Catalyst and process for thermo-neutral reforming of liquid hydrocarbons

Patent metadata

Field	Value
Publication number	US-2016257564-A1
Application number	US-201615082531-A
Country	US
Kind code	A1
Filing date	Mar 28, 2016
Priority date	Jul 10, 2013
Publication date	Sep 8, 2016
Grant date	—

Abstract

The invention relates to a four-component catalyst and a seven-component catalyst and refractory supports for use in the thermoneutral reforming of petroleum-based liquid hydrocarbon fuels.

First claim

What is claimed is:

1 . A thermo-neutral reforming process for the production of a hydrogen-rich synthesis gas from a liquid hydrocarbon fuel, which comprises:
a. providing a mixture of a liquid hydrocarbon fuel, an O 2 gas and steam to an interior zone of a reactor, said interior zone including a catalyst bed consisting of a combined combustion and steam and/or O 2 reforming catalyst containing Ni, La 2 O 3 , Ce 2 O 3 , Pt, Z r O 2 , Rh and Re supported on magnesium aluminate; b. pre-heating the fuel, the O 2 gas and steam mixture to a temperature in the range of about 350° C.; and, c. heating the mixture to about 410° C. and bringing, it into contact with the catalyst bed at a gas hour space velocity of about 30,000 h −1 to about 70,000 h −1 causing an exothermic combustion reaction raising the reaction temperature to about 800° C. to about 820° C., and also causing an endothermic steam reforming reaction for a period of time sufficient to reform the liquid fuel to yield a hydrogen-rich synthesis gas.

2 . The process of claim 1 , wherein the liquid hydrocarbon file l is a petroleum-based fuel.

3 . The process of claim 2 , wherein the liquid petroleum-based fuel is selected from the group consisting of iso-octane, light naphtha, heavy-naphtha, kerosene and diesel.

4 . The process of claim 1 , wherein the gas hour space velocity is between about 35,000 h−1 and about 50,000 h−1 .

5 . The process of claim 1 , wherein the heat generated from the exothermic combustion reaction is neutralized and compensated for by the endothermic reaction on the same catalyst bed.

6 . The process of claim 1 , wherein the reaction is carried out in the absence of externally supplied heat.

7 . The process of claim 1 , wherein coke formation is avoided.

8 . The process of claim 1 , wherein the catalyst can reform feedstocks containing less than 200 ppm sulfur.

9 . The process of claim 3 , wherein about 99% of the liquid petroleum-based fuel is converted into synthesis gas (H 2 CO/CO 2 /CH 4 ).

10 . The process of claim 1 , wherein the synthesis gas produced from the process is further purified using a hydrogen purification technology selected from the group consisting of water gas shift and preferential oxidation, methanation and membrane technologies, and PSA.

11 . The process of claim 1 , wherein the hydrogen-rich synthesis gas is used as a feed for on-board reformers in vehicles incorporating a high temperature or low temperature fuel cell.

12 . The process of claim 1 , wherein the hydrogen-rich synthesis gas is used as a feed for hydrogen enrichment in internal combustion engines.

13 . The process of claim 1 , wherein the hydrogen-rich synthesis gas is employed in stationary power generating facilities applications.

14 . A thermo -neutral reforming process for the production of a hydrogen-rich synthesis gas from liquid hydrocarbon fuels, which comprises:
a. providing a mixture of a liquid hydrocarbon fuel, an O 2 gas and steam to an interior zone of a reactor, said interior zone including a catalyst bed consisting of a Ni—Ce 2 O 3 —Pt—Rh combined combustion and steam and/or CO 2 reforming catalyst supported on magnesium aluminate and containing a potassium compound as a promoter; b. pre-heating the mixture to a temperature of about 350° C.; and c. heating the mixture to about 410° C. and bringing it into contact with the catalyst bed at a gas hour space velocity of about 30,000 h−1 to about 70,000 h−1 causing an exothermic combustion reaction raising the reaction temperature to about 800° C. to about 820° C. and also causing an endothermic steam reforming reaction for a period of time sufficient to reform the liquid fuel to yield a hydrogen-rich synthesis gas.

15 . The process of claim 14 , wherein the liquid hydrocarbon fuel is a petroleum-based fuel.

16 . The process of claim 15 , wherein the petroleum-based liquid is selected from the group consisting of iso-octane, light naphtha, heavy-naphtha, kerosene and diesel.

17 . The process of claim 14 , wherein the gas hour space velocity is between about 25,000 and about 40 000 h−1 .

18 . The process of claim 14 , wherein the heat generated from the exothermic combustion reaction is neutralized and compensated for by the endothermic reaction on the same catalyst bed.

19 . The process of claim 14 , wherein the reaction is carried out without the need of an external heat supply.

20 . The process of claim 14 , wherein coke formation is avoided.

21 . The process of claim 16 , wherein about 99% of the iso-octane and light naphtha feedstocks are converted into syngas (H 2 CO/CO 2 /CH 4 ).

22 . The process of claim 16 , wherein about 99% of the heavy naphtha feedstock is converted into syngas (H 2 CO/CO 2 /CH 4 ).

23 . The process of claim 14 , wherein the syngas produced from the process can be further purified to produce highly pure hydrogen.

24 . The process of claim 14 , wherein the hydrogen rich syngas is used as a feed fur on-board reformers in vehicles incorporating a high temperature or low temperature fuel cell.

25 . The process of claim 14 , wherein the hydrogen-rich syngas is used as a feed for hydrogen enrichment in internal combustion engines.

26 . The process of claim 14 , wherein the hydrogen-rich syngas is employed in stationary applications.

27 . The process of claim 14 , wherein the sulfur content of the liquid hydrocarbons fuel is 200 ppm or less.

28 . A process for preparing a Ni—Ce 2 O 3 —LaO 3 Pt—ZrO 2 —Rh—Re catalyst supported on magnesium aluminate for use in a thermo-neutral reforming process, which comprises steps of:
impregnating a magnesium aluminate support with an aqueous solution containing rhodium nitrate and rhenium oxide, followed by drying in an NH 3 -rich atmosphere, calcination and hydrogen reduction to obtain a rhodium-rhenium/magnesium aluminate support;
b. impregnating the rhodium-rhenium/magnesium aluminate support with an aqueous solution of zirconium oxynitrate hydrate and tetraminoplantino chloride followed by drying in an NH 3 -rich atmosphere, calcination and hydrogen reduction to obtain a Pt—ZrO 2 —Rh—Re/magnesium aluminate support;
c. impregnating the Pt—ZrO 2 —Rh—Re:/magnesium aluminate support with an aqueous solution of lanthanum nitrate hexahydrate, cerium (iii) nitrate and nickel nitrate hexahydrate followed by drying in an NH 3 -rich atmosphere, calcination and reduction at 730° C.

29 . A process for preparing a Ni—Ce 2 O 3 —LaO 3 catalyst supported on magnesium aluminate and promoted by potassium for use in a thermo-neutral reforming process, which comprises;
a. impregnating a magnesium aluminate support with an aqueous solution of potassium hydroxide followed by drying and calcining;
b. impregnating the potassium hydroxide impregnated support with tetraaminoplatinate chloride (II) monohydrate, lanthanum nitrate hexahydrate, cerium nitrate and nickel nitrate hexahydrate followed by drying, calcination and hydrogen reduction.

30 . A catalyst which comprises 0.2% Rh w/w, 0.3% R Re w/w, 0.8% Pt w/w, 1.0% ZrO 2 w/w, 1.0% La 2 O 3 w/w, 6% Ni w/w and supported on a single refractory support, 3% Ce 2 O 3 of magnesium aluminate for use in a thermoneutral reforming process.

31 . The catalyst according to claim 30 wherein the support is in the shape

Assignees

• Al-Muhaish Fahad Ibrahim
• Ahmed Shakeel
• Bittencourt Roberto Carlos Pontes
• Cardoso Mauri Jose Baldini
• De Souza Vivian Passos
• Petroleo Brasileiro Sa
• Univ King Fahd Pet & Minerals
• Saudi Arabian Oil Co

Inventors

• Al-Muhaish Fahad Ibrahim
• Ahmed Shakeel
• Bittencourt Roberto Carlos Pontes
• Cardoso Mauri Jose Baldini
• De Souza Vivian Passos

Classifications

• B01J23/8946 Primary

  with alkali or alkaline earth metals · CPC title

• C01B2203/0811

  by combustion of fuel · CPC title

• C01B2203/1082

  Composition of support materials · CPC title

• C01B2203/0233

  the reforming step being a steam reforming step · CPC title

• C01B2203/047

  the impurity being carbon monoxide · CPC title