Heteroatom-containing nanocarbon material, preparation method and use thereof, and method for dehydrogenation reaction of hydrocarbons

Patent metadata

Field	Value
Publication number	US-10537882-B2
Application number	US-201615546791-A
Country	US
Kind code	B2
Filing date	Jan 27, 2016
Priority date	Jan 27, 2015
Publication date	Jan 21, 2020
Grant date	Jan 21, 2020

Abstract

A heteroatom-containing nano-carbon material, based on the total weight of said heteroatom-containing nano-carbon material and calculated as the elements, has an oxygen content of 1-6 wt %, a nitrogen content of 0-2 wt %, a carbon content of 92-99 wt %. In its XPS, the ratio of the oxygen content as determined with the peak(s) in the range of 531.0-532.5 eV to the oxygen content as determined with the peak(s) in the range of 532.6-533.5 eV is 0.2-0.8; the ratio of the carbon content as determined with the peak(s) in the range of 288.6-288.8 eV to the carbon content as determined with the peak(s) in the range of 286.0-286.2 eV is 0.2-1; the ratio of the nitrogen content as determined with the peak(s) in the range of 398.5-400.1 eV to the total nitrogen content is 0.7-1. The heteroatom-containing nano-carbon material shows a good catalytic capability in dehydrogenation of hydrocarbons.

First claim

The invention claimed is:

1. A heteroatom-containing nano-carbon material, comprising: 92.2-97.8 wt % of carbon, 2-6 wt % oxygen, and 0.2-1.8 wt % nitrogen, wherein each of the weight percentages is of a weight of the corresponding element in a total weight of said heteroatom-containing nano-carbon material,
wherein, in said heteroatom-containing nano-carbon material, the content of the oxygen element as determined with the peak(s) in the range of 531.0-532.5 eV in an X-ray photoelectron spectrum is I O c , the content of the oxygen element as determined with the peak(s) in the range of 532.6-533.5 eV in the X-ray photoelectron spectrum is I O e , and I O c /I O e is 0.2-0.8;
the content of the carbon element as determined with the peak(s) in the range of 288.6-288.8 eV in the X-ray photoelectron spectrum is I C c , the content of the carbon element as determined with the peak(s) in the range of 286.0-286.2 eV in the X-ray photoelectron spectrum is I C e , and I C c /I C e is 0.2-1; and
the total content of the nitrogen element as determined with the X-ray photoelectron spectroscopy is I N t , the content of the nitrogen element as determined with the peak(s) in the range of 398.5-400.1 eV in the X-ray photoelectron spectrum is I N c , and I N c /I N t is 0.7-1.

2. The heteroatom-containing nano-carbon material according to claim 1 , wherein I O c /I O e is 0.35-0.85, and I C c /I C e is 0.3-0.98.

3. The heteroatom-containing nano-carbon material according to claim 1 , wherein I N c /I N t is 0.8-0.95.

4. The heteroatom-containing nano-carbon material according to claim 1 , wherein the content of the carbon element determined with the peak(s) in the range of 284.7-284.9 eV in the X-ray photoelectron spectrum is 20 wt % or higher; and the content of the carbon element determined with the peak(s) in the range of 284.7-284.9 eV in the X-ray photoelectron spectrum is 95 wt % or lower.

5. The heteroatom-containing nano-carbon material according to claim 1 , wherein said heteroatom-containing nano-carbon material is a heteroatom-containing carbon nanotube.

6. The heteroatom-containing nano-carbon material according to claim 5 , wherein said heteroatom-containing multi-walled carbon nanotube has a specific surface area of 50-500 m 2 /g.

7. The heteroatom-containing nano-carbon material according to claim 5 , wherein said heteroatom-containing multi-walled carbon nanotube has a weight loss difference w 800 in a temperature range of 400-800° C. and a weight loss difference w 500 in a temperature range of 400-500° C., w 500 /w 800 is 0.01-0.5, and said weight loss differences are measured in an air atmosphere.

8. The heteroatom-containing nano-carbon material according to claim 1 , wherein I O c /I O e is 0.3-0.8, the content of the carbon element determined with the peak(s) in the range of 284.7-284.9 eV in the X-ray photoelectron spectrum is 70-90 wt %, I C c /I C e is 0.3-0.9, and I N c /I N t is 0.7-0.98.

9. The heteroatom-containing nano-carbon material according to claim 1 , wherein I O c /I O e is 0.3-0.8, the content of the carbon element determined with the peak(s) in the range of 284.7-284.9 eV in the X-ray photoelectron spectrum is 70-90 wt %, I C c /I C e is 0.3-0.9, and I N c /I N t is 0.7-0.95.

10. The heteroatom-containing nano-carbon material according to claim 1 , wherein I O c /I O e is 0.3-0.8, the content of the carbon element determined with the peak(s) in the range of 284.7-284.9 eV in the X-ray photoelectron spectrum is 70-80 wt %, I C c /I C e is 0.4-0.98, and I N c /I N t is 0.7-0.95.

11. A process for preparing a heteroatom-containing nano-carbon material of claim 1 , comprising: placing a starting nano-carbon material dispersed in an aqueous dispersion in a close vessel to conduct a reaction, said aqueous dispersion contains an organic base, said organic base is an amine and/or a quaternary ammonium base, said aqueous dispersion is kept at a temperature in a range of 80-220° C. in the reaction.

12. The process of claim 11 , wherein the weight ratio of the starting nano-carbon material to water is 1:2-200.

13. The process according to claim 11 , wherein said aqueous dispersion contains at least one organic base, the weight ratio of the starting nano-carbon material to the organic base is 1:0.05-20.

14. The process according to claim 11 , wherein said organic base is selected from the group consisting of a compound represented by formula I, a compound represented by formula II, a compound represented by formula III and a substance represented by general formula R 12 (NH 2 ) 2 , R 12 is C 1 -C 6 alkylene or C 6 -C 12 arylene,

in formula I, R 1 , R 2 , R 3 and R 4 are each C 1 -C 20 alkyl or C 6 -C 12 aryl;

in the formula II, R 5 , R 6 and R 7 are each H, C 1 -C 6 alkyl or C 6 -C 12 aryl, and R 5 , R 6 and R 7 are not H at the same time; and

in the formula III, R 8 , R 9 and R 10 are each —R 11 OH, hydrogen or C 1 -C 6 alkyl, and at least one of R 8 , R 9 and R 10 is —R 11 OH, R 11 is C 1 -C 4 alkylene.

15. The process according to claim 11 , wherein said aqueous dispersion is kept at a temperature in a range of 120-180° C. in the reaction.

16. The process according to claim 11 , wherein said reaction is maintained for a period of 0.5-96 hours.

17. The process according to claim 11 , wherein in said starting nano-carbon material, the content of the oxygen element is lower than 1.2 wt %, the content of the nitrogen element is lower than 0.1 wt %.

18. The process according to claim 11 , wherein said starting nano-carbon material is a multi-walled carbon nanotube.

19. The process according to claim 18 , wherein said multi-walled carbon nanotube has a specific surface area of 20-500 m 2 /g.

20. The process according to claim 18 , wherein said multi-walled carbon nanotube has a weight loss difference w 800 in a temperature range of 400-800° C. and a weight loss difference w 500 in a temperature range of 400-500° C., w 500 /w 800 is 0.01-0.5, said weight loss differences are measured in an air atmosphere.

21. The process according to claim 11 , wherein the process further comprises separating a solid substance from the mixture obtained from the reaction, and drying and optionally calcining the separated solid substance.

22. The process according to claim 21 , wherein said drying is conducted at 50-200° C., said drying is maintained for a period of 0.5-48 hours.

23. The process according to claim 21 , wherein the separated solid substance is dried and calcined; wherein the calcination temperature is 250-500° C., and the calcination time is 1-24 hours.

24. The process according to claim 11 , wherein said organic base is a compound represented by formula I,

in formula I, R 1 , R 2 , R 3 and R 4 are each C 1 -C 20 alkyl or C 6 -C 12 aryl; and the weight ratio of the starting nano-carbon material to the organic base is 1:0.1-10, the temperature of the aqueous dispersion is maintained

Assignees

• China Petroleum & Chem Corp
• Res Institute Of Petroleum Processing
• Sinopec Res Inst Petroleum

Inventors

• Shi Chunfeng
• Rong Junfeng
• Yu Peng
• Xie Jingxin
• Zong Mingsheng
• Lin Weiguo

Classifications

• C07C11/08

  with four carbon atoms · CPC title

• B01J27/24 Primary

  Nitrogen compounds · CPC title

• B01J21/185

  Carbon nanotubes (carbon nanotubes per se C01B32/15) · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01B32/178 Primary

  Opening; Filling · CPC title