Modified carbon material and method for reducing carbonaceous material ignition temperature

Abstract

A modified carbon material, including a carbonaceous material and a water-insoluble modifier combined with the carbonaceous material, wherein the water-insoluble modifier is CuO, the carbonaceous material is one of or a mixture of biomass carbon or carbon black, a mass of the water-insoluble modifier is being 0.1-10 wt % of the carbonaceous material. The method for preparing the modified carbon material includes: (1) soaking the carbonaceous material in a copper sulfate solution for 5 to 36 hours, and (2) adding an alkali solution into a solution obtained in step (1) to provide a pH value ≥12, and after keeping the pH value for 0.5 to 2 hours, filtering and drying to obtain a solid. (3) using the carbonaceous material as a combustion heat source to reduce the ignition temperature, increase or reduce the peak thermal power temperature.

Claims

1. A method for preparing a modified carbon material comprising CuO wherein the method comprises the following steps: (1) obtaining a first solution by soaking a carbonaceous material in a copper sulfate solution for 5 to 36 hours, wherein a ratio of the carbonaceous material to the copper sulfate solution is controlled to control the CuO in the modified carbon material to be 1% by weight of the carbonaceous material; (2) adding an alkali solution into the first solution obtained in step (1) to provide a pH value ≥12, and after keeping the pH value for 0.5 to 2 hours, filtering and drying to obtain a solid, wherein the solid is the modified carbon material.

2. The method according to claim 1, wherein the copper sulfate solution in step (1) has a concentration of from 0.5 to 3 wt %.

3. The method according to claim 1, wherein the alkali solution in step (2) is a sodium hydroxide solution or a potassium hydroxide solution, with a concentration of from 1 to 50 wt %.

4. The method according to claim 1, wherein a drying temperature in step (2) is in a range from 80 to 95° C.

5. The method according to claim 1, wherein the carbonaceous material is carbon black.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a process flow diagram of the method for preparation of the modified carbon material of the invention.

(2) FIG. 2 shows thermogravimetric curves of the modified carbon powders in Examples 1-7 and 10000-mesh oak carbon powder.

(3) FIG. 3 shows differential thermogravimetric curves of the modified carbon powders in Examples 1-7 and 10,000-mesh oak carbon powder.

(4) FIG. 4 shows DSC curves of the modified carbon powders in Examples 1-7 and 10,000-mesh oak carbon powder.

(5) FIG. 5 shows thermogravimetric curves of the modified carbon powders in Examples 8-14 and C311 carbon black.

(6) FIG. 6 shows differential thermogravimetric curves of the modified carbon powders in Examples 8-14 and C311 carbon black.

(7) FIG. 7 shows DSC curves of the modified carbon powders in Examples 8-14 and C311 carbon black.

(8) FIG. 8 shows a thermogravimetric curve of the mixed carbon powder in Example 15.

(9) FIG. 9 shows a DSC curve of the mixed carbon powder in Example 15.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(10) The following specific embodiments are used to further describe the invention in detail. However, it should not be understood that the scope of the invention are only limited to the following examples. In the case of no departing from the concept of the method according to the invention, various substitutions and alterations that are made according to the common knowledge and conventional means in the art should be included within the scope of the invention.

(11) The process flow diagram of the method for producing the modified carbon material according to the invention is shown in FIG. 1.

Example 1

(12) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 6.25 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 6.25:100) for 24 h.

(13) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 10 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (2 wt % CuO) was obtained.

Example 2

(14) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 12.5 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 12.5:100) for 24 h.

(15) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 20 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (4 wt % CuO) was obtained.

Example 3

(16) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 18.75 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 18.75:100) for 24 h.

(17) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 20 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (6 wt % CuO) was obtained.

Example 4

(18) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 25 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 1:4) for 24 h.

(19) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 20 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (8 wt % CuO) was obtained.

Example 5

(20) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 3.13 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 3.13:100) for 24 h.

(21) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 1 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (1 wt % CuO) was obtained.

Example 6

(22) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 1.56 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 1.56:100) for 24 h.

(23) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 1 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (1 wt % CuO) was obtained.

Example 7

(24) (1) 10000-mesh oak carbon powder (prepared by carbonizing oak at high temperature and pulverizing it) was soaked in a CuSO.sub.4 solution with a concentration 1.56 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to oak carbon powder solid is 1.56:100) for 24 h.

(25) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 1 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with suction filtration to neutral and dried at 90° C., and after grinding, the modified carbon powder (0.5 wt % CuO) was obtained.

Example 8

(26) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 6.25 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 6.25:100) for 24 h.

(27) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 10 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the modified carbon powder (2 wt % CuO) was obtained.

Example 9

(28) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 12.5 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 12.5:100) for 24 h.

(29) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 20 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the modified carbon powder (4 wt % CuO) was obtained.

Example 10

(30) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 18.75 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 18.75:100) for 24 h.

(31) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 20 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the modified carbon powder (6 wt % CuO) was obtained.

Example 11

(32) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 25 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 1:4) for 24 h.

(33) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 20 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the modified carbon powder (8 wt % CuO) was obtained.

Example 12

(34) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 3.13 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 3.13:100) for 24 h.

(35) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 1 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the modified carbon powder (1 wt % CuO) was obtained.

Example 13

(36) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 1.56 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 1.56:100) for 24 h.

(37) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 1 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the modified carbon black (1 wt % CuO) was obtained.

Example 14

(38) (1) C311 carbon black (C311 is the trademark of the carbon black) was soaked in a CuSO.sub.4 solution with a concentration 1.56 g/L (the mass ratio of CuSO.sub.4.5H.sub.2O solid to C311 carbon black solid is 1.56:100) for 24 h.

(39) (2) The soaking solution in step (1) was stirred and during the stirring, a sodium hydroxide solution with a concentration of 1 wt % was slowly added thereto. Until the pH reaches 13, the addition of the sodium hydroxide solution was stopped and the solution was continuously stirred for 1 hour. The solution was washed with centrifugation to neutral and dried at 90° C., and after grinding, the CuO-modified carbon powder, cited as a modified carbon black (0.5 wt % CuO), was obtained.

(40) Tests and Analyses of Thermal Analytic Performances

(41) The tests used NETZSCH STA 449F3 thermal analyzer to conduct the thermal analytic tests directed to the products in Examples 1-14 and non-modified oak carbon powder and C311 carbon black at a temperature rising rate of 10° C./min in a simulated air atmosphere. Based on the thermal analytic data and according to GB/T 22204-2016 standards, the specific data of the combustion characteristics was calculated and shown in Tables 1 and 2. Table 1 shows the combustion characteristics of the modified oak carbon powder combined with different proportions of CuO; Table 2 shows the combustion characteristics of the modified C311 carbon black combined with different proportions of CuO.

(42) As shown in FIGS. 2, 3, 4 and Table 1, for the modified oak carbon powders with different amounts of CuO, the thermogravimetric curves, the differential thermogravimetric curves and the DSC curves exhibit regular movements toward low temperature zones, and the controls to the ignition temperature between 454.7 and 488.8° C. are realized. The other parameters of the combustion characteristics also can be effectively varied, in which the fractal of the DSC curve of the 4 wt % CuO-modified oak carbon powder has a peak in a widest and lowest shape, and the heat release is relatively mild during the temperature programming.

(43) TABLE-US-00001 TABLE 1 Combustion Characteristics of modified oak carbon powders combined with different proportions of CuO 0 wt % 0.5 wt % 1 wt % 2 wt % 4 wt % 6 wt % 8 wt % CuO CuO CuO CuO CuO CuO CuO Ignition 488.8 487.86 454.70 493.7 461.7 474.1 467.57 temperature ° C. Burning-off 583.2 554.91 528.95 564.7 545.2 554.1 548.4 temperature ° C. Maximum 10.32 12.90 10.89 12.17 9.71 10.23 10.06 combustion rate %/min Maximum 556.0 538.52 510.77 547.67 515.74 537.1 523.9 combustion rate temperature ° C. Peak heat power 40.12 56.61 46.74 45.00 37.51 38.96 40.77 mW/mg Peak thermal 565.7 545.12 518.86 556.3 518.1 546.0 531.5 power temperature ° C.

(44) As shown in FIGS. 5, 6, 7 and Table 1, for modified C311 carbon black with different amounts of CuO, the thermogravimetric curves, the differential thermogravimetric curves and the DSC curves remarkably move toward low temperature zone as compared to C311 carbon black, and the controls of the ignition temperature between 412.1 and 600.0° C. are realized. The other parameters of the combustion characteristics also can be effectively varied, and for example, the peak thermal powder is remarkably increased, and the peak thermal powder temperature is remarkably lowered.

(45) TABLE-US-00002 TABLE 2 Combustion Characteristics of modified C311 carbon black combined with different proportions of CuO 0 wt % 0.5 wt % 1 wt % 2 wt % 4 wt % 6 wt % 8 wt % CuO CuO CuO CuO CuO CuO CuO Ignition 600.0 412.1 413.1 449.34 443.76 443.10 431.93 temperature ° C. Burning-off 671 485.1 467 535.39 517.11 505.59 508.88 temperature ° C. Maximum 10.11 12.59 16.69 11.27 12.55 14.16 11.56 combustion rate %/min Maximum 644.83 460.56 446.91 486.92 493.63 479.46 468.51 combustion rate temperature ° C. Peak heat power 29.56 53.17 66.76 46.30 57.55 62.14 49.14 mW/mg Peak thermal 617.7 470 454.1 520.50 503.82 492.84 492.09 power temperature ° C.

Example 15

(46) The modified carbon black obtained in Example 2 and oak carbon powder were mixed in a mass ratio of 3:7 in a kneader while stirring to obtain a novel modified carbon powder which was further tested with the thermal analytical performances. From the curves shown in FIGS. 8 and 9, it can be seen that the novel modified carbon powder obtained after mixing has a wider and lower peak shape as compared to the modified carbon powder in Example 2 and the initial oak carbon powder, and it has a milder heat release during the temperature programming. The example demonstrates that for the CuO-modified carbon powder, a higher CuO amount will be not necessarily favorable.