Cobalt-based catalyst on metal structure for selective production of synthetic oil via fischer-tropsch reaction, method of preparing the same, and method of selectively producing synthetic oil using the same

Patent metadata

Field	Value
Publication number	US-2016303555-A1
Application number	US-201314391847-A
Country	US
Kind code	A1
Filing date	Oct 24, 2013
Priority date	Oct 22, 2013
Publication date	Oct 20, 2016
Grant date	—

Abstract

This invention relates to a cobalt-based catalyst on a metal structure for selective production of synthetic oil via Fischer-Tropsch reaction, a method of preparing the same and a method of selectively producing synthetic oil using the same, wherein zeolite, cobalt and a support are mixed and ground to give a catalyst sol, which is then uniformly thinly applied on the surface of a metal structure using a spray-coating process, thereby preventing generation of heat during Fischer-Tropsch reaction and selectively producing synthetic oil having a carbon chain shorter than that of wax. This catalyst is prepared by burning a powder mixture obtained by melt infiltration of a cobalt hydrate and a metal oxide support to give a catalyst powder including cobalt oxide/metal oxide support; hybridizing the catalyst powder including cobalt oxide/metal oxide support with a zeolite powder to give a hybrid catalyst powder; mixing the hybrid catalyst powder with an organic binder and an inorganic binder and grinding the mixed hybrid catalyst powder to give a hybrid catalyst sol; spray-coating a metal structure surface-treated with alumina by atomic layer deposition with the hybrid catalyst sol; and thermally treating the metal structure spray-coated with the hybrid catalyst sol.

First claim

1 . A method of preparing a cobalt-based catalyst on a metal structure for selective production of a synthetic oil via Fischer-Tropsch reaction, comprising:
burning a powder mixture obtained by melt infiltration of a cobalt hydrate and a metal oxide support to give a catalyst powder comprising cobalt oxide/metal oxide support; hybridizing the catalyst powder comprising cobalt oxide/metal oxide support with a zeolite powder to give a hybrid catalyst powder; mixing the hybrid catalyst powder with an organic binder and an inorganic binder and grinding the mixed hybrid catalyst powder to give a hybrid catalyst sol; spray-coating a metal structure surface-treated with alumina by atomic layer deposition with the hybrid catalyst sol; and thermally treating the metal structure spray-coated with the hybrid catalyst sol.

2 . The method of claim 1 , wherein mixing the hybrid catalyst powder with the organic binder and the inorganic binder and grinding the mixed hybrid catalyst powder to give the hybrid catalyst sol comprises preparing a hybrid catalyst sol further comprising ruthenium.

3 . The method of claim 1 , wherein the cobalt hydrate is any one selected from among Co(NO 3 ) 2 6H 2 O (m.p.=55° C.), CoCl 2 6H 2 O (m.p.=86° C.), and CoSO 4 7H 2 O (m.p.=96.8° C.).

4 . The method of claim 1 , wherein the cobalt oxide is loaded in an amount of 15˜40 wt % based on a total weight of the catalyst comprising the metal oxide support that is thermally decomposed at a high temperature after infiltration.

5 . The method of claim 1 , wherein the metal oxide support is a porous silica or alumina having a pore volume of 0.4 cm 3 /g or more and an effective surface area of 100 m 2 /g or more.

6 . The method of claim 1 , wherein the burning is performed by thermal treatment at 300˜500° C. in an atmosphere, thus obtaining cobalt oxide particles having a size of 5˜50 nm.

7 . The method of claim 1 , wherein the melt infiltration is performed for 1˜48 hr in a closed system at a temperature 2˜5° C. higher than a melting point of the cobalt hydrate.

8 . The method of claim 1 , wherein the zeolite is added such that an amount thereof is 5˜30 wt % based on a total weight of the hybrid catalyst.

9 . The method of claim 1 , wherein the hybrid catalyst sol is prepared in such a manner that the hybrid catalyst powder is added in an amount of 1˜10 wt % to a dispersion solution comprising the organic binder, the inorganic binder and a solvent mixture of distilled water and ethanol, ground to a size of 900 nm or less and dispersed.

10 . The method of claim 9 , wherein the organic binder is PVB (Polyvinyl butyral), PVP (Polyvinylpyrrolidone) or PVA (Polyvinyl alcohol), and the inorganic binder is alumina sol or silica sol.

11 . The method of claim 1 , wherein the metal structure comprises nickel, copper or a combination of nickel and copper, with a pore size of 1.2˜0.45 mm.

12 . The method of claim 1 , wherein the atomic layer deposition is performed a total of 60˜100 cycles at a substrate temperature of 120° C. so that alumina has a thickness of 12˜20 nm.

13 . The method of claim 1 , wherein the hybrid catalyst sol is sprayed on the metal structure at a rate of 1˜10 mL/sec upon spray-coating, so that an amount of loaded hybrid catalyst sol per an area of the metal structure is 4˜40 mg/cm 2 .

14 . The method of claim 13 , wherein a temperature of a support plate for supporting a bottom of the metal structure is maintained at 40˜90° C.

15 . The method of claim 2 , wherein the ruthenium is contained in an amount of 1˜5 wt % based on a total weight of a catalyst comprising cobalt oxide/ruthenium/metal oxide support obtained by dissolving a ruthenium salt in a hybrid catalyst sol solution, coating the metal structure with the hybrid catalyst sol, and performing burning and thermal treatment to result in decomposition.

16 . A cobalt-based catalyst on a metal structure for selective production of a synthetic oil via Fischer-Tropsch reaction, prepared by the method of claim 1 .

17 . A method of selectively producing a synthetic oil using a cobalt-based catalyst on a metal structure via Fischer-Tropsch reaction, comprising: reacting the cobalt-based catalyst of claim 16 with a synthetic gas comprising carbon monoxide and hydrogen at a volume ratio of 1:2 in a reactor, thus producing a C 5-12 synthetic oil without formation of wax.

18 . The method of claim 17 , wherein the synthetic gas is fed into the reactor at a space velocity of 1.0˜9.0 NL/g cat /hr, and the reacting is performed at 240˜280° C.

Assignees

• Korea Energy Research Inst

Inventors

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

Classifications

• B01J37/0225

  of metal substrates · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• B01J37/0201

  Impregnation · CPC title

• B01J2531/005

  Catalytic metals · CPC title

• B01J37/0219

  the coating containing organic compounds · CPC title