Ni nano cluster support on MgO—CeO2—ZrO2 catalyst for tri-reforming of methane and a process for preparation thereof

Patent metadata

Field	Value
Publication number	US-9630167-B2
Application number	US-201615093984-A
Country	US
Kind code	B2
Filing date	Apr 8, 2016
Priority date	Apr 9, 2015
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

The present invention provides a Ni nano-cluster supported on MgO—CeO 2 —ZrO 2 catalyst and processes the production of the catalyst. Further, the present invention discloses use of Ni nano-cluster supported on MgO—CeO 2 —ZrO 2 catalyst for the synthesis gas (a mixture of CO and H 2 ) by tri-reforming of methane. The process provides a direct single step selective vapor phase tri-reforming of methane to synthesis gas over NiO—MgO—CeO 2 —ZrO 2 oxide catalyst between temperature range of 600° C. to 800° C. at atmospheric pressure. The process provides a methane conversion of 1-99% with H 2 to CO mole ratio of 1.6 to 2.3.

First claim

We claim:

1. A nano Ni—Mg—Ce—Zr oxide catalyst having a formula NiO—MgO—CeO 2 —ZrO 2 (NiO-MCZ) which comprises NiO in a range of 2.5-10 wt %, MgO in a range of 1-5 wt %, CeO 2 in a range of 20-25 wt % and ZrO 2 in a range of 60-72.5 wt %.

2. The catalyst as recited in claim 1 , having a particle size of 5-10 nm.

3. The catalyst as recited in claim 1 , wherein the wt % ratio of Ni and MCZ is in range of 2.5:97.5-10:90.

4. A process for the preparation of nano Ni—Mg—Ce—Zr oxide catalyst as recited in claim 1 , wherein said process comprises the steps of:
a) stirring zirconium salt with ethanol for a period ranging between 1-2 hours at a temperature ranging between 25-35° C.;
b) preparing a second solution by stirring a surfactant and ethanol for a period ranging between 1-2 hours at a temperature ranging between 25-30° C. subsequently adding magnesium salt and cerium salt and ethanol during continuous stirring and covering with paraffin film and stirring at a temperature ranging between 25-35° C. for a period ranging between 10-14 hours;
c) mixing both solutions as prepared in step (a) and step (b) and stirring for 7-8 hours at a temperature ranging between 25-35° C. followed by drying at temp a temperature ranging between 50-70° C. and calcining at a temperature ranging between 400° C.-600° C. for a period ranging between 5-7 hours to obtain a magnesium-cerium-zirconium oxide support;
d) preparing an aqueous solution of nickel salt with stirring for a period ranging between 1-2 hours at a temperature ranging between 25-30° C. and adding the magnesium-cerium-zirconium oxide support as obtained in step (c) into it;
e) preparing a separate solution of urea in water with stirring for a period ranging between 1-2 hours at a temperature ranging between 25-30° C.; and
f) mixing both solutions as obtained in step (d) and (e) with stirring for a period ranging between 10-14 hours at a temperature ranging between 25-30° C., subsequently setting the temperature at 70-100° C. followed by cooling after 24-48 hours and filtering and calcining at a temperature ranging between 400° C.-600° C. for a period ranging between 5-7 hours to obtain nano Ni—Mg—Ce—Zr oxide catalyst.

5. The process as recited in claim 4 , wherein Zr the zirconium salt used in step (a) is zirconium isopropoxide.

6. The process as recited in claim 4 , wherein the magnesium and cerium salt used in step (b) are magnesium nitrate hexahydrate and cerium nitrate hexahydrate, respectively.

7. The process as recited in claim 4 , wherein the surfactant used in step (b) is P123 (Pluronic acid).

8. The process as recited in claim 4 , wherein the nickel salt used in step (d) is nickel nitrate.

9. The process as recited in claim 4 , wherein the wt % ratio of Ni and MCZ is in range of 2.5:97.5-10:90.

10. The process as recited in claim 4 , wherein the mole ratio of zirconium salt, cerium salt and magnesium salt is in a range of 23:5:6 to 25:6:7.

11. A process for production of methane using nano Ni—Mg—Ce—Zr oxide catalyst to obtain syngas, wherein said process comprises passing an O 2 :CO 2 :H 2 O:CH 4 :He mixture with a molar ratio of 1:1:1.7:5:18 to 1:1:2.4:5:18 in a reactor at atmospheric pressure in the presence of a nano Ni—Mg—Ce—Zr oxide catalyst at a temperature ranging between 600°-800° C. for a period ranging between 1-100 hours at a gas hourly space velocity (GSHV) ranging between 20,000-200,000 mlg −1 h −1 to obtain syngas.

12. The process as claimed in claim 11 , wherein the process produces a H 2 /CO ratio 2.

13. The process as claimed in claim 11 , wherein the conversion of methane is in a range of 50-99% over 5-10 nm catalyst particles.

14. The process as claimed in claim 11 , wherein a H 2 /CO ratio of syngas obtained in a range of 1.6-2.3 over 5-10 nm catalyst particles.

Assignees

• Council Scient Ind Res

Inventors

• Bordoloi Ankur
• Singha Rajib Kumar
• Bal Rajaram
• Kumar Manoj
• Pendem Chandrashekar

Classifications

• B01J23/002 Primary

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• B01J23/83 Primary

  with rare earths or actinides · CPC title

• C01B3/40

  characterised by the catalyst · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title