Method of preparing iron carbide/carbon nanocomposite catalyst containing potassium for high temperature fischer-tropsch synthesis reaction and the iron carbide/carbon nanocomposite catalyst prepared thereby, and method of manufacturing liquid hydrocarbon using the same and liquid hydrocarbon manufactured thereby

Patent metadata

Field	Value
Publication number	US-9533292-B2
Application number	US-201314099083-A
Country	US
Kind code	B2
Filing date	Dec 6, 2013
Priority date	Mar 27, 2013
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

This invention relates to a method of preparing an iron carbide/carbon nanocomposite catalyst containing potassium for high temperature Fischer-Tropsch (FT) synthesis reaction and the iron carbide/carbon nanocomposite catalyst prepared thereby, and a method of manufacturing a liquid hydrocarbon using the same and a liquid hydrocarbon manufactured thereby, wherein a porous carbon support is uniformly impregnated with an iron hydrate using melt infiltration, and potassium is also supported together via various addition processes, including a pre-addition process of a potassium salt which is ground upon impregnation with the iron hydrate, or a mid- or post-addition process of a potassium solution using incipient wetness impregnation after impregnation with the iron hydrate. Accordingly, the highly active iron carbide/potassium/carbon composite catalyst for high temperature FT reaction in which 5˜30 wt % of active iron carbide particles are supported on the porous carbon support can be obtained and is structurally stable to heat even in high temperature FT reaction of 300° C. or more, and liquid hydrocarbons can be selectively obtained at high yields.

First claim

What is claimed is:

1. A method of preparing an iron carbide and carbon carbide/carbon nanocomposite catalyst containing potassium for high temperature Fischer-Tropsch synthesis reaction, comprising:
mechanically uniformly grinding non-liquid reagents: an iron hydrate powder, a potassium salt powder and a porous carbon support powder, thus forming a mixed powder wherein the carbon support is not in the form of carbon nanotubes;
subjecting the mixed powder to melt infiltration at a temperature near a melting point of the iron hydrate in a reaction vessel;
drying the mixed powder at room temperature;
calcining the dried mixed powder at a high temperature in an activation gas atmosphere selected from CO and a mixture of CO and H 2 , so as to be activated to form iron carbide particles containing potassium on the carbon support, thus obtaining an iron carbide and carbon nanocomposite catalyst containing potassium;
adding the calcined iron carbide and carbon nanocomposite catalyst containing potassium to an organic solvent so as to be stabilized via anti-oxidation passivation; and
recovering the iron carbide and carbon nanocomposite catalyst containing potassium from the organic solvent using a magnet, and then performing vacuum drying.

2. The method of claim 1 , wherein the iron hydrate is supported in an amount of 0.5˜3.0 g per unit gram of the carbon support.

3. The method of claim 1 , wherein an amount of an iron element decomposed from the iron hydrate is 5˜30 wt %, and an amount of a potassium element is 0.1˜3.0 wt %, based on a total amount of the catalyst including the carbon support.

4. The method of claim 1 , wherein the iron hydrate has a melting point of 30˜100° C.

5. The method of claim 4 , wherein the melt infiltration is performed in a closed system under a temperature condition in which a temperature of the reaction vessel is set to be higher by 2˜5° C. than the melting point of the iron hydrate.

6. The method of claim 1 , wherein the iron hydrate is at least one selected from among Fe(NO 3 ) 3 9H 2 O (d=1.68 g/cm 3 , m.p.=47.2° C.), FeCl 3 6H 2 O (d=1.82 g/cm 3 , m.p.=37° C.), and FeSO 4 7H 2 O (1.898 g/cm 3 , m.p.=70° C.).

7. The method of claim 1 , wherein the porous carbon support has a minimum pore volume of 0.2 cm 3 /g or more.

8. The method of claim 1 , wherein the porous carbon support is any one selected from among commercially available activated carbon, commercially available activated charcoal, commercially available acetylene carbon black, and ordered mesoporous carbon CMK (CMK-3, CMK-5, CMK-8).

9. The method of claim 1 , wherein the calcining is performed at 300˜400° C.

10. The method of claim 1 , wherein the calcining is performed for 1˜24 hr while allowing the activation gas at a rate of 100 ml or more per min.

11. The method of claim 1 , wherein the organic solvent is any one selected from among ethanol and mineral oil.

12. A method of preparing an iron carbide and carbon nanocomposite catalyst containing potassium for high temperature Fischer-Tropsch synthesis reaction, comprising:
mechanically uniformly grinding non-liquid reagents: an iron hydrate powder and a porous carbon support powder, thus forming a mixed powder wherein the carbon support is not in the form of carbon nanotubes;
subjecting the mixed powder to melt infiltration at a temperature near a melting point of the iron hydrate in a reaction vessel;
drying the mixed powder at room temperature;
impregnating the dried mixed powder with a potassium salt aqueous solution using incipient wetness impregnation;
calcining the mixed powder impregnated with potassium at a high temperature in an activation gas atmosphere selected from CO and a mixture of CO and H 2 so as to be activated to form iron carbide particles containing potassium on the carbon support, thus obtaining an iron carbide and carbon nanocomposite catalyst containing potassium;
adding the calcined iron carbide and carbon nanocomposite catalyst containing potassium to an organic solvent so as to be stabilized via anti-oxidation passivation; and
recovering the iron carbide and carbon nanocomposite catalyst containing potassium from the organic solvent using a magnet, and then performing vacuum drying.

13. The method of claim 12 , wherein the iron hydrate is supported in an amount of 0.5˜3.0 g per unit gram of the carbon support.

14. The method of claim 12 , wherein an amount of an iron element decomposed from the iron hydrate is 5˜30 wt %, and an amount of a potassium element is 0.1˜3.0 wt %, based on a total amount of the catalyst including the carbon support.

15. The method of claim 12 , wherein the iron hydrate has a melting point of 30˜100° C.

16. The method of claim 12 , wherein the iron hydrate is at least one selected from among Fe(NO 3 ) 3 9H 2 O (d=1.68 g/cm 3 , m.p.=47.2° C.), FeCl 3 6H 2 O (d=1.82 g/cm 3 , m.p.=37° C.), and FeSO 4 7H 2 O (1.898 g/cm 3 , m.p.=70° C.).

17. The method of claim 12 , wherein the porous carbon support has a minimum pore volume of 0.2 cm 3 /g or more.

18. The method of claim 12 , wherein the porous carbon support is any one selected from among commercially available activated carbon, commercially available activated charcoal, commercially available acetylene carbon black, and ordered mesoporous carbon CMK (CMK-3, CMK-5, CMK-8).

19. The method of claim 12 , wherein the calcining is performed at 300˜400° C.

20. The method of claim 12 , wherein the calcining is performed for 1˜24 hr while allowing the activation gas at a rate of 100 ml or more per min.

21. The method of claim 12 , wherein the melt infiltration is performed in a closed system under a temperature condition in which a temperature of the reaction vessel is set to be higher by 2˜5° C. than the melting point of the iron hydrate.

22. The method of claim 12 , wherein the organic solvent is any one selected from among ethanol and mineral oil.

23. The method of claim 12 , wherein the potassium salt is used in a solution form by being dissolved in water or an organic solvent, and is any one or more selected from among KOH, KI, KCl, KBr, K 2 CO 3 , K 2 Cr 2 O 7 , KNO 3 , KC 2 H 3 O 2 , KMnO 4 , KCN, KIO 3 , K 2 S 2 O 8 , K 2 SO 4 , KSCN, KClO 3 , KF, KH, KH 2 PO 4 , C 4 H 9 KO, and C 6 H 5 K 3 O 7 .

24. A method of preparing an iron carbide and carbon nanocomposite catalyst containing potassium for high temperature Fischer-Tropsch synthesis reaction, comprising:
mechanically uniformly grinding non-liquid reagents: an iron hydrate powder and a porous carbon support powder, thus forming a mixed powder wherein the carbon support is not in the form of carbon nanotubes;
subjecting the mixed powder to melt infiltration at a temperature near a melting point of the iron hydrate in a reaction vessel;
drying the mixed powder at room temperature;
calcining the dried mixed powder at a high temperature in an activation gas atmosphere selected from CO and a mixture of CO and H 2 so as to be activated to form pure iron carbide particles on the carbon support, thus obtaining an iron carbide and carbon nanocomposite catalyst;
adding the calcined iron carbide and carbon nanocomposite catalyst to an organic solvent so as to be stabilized via anti-oxidation passivation, and then performing drying;
impregnating the dried mixed powder with a potassium salt aqueous solution using incipient wetness impregnation;
calcining the mixed powder impregnated with potassium at a high temperature in an activation gas at

Assignees

• Korea Energy Research Inst

Inventors

• Park Ji Chan
• Jung Heon
• Lee Ho Tae
• Yang Jung Il
• Chun Dong Hyun
• Hong Sung Jun

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J37/08 Primary

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title