Synthesis of ordered microporous carbons by chemical vapor deposition

Patent metadata

Field	Value
Publication number	US-9604194-B2
Application number	US-201414513707-A
Country	US
Kind code	B2
Filing date	Oct 14, 2014
Priority date	Oct 14, 2014
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

A methane microporous carbon adsorbent comprising a thermally-treated CVD carbon having a shape in the form of a negative replica of a crystalline zeolite has a BET specific surface area, a micropore volume, a micropore to mesopore volume ratio, a stored methane value and a methane delivered value and a sequential carbon synthesis method for forming the methane microporous carbon adsorbent. Introducing an organic precursor gas for a chemical vapor deposition (CVD) period to a crystalline zeolite that is maintained at a CVD temperature forms the carbon-zeolite composite. Introducing a non-reactive gas for a thermal treatment period to the carbon-zeolite composite maintained at a thermal treatment temperature forms the thermally-treated carbon-zeolite composite. Introducing an aqueous strong mineral acid mixture to the thermally-treated carbon-zeolite composite forms the methane microporous carbon adsorbent.

First claim

What is claimed is:

1. A sequential carbon synthesis method for forming a methane microporous carbon adsorbent, the method comprising the steps of:
introducing an organic precursor gas comprising an organic precursor for a chemical vapor deposition (CVD) period to a crystalline zeolite that is maintained at a CVD temperature such that a carbon-zeolite composite forms, where the introduced organic precursor adsorbs via CVD into the crystalline zeolite, the organic precursor converts into carbon within the crystalline zeolite forming a carbon template of a zeolite;
introducing a non-reactive gas for a thermal treatment period to the carbon-zeolite composite maintained at a thermal treatment temperature such that the thermally-treated carbon-zeolite composite forms, where the carbon template of the zeolite within the crystalline zeolite converts into a thermally-treated carbon template of the zeolite;
introducing an aqueous strong mineral acid mixture to the thermally-treated carbon-zeolite composite such that crystalline zeolite dissolves and the methane microporous carbon adsorbent forms, where the methane microporous carbon adsorbent is a negative replica of the crystalline zeolite, has a BET specific surface area, a micropore volume, a micropore to mesopore volume ratio, a stored methane value and a methane delivered value; and
forming the crystalline zeolite, wherein forming the crystalline zeolite comprises ion-exchanging a first crystalline zeolite with calcium ions to form a second crystalline zeolite.

2. The method of claim 1 where the organic precursor is selected from the group consisting of acetylene, ethylene, propylene, ethanol and combinations thereof.

3. The method of claim 1 where the organic precursor gas further comprises the non-reactive gas.

4. The method of claim 1 where the CVD period is in a range of from 2 hours to 9 hours.

5. The method of claim 1 where the CVD temperature is in a range of from 800 K to 900 K.

6. The method of claim 1 where the non-reactive gas is selected from the group consisting of helium, argon and combinations thereof.

7. The method of claim 1 where the thermal treatment period is in a range of from 2 hours to 4 hours.

8. The method of claim 1 where the thermal treatment temperature is in a range of from 1100 K to 1200 K.

9. The method of claim 1 where the strong mineral acid is selected from the group consisting of hydrochloric acid (HCl), hydrofluoric acid (HF) and combinations thereof.

10. The method of claim 1 where the crystalline zeolite is selected from the group consisting of FAU, EMT, BEA zeolite structures, and combinations of the zeolite structures thereof.

11. The method of claim 1 where the crystalline zeolite has a shape that is orthogonal with a mid-edge length in a range of 8 μm to 20 μm.

12. The method of claim 1 where the crystalline zeolite comprises tri-ethanolamine (TEA).

13. The method of claim 1 further comprising the steps of:
introducing the organic precursor gas comprising the organic precursor for a second CVD period to the thermally-treated carbon-zeolite composite that is maintained at a second CVD temperature such that a second carbon-zeolite composite forms, where the organic precursor adsorbs via CVD into the thermally-treated carbon-zeolite composite, the organic precursor converts into carbon within the thermally-treated carbon-zeolite composite and both the carbon and the thermally-treated carbon-zeolite composite form a second carbon template of a zeolite; and
introducing the non-reactive gas for a second thermal treatment period to the second carbon-zeolite composite maintained at a second thermal treatment temperature such that a second thermally-treated carbon-zeolite composite forms, where the second carbon template of the zeolite within the second carbon-zeolite composite converts into a second thermally-treated carbon-zeolite composite;
where both of these steps occur before the introduction of the aqueous strong mineral acid mixture, and
where the aqueous strong mineral acid mixture is introduced to the second thermally-treated carbon-zeolite composite instead of the thermally-treated carbon-zeolite composite.

14. The method of claim 13 where the CVD temperature and the second CVD temperature are the same.

15. The method of claim 13 where the CVD period and the second CVD period are the same.

16. The method of claim 13 where the thermal treatment temperature and the second thermal treatment temperature are the same.

17. The method of claim 13 where the thermal treatment period and the second thermal treatment period are the same.

Assignees

• Saudi Arabian Oil Co
• Korea Advanced Inst Sci & Tech

Inventors

• Wang Yuguo
• Ercan Cemal
• Othman Rashid M
• Choi Minkee
• Choi Seokin

Classifications

• C01B32/306

  with molecular sieve properties · CPC title

• C01B32/05

  Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30 · CPC title

• Y02C20/20

  of methane · CPC title

• B01J2219/00157

  by means of a burner · CPC title

• B01D2259/4525

  for storage and dispensing systems · CPC title