbon foam prevent it from heating faster and achieving carbonization and / or graphitization.

  Thus, a method for heating a carbon foam that allows acceleration of the heating cycle and thus reduces the overall processing time required to obtain carbonization and / or graphitization of the carbon foam It is highly desirable to provide

(Object of invention)
Accordingly, it is an object of the present invention to provide a method for accelerating the heating rate of carbon foam in such carbonization and graphitization processes.

  It is another object of the present invention to provide a process that does not adversely affect the physical and structural properties of the carbon foam during such accelerated heating.

(Summary of the Invention)
In accordance with the present invention, accelerated heating of the carbon foam material is achieved through the use of microwaves and induction heating devices while the carbon foam is in an inert atmosphere. In accordance with various preferred embodiments of the present invention, such microwave / induction heating acceleration is obtained through use of the microwave / induction heating device alone or in combination with more conventional radiation or convection-based heating devices. . The method and apparatus of the present invention allows for relatively rapid heating of the carbon foam material (especially in its carbonization and / or graphitization process).

(Detailed explanation)
US patent application Ser. No. 09 / 902,828 (filed Jul. 10, 2001) entitled “Cellular Coal Products and Processes” preferably has about 0.1 g / cm ³ and about 0.8 g / cm ³ . Production of a coal-based carbon foam having a density between, preferably up to 0.635 cm ( ¼ inch ) in diameter in a “mold” under non-oxidizing atmosphere, preferably it is prepared by highly volatile bituminous coal controlled pressurized thermal particles. In accordance with a particularly preferred embodiment, the starting coal has a free expansion index as determined by the ASTM D720 test described above. This index is between about 3.5 and about 5.0, and preferably between about 3.75 and 4.5. Thereby, preferably the porous product / carbon foam produced as net shape or close to net shape is machined, fixed and manufactured in other ways, with a wide variety of low-cost, low-cost It can produce a product of density or can be used as a filter, thermal insulator or electrical insulator in a matrix form. Such carbon foam has been shown to exhibit a compressive strength of about 272.18 atm ( 4000 psi ) without further processing and / or addition of reinforcing additives. Further processing by carbonization or graphitization yields a carbon foam that can be used as an electrical or thermal insulator.

The manufacturing method described in the U.S. Patent Application includes the following steps: 1) Coal particles, preferably small (ie, less than about 1/4 inch ) particle size, are placed in a “mold”. Heating to a temperature between about 300 ° C. and about 700 ° C. at a heating rate of about 1 to about 20 ° C. in a non-oxidizing atmosphere; 2) about 10 at a temperature between about 300 ° C. and about 700 ° C. immersed from minute to about 12 hours, the step of forming the preform product or final product; and 3) the matrix product or the final product, and controllably cooled to a temperature below about 100 ° C., "raw Obtaining a “ green foam”. Non-oxidizing atmosphere, an inert or non-oxidizing gas, about) 0 atm (0 psi) (i.e., provided by introducing into the "template" in the pressure from the flowing gas is not) to about 34.02atm (500psi) obtain. The inert gas used can be any of the commonly used inert or non-oxidizing gases (eg, nitrogen, helium, argon, CO _2, etc.).

Following the production of a “ raw foam” as described; the “ raw foam” can be subjected to carbonization and / or graphitization according to conventional processes to obtain specific properties desirable for a particular application. .

Carbonization (sometimes called calcination) heats the “ raw foam” to a temperature between about 800 ° C. and about 1200 ° C. under a suitable inert gas at a heating rate of less than about 5 ° C./min. Conventionally, by immersing for about 1 hour to about 3 hours or more. Suitable inert gases are those described above and they are resistant to these high temperatures. The inert atmosphere is supplied at atmospheric pressures from about 0 atm ( 0 psi ) to several atmospheres . The carbonization / calcination process serves to remove substantially all non-carbon volatile elements (eg, sulfur, oxygen, hydrogen, etc.) present in the “ raw foam”.

Graphitization is generally about 1700 at a heating rate of less than about 10 ° C./min (preferably about 1 ° C./min to about 5 ° C./min) in a helium or argon atmosphere either before or after carbonization. Heating the “ raw foam” to a temperature between 0 ° C. and about 3000 ° C. and soaking for a period of less than about 1 hour. Again, the inert gas may be supplied at a pressure in the range of about 0 atm ( 0 psi ) to several atmospheres.

As is apparent, carbonization and graphitization at a heating rate of 1-5 ° C./min at temperatures between about 1000 ° C. and about 3000 ° C. involves very long processing times (sometimes on a daily order). obtain. Such processing time is essentially necessary, in part due to the need to avoid cracking of the “ raw foam” due to heating too fast, but within the carbon foam mass This is mainly due to the inherent thermal insulation properties of “ raw foam” that resist the transfer of thermal energy from the outside of the structure to the internal location of the structure. Of course, the heating rate and total heating time will vary according to the shape, thickness, etc. of the particular carbon foam structure being processed, but as a general rule such heating in conventional radiant energy or convection ovens or ovens The time is excessively long, consuming large amounts of energy and variable device usage time. In addition, high temperature treatment of carbon foam in such devices often results in differential treatment of portions near the surface of the structure that reach the desired carbonization or graphitization temperature for several hours. Without being subjected to a high temperature for a longer period of time than the portion of the structure, at the “core” or center of the structure, which is maintained at that temperature for a minimum time to obtain the desired result. Such differential heating can result in “directional coking” from the outside to the inside of the carbon foam structure.

Microwave heating units may be advantageous in that they are more efficient and heat more uniformly than conventional radiant energy or convection ovens and convection ovens. A microwave oven or a microwave furnace generates electromagnetic waves, which move and rotate target molecules contained therein, thereby generating intramolecular friction. This intermolecular friction results in the internal generation of heat. On the other hand, such “internal” “frictional” heating is also more uniform, as shown below as being more rapid. This is because the whole mass to be heated tends to increase in temperature at a relatively uniform rate. Thus, relatively little difference exists between the part located outside and the part located inside the mass of the structure to be heated. Such relatively more uniform heating also results from significantly different temperatures achieved at different parts of the carbon structure during heating, while resulting in a more uniform generation of properties within the structure being heated. Resulting in less propensity to thermal cracks. The air or inert atmosphere in the microwave chamber does not heat due to the fact that the molecules in the gas are too dispersed to produce more friction or absorb most of the electromagnetic energy, and therefore even if radiation or convective pressurized heat occurs, it is small.

  The amount of thermal energy applied to the sample as a result of the microwave can change the power setting change in%. Using the equipment used for the studies reported below, the power setting actually only sets the time for the microwave to heat up to the adjusted actual power. For example, if the power is set to 40%, the microwave will heat for 40% of the time instead of 40% power. There are commercially available microwave ovens / furnaces with adjustable power settings that vary the power delivered to the contained sample, which are equally useful and possibly preferred and reduced for such systems. Continuous and uniform heating at a high power level is possible.

In accordance with the method of the present invention, by “ raw foam” (ie, as described hereinabove, US patent application Ser. No. 09 / 902,828, which is hereby incorporated by reference in its entirety). The material produced by controlled foaming of coal-based particles as detailed) is carbonized and / or graphitized using microwave energy to obtain more rapid and uniform heating, thereby producing carbon Reduces thermal cracking of the foam and significantly shortens the carbonization and / or graphitization treatment cycle.

  As will be apparent to those skilled in the art, the microwave-based heating method of the present invention can be applied alone or in conjunction with more conventional radiant energy or convection-based heating devices. In addition, although the microwave heating methods described herein are primarily described with respect to carbonization / graphitization of carbon foams produced from coal particles, these methods can include other starting materials (eg, Carbon foam that is the product of carbonization / graphitization of carbon foams produced from petroleum or synthetic pitch) and controlled foaming of blends of coal particles and petroleum or synthetic pitch, should be equally applicable Should be recognized.

Accordingly, the method of the present invention uses microwave energy to carbonize and / or carbonize “ raw foam” structures (ie, carbon foam masses) that have not been subjected to carbonization and / or graphitization in an inert atmosphere. Including graphitizing to obtain relatively more rapid and uniform heating .

  The power capability of the microwave device used in accordance with the present invention is particularly significant except that it should be a suitable power capability to achieve heating of the carbon foam structure in a short period of time. I don't have it.

  The applied microwave and the duration and change of power application varies from carbon foam material to carbon foam material according to the mass of carbon foam (ie, thickness, concentration, etc.), while the output parameters are trial and error Or it can be easily determined by experiment and can therefore vary widely depending on the characteristics of the carbon foam described above. As shown in the examples below, it has been found advantageous to increase the power level so that heating occurs. Such an increase in output can be easily determined again by experiment.

  The following examples serve to better illustrate the successful implementation of the present invention.

In all cases reported below, three holes are drilled into a 15.24 cm ( 6 inch ) thick sample of “ raw foam” and then placed in a 1500 watt microwave oven under an inert atmosphere, The output then increases over the time reported in Tables 1, 2 and 3 below. The table shows the Dwell time at a specific power level. Temperature measurements are made by inserting a thermocouple into a pre-drilled hole while the microwave is extinguished and at the indicated time intervals. In Example 1 (reported in Table 1), a “ raw foam” sample was placed directly on a microwave oven turntable. In Example 2 (reported in Table 2), the sample was placed on a refractory brick located on an oven turntable. In Example 3 (reported in Table 3), samples were placed on oven bricks and covered with insulating material.

Example 1
(Table 1)

.

(Example 2)
(Table 2)

.

Example 3
(Table 3)

.

  Thus, microwaves are very effective in heating carbon foams, indicating that tens of minutes can lead samples to 1000 ° C. The use of an insulating blanket is desirable for the experimental setup used in these tests. This is due to the need to access the sample to obtain temperature measurements. The location of the thermocouple in the sample, with access to it from the outside of the microwave device, eliminates the need for an insulating blanket. In the absence of inert atmosphere, samples (not reported) tend to be oxidized and in some cases burn, and thus such atmosphere is necessary.

  This experiment shows that a controlled atmospheric microwave heating unit with a programmable power / temperature controller can substantially reduce the time, energy and cost of producing calcined / graphitized carbon foam. .

  Fully graphitized foam samples at 2600 ° C. also show successful heating using microwave heating. This can complete graphitization to at least 2600 ° C. using microwaves at a calcination temperature of 1000 ° C., ranging from heat treatment to partial calcination of the carbon foam.

The above examples illustrate microwaves in reducing the processing time required for carbonization and / or graphitization of raw carbon foam (which is foamed and then processed separately in a microwave device). Although showing the effectiveness of heating, such operations can equally be performed by incorporating the microwave device into an autoclave or “mold” as described in the above-mentioned US patent application Ser. No. 09 / 902,828. It is. As a result, carbonization and / or graphitization can be achieved through the use of microwave heating in the same equipment used to achieve foaming.

In addition, a combination of microwave heating and convection or radiant heating can also be used under certain circumstances to ensure a complete and uniform temperature of the raw carbon foam.

Although the present invention has been described herein for the most part in terms of the use of microwave heating, induction heating can also be applied as well, which is a raw carbon foam structure for heating purposes. It shows the same result that induction heating, including the introduction of magnetic energy into, is equally useful. As in microwave device applications, the power level in an induction heating device and the duration of its application varies with the particular carbon foam being treated according to its density, thickness, composition, etc., but the appropriate processing parameters Can be readily determined by experiment.

  It will be apparent to those skilled in the art that as the invention has been described, the same can be modified in many ways without departing from the spirit and scope of the invention. Any and all such modifications are intended to be included within the scope of the appended claims.

Claims (8)

A method of carbonizing and / or graphitizing a raw carbon foam comprising:
Comprising the step of heating the carbon foam in the raw under an inert atmosphere by contacting the carbon foam microwave for a sufficient treatment period to achieve carbonization and / or graphitization method . A method of carbonizing and / or graphitizing a raw carbon foam comprising:
Comprising the step of heating the carbon foam in the raw under an inert atmosphere by contacting the carbon foam and magnetic energy for a sufficient treatment period to achieve carbonization and / or graphitization method . The method of claim 1, wherein the raw carbon foam is produced by controlled foaming of small particle size, highly volatile bituminous coal particles. The method of claim 1, wherein the raw carbon foam is produced by controlled foaming of a blend of small particle size highly volatile bituminous coal particles and petroleum pitch. The method of claim 1, wherein the raw carbon foam is produced by foaming a member selected from the group consisting of synthetic pitch, petroleum pitch, highly volatile bituminous coal particles and combinations and blends thereof. To be the way. The method of claim 1, wherein a power level or application time of the microwave irradiation varies over the processing period. The method according to claim 6, wherein the output level is increased over the processing period, method. The method according to claim 1, wherein said inert atmosphere is helium, argon, is selected from the group consisting of nitrogen and CO _2, the method.