Lignite char supported nano-cobalt composite catalyst and preparation method thereof

Abstract

The present disclosure provides a lignite char supported nano-cobalt composite catalyst and a preparation method thereof. In the method, lignite is used as a raw material, and a lignite char supported high dispersion nano-cobalt composite catalyst is obtained by a modified impregnation method followed by a high temperature pyrolysis process. The composite catalyst prepared by the present disclosure has a hierarchical pore structure, a high specific surface area, and uniformly dispersing nano-sized cobalts on the lignite char with controllable particle size, so that the obtained catalyst has an excellent catalytic activity for low-temperature CO.sub.2 methanation; moreover, the preparation process is simple and feasible, the raw materials used are cheap and easily available. Therefore, the composite catalyst is very suitable for industrial production and application.

Claims

1. A method for preparing a lignite char supported nano-cobalt composite catalyst, comprising the following steps: 1) crushing and screening original lignite blocks to obtain lignite particles; 2) adding a cobalt precursor and the lignite particles into a solvent and mixing, subjecting the lignite particles to an impregnating, and drying a resulting mixture after impregnating to obtain a solid substance A; and 3) subjecting the solid substance A to a high-temperature pyrolysis treatment to obtain the lignite char supported nano-cobalt composite catalyst; wherein adding the cobalt precursor and the lignite particles into a solvent and mixing, subjecting the lignite particles to the impregnating, and drying the resulting mixture after impregnating to obtain the solid substance A in step 2) comprises: adding the lignite particles to the solvent and ultrasonically dispersing, and then adding the cobalt precursor and continuing ultrasonically dispersing to form a mixed solution; stirring the mixed solution at a certain temperature until the solvent is fully volatilized, and drying remaining substance to obtain the solid substance A; and subjecting the solid substance A to a high-temperature pyrolysis treatment to obtain the lignite char supported nano-cobalt composite catalyst in step 3) comprises: heating the solid substance A to 700-900° C. at a heating rate of 0.5-10° C./min in an inert atmosphere, and holding for 1-6 h to obtain the lignite char supported nano-cobalt composite catalyst; wherein the lignite char supported nano-cobalt composite catalyst has a specific surface area of 350 m.sup.2/g-470 m.sup.2/g and a loading amount of nano-cobalt of 9 wt %-27 wt %.

2. The method as claimed in claim 1, wherein the process of stirring the mixed solution at a certain temperature until the solvent is fully volatilized comprises: stirring the mixed solution at ambient temperature until the solvent is fully volatilized, or stirring the mixed solution in a water bath at 30-60° C. for a period of time, and then continuing stirring the mixed solution at ambient temperature until the solvent is fully volatilized.

3. The method as claimed in claim 2, wherein before the process of adding a cobalt precursor and the lignite particles into a solvent and mixing in step 2), the method further comprises: subjecting the lignite particles to an acid treatment.

4. The method as claimed in claim 3, wherein the acid treatment comprises: adding the lignite particles into an acid solution that is selected from the group consisting of a nitric acid solution, a sulfuric acid solution and a hydrochloric acid solution, and stirring the resulting mixture in a water bath at a temperature ranging from ambient temperature to 55° C. for not less than 2 h.

5. The method as claimed in claim 1, wherein before the process of adding a cobalt precursor and the lignite particles into a solvent and mixing in step 2), the method further comprises: subjecting the lignite particles to an acid treatment.

6. The method as claimed in claim 5, wherein the acid treatment comprises: adding the lignite particles into an acid solution that is selected from the group consisting of a nitric acid solution, a sulfuric acid solution and a hydrochloric acid solution, and stirring the resulting mixture in a water bath at a temperature ranging from ambient temperature to 55° C. for not less than 2 h.

7. The method as claimed in claim 1, wherein a feeding percentage of cobalt in the cobalt precursor to the lignite particles in step 2) is in a range of 5 wt % to 15 wt %.

8. The method as claimed in claim 1, wherein in step 2), the cobalt precursor is selected from the group consisting of a cobalt salt and a cobalt salt solution, wherein the cobalt salt is selected from the group consisting of cobalt nitrate, cobalt carbonate and cobalt acetate, the solute of the cobalt salt solution is selected from the group consisting of cobalt nitrate, cobalt carbonate and cobalt acetate, and the solvent of the cobalt salt solution is selected from the group consisting of ethanol, water and a mixture of ethanol and water; and the solvent is selected from the group consisting of ethanol, water and a mixture of ethanol and water.

9. The method as claimed in claim 1, wherein the inert atmosphere is selected from the group consisting of argon, nitrogen and a mixed gas of argon and nitrogen.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The drawings forming a part of the present disclosure are intended to further assist in understanding the present disclosure, and the illustrative embodiments of the present disclosure and their descriptions are intended to illustrate the present disclosure, and do not make improper limitations to the scope of the present disclosure. In the drawings:

(2) FIG. 1 shows an XRD (Powder X-ray Diffraction) pattern of the lignite char supported nano-cobalt composite catalyst obtained in Example 1 of the present disclosure;

(3) FIG. 2 shows a TEM (Transmission Electron Microscopy) dark-field image (a) and a TEM bright-field image (b) of the lignite char supported nano-cobalt composite catalyst obtained in Example 1 of the present disclosure in the HAADF-STEM mode;

(4) FIG. 3 shows the nitrogen adsorption-desorption isotherm curves of the lignite char supported nano-cobalt composite catalysts obtained in Examples 1-4 of the present disclosure;

(5) FIG. 4 shows the CO.sub.2 conversion rate (a) and CH.sub.4 selectivity (b) of the lignite char supported nano-cobalt composite catalysts obtained in Examples 1 and 2 of the present disclosure at different temperatures and atmospheric pressure;

(6) FIG. 5 shows FT-IR spectra of the acid-washed lignite as prepared in Example 2 of the present disclosure and the lignite without the acid washing;

(7) FIG. 6 shows a TEM image (a) and the corresponding cobalt particle size distribution (b) of the lignite char supported nano-cobalt composite catalyst obtained in Example 2 of the present disclosure.

DETAILED DESCRIPTION

(8) It should be noted that the embodiments of the present disclosure and the features in the embodiments can be combined with each other when free from conflict.

(9) The present disclosure will be described in detail with reference to the drawings and examples.

Example 1

(10) A lignite char supported nano-cobalt composite catalyst was specifically prepared by the following process:

(11) 1) raw lignite blocks were crushed and screened to obtain lignite particles;

(12) 2) 2 g of lignite particles were weighed and dispersed in 100 g of ethanol, and the resulting mixture was ultrasonically dispersed for 5 min; 4.93 g of Co(NO.sub.3).sub.2 solution in ethanol (20 wt %) was added thereto (the feeding percentage of cobalt in the Co(NO.sub.3).sub.2 solution in ethanol to the lignite particles was 10 wt %), and the resulting mixture was ultrasonically dispersed for another 5 min; the mixed solution obtained by the ultrasonic dispersion was transferred to a stirrer and stirred in a water bath at 45° C. for 2 h to volatilize most of ethanol, then the water bath was cooled to ambient temperature, and the stirring was kept until the ethanol was fully volatilized, and the remaining substance was vacuum dried at 45° C. for 10 h to obtain a solid substance A;

(13) 3) the solid substance A was subjected to a high-temperature pyrolysis treatment at 700° C. in Ar for 2 h to obtain a lignite char supported nano-cobalt composite catalyst.

(14) The lignite char supported nano-cobalt composite catalyst of this example was subjected to an XRD test. The test result is shown in FIG. 1.

(15) It can be observed from FIG. 1 that the lignite char supported nano-cobalt composite catalyst of this example has a diffraction peak near 20=44°, corresponding to the crystal plane of Co (111), and the diffraction peak is weak and widened, indicating that the nano-cobalt particles have a small size.

(16) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a transmission electron microscope test, and the size of the cobalt particles was investigated and statistically analyzed. The test result is shown in FIG. 2.

(17) It can be observed from FIG. 2 that in the lignite char supported nano-cobalt composite catalyst of this example, the nano-cobalt particles were uniformly dispersed on the lignite char; the cobalt particles have a size distribution range of 3-15 nm and an average size of 9.3 nm.

(18) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a nitrogen absorption-desorption test. The result is shown in FIG. 3.

(19) It can be observed from FIG. 3 that the nitrogen adsorption-desorption isotherm curve of the lignite char supported nano-cobalt composite catalyst in this example shows that there are nano-scale pores in the sample, and the pore size calculation and analysis show that there are micropores, mesopores and macropores in the sample; the catalyst has a specific surface area of 359 m.sup.2/g and a pore volume of 0.158 cm.sup.3/g.

(20) The catalytic activity of the lignite char supported nano-cobalt composite catalyst in this example was evaluated as follows: a CO.sub.2 hydrogenation test was carried out on a fixed reaction bed under atmospheric pressure. The CO.sub.2 hydrogenation test under atmospheric pressure was carried out in a self-made fixed bed reactor, and the specific process was as follows:

(21) 200 mg of the composite catalyst sample was weighed and mixed with quartz sand, and the obtained mixture was added to a reaction tube; 10 wt % H.sub.2 was introduced into the reaction tube at a rate of 50 mL/min for pre-reduction at 400° C. for 2 h, and then it was switched to a reaction gas (H.sub.2:CO.sub.2=4:1) for a CO.sub.2 hydrogenation test, wherein during the test, the flow rate of the reaction gas was 25 mL/min; the reaction product was introduced into a gas chromatograph for analysis, and the analysis result was shown in FIG. 4.

(22) It can be observed from FIG. 4 that the lignite char supported nano-cobalt composite catalyst in this example has a CO.sub.2 conversion of 19.1% and a CH.sub.4 selectivity of 16.7% at 350° C.

Example 2

(23) A lignite char supported nano-cobalt composite catalyst was specifically prepared by the following process:

(24) 1) raw lignite blocks were crushed and screened to obtain lignite particles;

(25) 2) a certain amount of lignite particles were weighed and added into a 2 mol/L nitric acid solution, the resulting mixture was stirred in a water bath at 50° C. for 2 h to obtain a mixed solution; the mixed solution was filtered, and the obtained solid was washed with deionized water for several times and dried at 120° C. to obtain acid-washed lignite particles;

(26) 3) 2 g of the acid-washed lignite particles were weighed and dispersed in 100 g of ethanol, and the resulting mixture was ultrasonically dispersed for 5 min; 4.93 g of Co(NO.sub.3).sub.2 solution in ethanol (20 wt %) was added thereto (the feeding percentage of cobalt in the Co(NO.sub.3).sub.2 solution in ethanol to the lignite particles was 10 wt %) and the resulting mixture was ultrasonically dispersed for another 5 min; the mixed solution obtained by the ultrasonic dispersion was transferred to a stirrer and stirred in a water bath at 45° C. for 2 h to volatilize most of ethanol, then the water bath was cooled to ambient temperature and the stirring was kept until the ethanol was fully volatilized, and the remaining substance was vacuum dried at 45° C. for 10 h to obtain a solid substance A;

(27) 4) the solid substance A was subjected to a high-temperature pyrolysis treatment at 700° C. in Ar for 2 h to obtain a lignite char supported nano-cobalt composite catalyst.

(28) The acid-washed lignite particles of this example was analyzed by FT-IR and compared with the lignite particles without the acid washing. The test results are shown in FIG. 5.

(29) It can be observed from FIG. 5 that the absorption peak at 1710 cm.sup.−1 is assigned to the stretching vibration of C═O, which indicates that there are oxygen-containing functional groups on the surface of the lignite and the oxygen-containing functional groups on the surface are increased after the acid washing.

(30) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a nitrogen absorption-desorption test. The result is shown in FIG. 3.

(31) It can be observed from FIG. 3 that the nitrogen adsorption-desorption isotherm curve of the lignite char supported nano-cobalt composite catalyst in this example shows that there are nano-scale pores in the sample, and the pore size calculation and analysis show that there are micropores, mesopores and macropores in the sample; the catalyst has a specific surface area of 408 m.sup.2/g and a pore volume of 0.196 cm.sup.3/g.

(32) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a TEM test, and the size of the cobalt particles was investigated and statistically analyzed. The test result is shown in FIG. 6.

(33) It can be observed from FIG. 6 that the cobalt particles in the lignite char supported nano-cobalt composite catalyst have a size distribution range of 1-9 nm and an average size of 5.5 nm, and the nano-cobalt particles were uniformly dispersed on the lignite char.

(34) The catalytic activity of the lignite char supported nano-cobalt composite catalyst in this example was evaluated as follows: a CO.sub.2 hydrogenation test was carried out on a fixed reaction bed under atmospheric pressure. The CO.sub.2 hydrogenation test under atmospheric pressure was carried out in a self-made fixed bed reactor, and the specific process was as follows:

(35) 200 mg of the composite catalyst sample was weighed and mixed with quartz sand, and the obtained mixture was added to a reaction tube; 10 wt % H.sub.2 was introduced into the reaction tube at a rate of 50 mL/min for pre-reduction at 400° C. for 2 h, and then it was switched to a reaction gas (H.sub.2:CO.sub.2=4:1) for a CO.sub.2 hydrogenation test, wherein during the test, the flow rate of the reaction gas was 25 mL/min; the reaction product was introduced into a gas chromatograph for analysis, and the analysis result is shown in FIG. 4.

(36) It can be observed from FIG. 4 that the lignite char supported nano-cobalt composite catalyst in this Example has a CO.sub.2 conversion of 28.7% and a CH.sub.4 selectivity of 85.3% at 350° C.

Example 3

(37) This example differed from Example 2 only in that: in the preparation process of this example, the amount of Co(NO.sub.3).sub.2 solution in ethanol (20 wt %) added in step 3) was 2.47 g, corresponding to which the feeding percentage of cobalt in the Co(NO.sub.3).sub.2 solution in ethanol to the acid-washed lignite particles was 5 wt %, and other operations were the same as those in Example 2.

(38) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a TEM test, and the size of the cobalt particle was investigated and statistically analyzed.

(39) It can be known from the test that the cobalt particles in the lignite char supported nano-cobalt composite catalyst of this example have an average size of 5 nm.

(40) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a TG (Thermogravimetry) test in O.sub.2.

(41) From the calculation of the test results, it can be known that the loading amount of cobalt in the lignite char supported nano-cobalt composite catalyst of this example (cobalt:lignite char) is 9 wt %.

(42) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a nitrogen absorption-desorption test. The result is shown in FIG. 3.

(43) It can be observed from FIG. 3 that the nitrogen adsorption-desorption isotherm curve of the lignite char supported nano-cobalt composite catalyst in this example shows that there are nano-scale pores in the sample, and the pore size calculation and analysis show that there are micropores, mesopores and macropores in the sample; the catalyst has a specific surface area of 461 m.sup.2/g and a pore volume of 0.230 cm.sup.3/g.

Example 4

(44) This example differed from Example 2 only in that: in the preparation process of this example, the amount of Co(NO.sub.3).sub.2 solution in ethanol (20 wt %) added in step 3) was 7.41 g, corresponding to which the feeding percentage of cobalt in the Co(NO.sub.3).sub.2 solution in ethanol to the acid-washed lignite particles was 15 wt %, and other operations were the same as those in Example 2.

(45) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a TEM test, and the size of the cobalt particles was investigated and statistically analyzed.

(46) It can be known from the test that the cobalt particles in the lignite char supported nano-cobalt composite catalyst of this example have an average size of 6 nm.

(47) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a TG test in O.sub.2.

(48) From the calculation of the test results, it can be known that the loading amount of cobalt in the lignite char supported nano-cobalt composite catalyst of this example (cobalt:lignite char) is 27 wt %.

(49) The lignite char supported nano-cobalt composite catalyst of this example was subjected to a nitrogen absorption-desorption test. The result is shown in FIG. 3.

(50) It can be observed from FIG. 3 that the nitrogen adsorption-desorption isotherm curve of the lignite char supported nano-cobalt composite catalyst in this example shows that there are nano-scale pores in the sample, and the pore size calculation and analysis show that there are micropores, mesopores and macropores in the sample; the catalyst has a specific surface area of 380 m.sup.2/g and a pore volume of 0.175 cm.sup.3/g.

(51) The above are only preferred embodiments of the present disclosure, and are not used to limit the present disclosure. Any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present disclosure should be fall within the protection scope of the present disclosure.