Abstract
The invention provides a method for making multiporous carbon material from a bio-oil produced by a biomass thermochemical process. The bio-oil is blended with a resin and a Zinc Oxide (ZnO) template as a major component of a precursor. The pore sizes of the carbon material made by the invention comprise mesopores and micropores to form the multiporous carbon material. The main production steps include: (1) mixing the precursor with a crusher, (2) packing the precursor, (3) heating for carbonization: holding 350 C. for 1 hour then holding 900 C. for 2 hours, and (4) washing the ZnO with hydrochloric acid by adjusting the pH value to less than 1.
Claims
1. A method for making a multiporous carbon material, which comprises the steps of: (1) mixing a carbon source and a template to obtain a precursor; wherein the template comprises zinc oxide, the carbon source is a bio-oil, and the weight percentage of the carbon source and the template relative to the precursor is 15-25% and 75-85%, respectively; (2) placing the precursor in a low oxygen atmosphere; (3) raising a temperature to 250400 C. in an environment of the low oxygen atmosphere, and waiting for the precursor to carbonize; (4) raising the temperature to 800900 C. in the environment of the low oxygen atmosphere, and holding the temperature for a reaction time to obtain a carbonized mixture; (5) washing the carbonized mixture with an acidic solution having a pH lower than 1 to remove the template; and (6) washing the carbonized mixture to remove the remaining acidic solution, and obtaining the multiporous carbon material; wherein the low oxygen atmosphere is an environment in which the oxygen content is 0.5% or less, wherein the bio-oil is carbonized tar, wherein a high calorific value of the carbonized tar is in the range of 3,5007,000 cal/g.
2. The method of claim 1, wherein an oxygen content of the bio-oil is in the range of 2060%.
3. The method of claim 1, wherein the template comprises calcium carbonate.
4. The method of claim 1, wherein the template has a size ranging from 5100 nm.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) FIG. 1 is a schematic diagram of the process making multiporous carbon material by mixing raw biomass chemical oil of the present invention.
(2) FIG. 2 is a characteristic curve shows the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:bio-oil=4:1) in the example 1 of the present invention.
(3) FIGS. 3A and 3B show the transmission electron microscopic images of the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:bio-oil=4:1) in the example 1 of the present invention.
(4) FIG. 4 shows the characteristic curve of the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:carbon powder=6:1) in the example 2 of the present invention.
(5) FIG. 5 shows a representative perforated electron microscope image of the multiporous carbon material of the second embodiment of the present invention.
(6) FIG. 6 is a characteristic curve of the multiporous carbon material measured at an average value and maximum value (precursor:ZnO:bio-oil:carbon powder=22:4:1) in the example 3 of the present invention.
(7) FIG. 7 is a characteristic curve of the multiporous carbon material measured at an average value and maximum value (precursor:ZnO:carbonized tar=4:1) in the example 4 of the present invention.
(8) FIG. 8 is a characteristic curve of the multiporous carbon material measured at an average value and maximum value (precursor:ZnO:carbonized tar:phenolic resin=8:1:1) in the example 4 of the present invention.
(9) FIG. 9 shows a representative perforated electron microscope image of the multiporous carbon material in the example 5 of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
(10) By way of illustration, the specific embodiments will be disclosed in detail below, however, the features of the invention are not limited to these embodiments.
(11) Please refer to FIG. 1 to FIG. 9, which further illustrate the details of method for making multiporous carbon material of the present invention.
(12) Please refer to FIG. 1, which is a flow chart showing a method for making multiporous carbon material, which comprises the steps of: (1) Mixing a carbon source, a template and a resin, to obtain a precursor S201, wherein the carbon source is a bio-oil or a carbon powder; the bio-oil is a pyrolysis oil, a carbonized tar, a lignin or a liquid phase product by carbonization, thermal cracking, gasification from a raw material; the oxygen content of the bio-oil is in the range of 2060%; the high calorific value of the bio-oil is in the range of 3,5004,500 cal/g; the high value of the carbonized tar is in the range of 3,5007,000 cal/g; the carbon powder is produced by a pyrolysis process; the resin is a phenolic resin; the template is zinc oxide or calcium carbonate; the template has a size ranging from 5100 nm; the weight of the template is 5095% by weight based on the total weight of the precursor. (2) Placing the precursor in a low oxygen atmosphere S102, wherein the low oxygen environment is an environment in which the oxygen content is 0.5% or less; (3) Raising the temperature to 250400 C. in the environment of the low oxygen atmosphere, and waiting the mixture to carbonization S103; (4) Raising the temperature to 800900 C. in the environment of the low oxygen atmosphere, and holding the temperature for a reaction time to obtain a carbonated mixture S104; (5) Washing the carbonized mixture with an acidic solution having a pH lower than 1 to remove the template S105; and (6) Washing the carbonized mixture to remove the remaining acidic solution, and obtaining a multiporous carbon material S106.
(13) The multiporous carbon material obtained by the method for making multiporous carbon material of the present invention, having micropores and mesopores, wherein the surface area ratio of the micropores ranges from 0 to 30%.
(14) The following five examples show the process for producing a multiporous carbon material by using different components and different weight ratios of mixture from the bio-oil as a precursor respectively. The and the process of producing the multiporous carbon material of FIG. 1 show the characteristics of multiporous carbon material.
Example 1
(15) As shown in FIG. 2, FIG. 3 and Table 1, the characteristic curve shows the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:bio-oil=4:1) in the example 1 of the present invention and the multiporous carbon material. The process of making the multiporous carbon material by using the bio-oil is shown in FIG. 1, The precursor is prepared at a 4:1 weight ratio of ZnO and bio-oil. From the above measurement data, the multiporous carbon material has high surface area, which is mainly contributed by the surface area of the micropores and mesopores.
(16) TABLE-US-00001 TABLE 1 Surface area micropores mesopores yield ratio (m.sup.2/g) (m.sup.2/g) (m.sup.2/g) (%) 4/1 1505 337 1167 13.2
Example 2
(17) As shown in FIG. 4, FIG. 5 and Table 2, the transmission electron microscopic images show the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:carbon powder=6:1) in the example 2 of the present invention and the multiporous carbon material. The process of making the multiporous carbon material by using the bio-oil is shown in FIG. 1, The precursor is prepared at a 6:1 weight ratio of ZnO and carbon powder. From the above measurement data, the multiporous carbon material has high surface area, which is mainly contributed by the surface area of the micropores and mesopores.
(18) TABLE-US-00002 TABLE 2 Surface area micropores mesopores yield ratio (m.sup.2/g) (m.sup.2/g) (m.sup.2/g) (%) 6/1 1127 661 466 30.2
Example 3
(19) As shown in FIG. 6 and Table 3, the characteristic curve shows the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:bio-oil:carbon powder=22:4:1) in the example 1 of the present invention and the multiporous carbon material. The process of making the multiporous carbon material by using the bio-oil is shown in FIG. 1, The precursor is prepared at a 22:4:1 weight ratio of ZnO, bio-oil and carbon powder. From the above measurement data, the multiporous carbon material has high surface area, which is mainly contributed by the surface area of the micropores and mesopores.
(20) TABLE-US-00003 TABLE 3 Surface area micropores mesopores yield ratio (m.sup.2/g) (m.sup.2/g) (m.sup.2/g) (%) 22/4/1 1454 636 818 13.7
Example 4
(21) As shown in FIG. 7 and Table 4, the characteristic curve shows the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:carbonized tar=4:1) in the example 1 of the present invention and the multiporous carbon material. The process of making the multiporous carbon material by using the bio-oil is shown in FIG. 1, The precursor is prepared at a 4:1 weight ratio of ZnO and carbonized tar. From the above measurement data, the multiporous carbon material has high surface area, which is mainly contributed by the surface area of the micropores and mesopores.
(22) TABLE-US-00004 TABLE 4 Surface area micropores mesopores yield ratio (m.sup.2/g) (m.sup.2/g) (m.sup.2/g) (%) 4/1 983 265 718 6.2
Example 5
(23) As shown in FIG. 8, FIG. 9 and Table 5, the characteristic curve shows the multiporous carbon material measured at an average value and maximum value (precursor-ZnO:carbonized tar:phenolic resin=8:1:1) in the example 5 of the present invention and the multiporous carbon material. The process of making the multiporous carbon material by using the bio-oil is shown in FIG. 1, The precursor is prepared at a 8:1:1 weight ratio of ZnO, carbonized tar and phenolic resin. From the above measurement data, the multiporous carbon material has surface area, which is mainly contributed by the surface area of the micropores and mesopores.
(24) TABLE-US-00005 TABLE 5 Surface area micropores mesopores yield ratio (m.sup.2/g) (m.sup.2/g) (m.sup.2/g) (%) 8/1/1 1685 102 1583 7.5
(25) Although the present invention has been described in terms of specific exemplary embodiments and examples, it will be appreciated that the embodiments disclosed herein are for illustrative purposes only and various modifications and alterations might be made by those skilled in the art without departing from the spirit and scope of the invention as set forth in the following claims.
