# US 2016/0257564 A1 · Catalyst and process for thermo-neutral reforming of liquid hydrocarbons

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- Number: US 2016/0257564 A1
- Document ID: US20160257564A1
- Status: Published application
- Kind: A1
- Application number: 15/082,531
- Filed: 2016-03-28
- Published: 2016-09-08
- Earliest claimed: 2013-07-10
- Assignees: Petroleo Brasileiro S.A.; King Fahd University of Petroleum and Minerals; Saudi Arabian Oil Company
- Inventors: Fahad Ibrahim AL-MUHAISH; Shakeel AHMED; Roberto Carlos Pontes BITTENCOURT; Mauri Jose Baldini CARDOSO; Vivian Passos DE SOUZA
- Web page: https://patentgrep.com/patent/US20160257564A1

## CPC

- C01B 3/36: using oxygen; using mixtures containing oxygen as gasifying agents
- B01J 21/10: Magnesium; Oxides or hydroxides thereof
- B01J 23/894: {with rare earths or actinides}
- B01J 23/8946: {with alkali or alkaline earth metals}
- B01J 23/8986: {with manganese, technetium or rhenium}
- B01J 35/613: {10-100 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/0244: {Coatings comprising several layers}
- C01B 3/40: characterised by the catalyst
- C01B 3/50: Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0238: the reforming step being a carbon dioxide reforming step
- C01B 2203/0261: containing a catalytic partial oxidation step [CPO]
- C01B 2203/047: the impurity being carbon monoxide
- C01B 2203/0811: by combustion of fuel
- C01B 2203/0844: the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
- C01B 2203/1017: characterised by the form of the structure
- C01B 2203/1047: Group VIII metal catalysts
- C01B 2203/1058: Nickel catalysts
- C01B 2203/1064: Platinum group metal catalysts
- C01B 2203/107: Platinum catalysts
- C01B 2203/1082: Composition of support materials
- C01B 2203/1247: Higher hydrocarbons
- C01B 2203/1252: Cyclic or aromatic hydrocarbons
- Y02P 20/141: Feedstock
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## 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.

## Claims

### Claim 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 O2 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 O2 reforming catalyst containing Ni, La2O3, Ce2O3, Pt, ZrO2, Rh and Re supported on magnesium aluminate;
b. pre-heating the fuel, the O2 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.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 2)

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.

### Claim 4 (depends on 1)

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

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 1)

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

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 3)

The process of claim 3, wherein about 99% of the liquid petroleum-based fuel is converted into synthesis gas (H2CO/CO2/CH4).

### Claim 10 (depends on 1)

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.

### Claim 11 (depends on 1)

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.

### Claim 12 (depends on 1)

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

### Claim 13 (depends on 1)

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

### Claim 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 O2 gas and steam to an interior zone of a reactor, said interior zone including a catalyst bed consisting of a Ni—Ce2O3—Pt—Rh combined combustion and steam and/or CO2 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.

### Claim 15 (depends on 14)

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

### Claim 16 (depends on 15)

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.

### Claim 17 (depends on 14)

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

### Claim 18 (depends on 14)

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.

### Claim 19 (depends on 14)

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

### Claim 20 (depends on 14)

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

### Claim 21 (depends on 16)

The process of claim 16, wherein about 99% of the iso-octane and light naphtha feedstocks are converted into syngas (H2CO/CO2/CH4).

### Claim 22 (depends on 16)

The process of claim 16, wherein about 99% of the heavy naphtha feedstock is converted into syngas (H2CO/CO2/CH4).

### Claim 23 (depends on 14)

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

### Claim 24 (depends on 14)

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.

### Claim 25 (depends on 14)

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

### Claim 26 (depends on 14)

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

### Claim 27 (depends on 14)

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

### Claim 28

A process for preparing a Ni—Ce2O3—LaO3Pt—ZrO2—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 NH3-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 NH3-rich atmosphere, calcination and hydrogen reduction to obtain a Pt—ZrO2—Rh—Re/magnesium aluminate support;
c. impregnating the Pt—ZrO2—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 NH3-rich atmosphere, calcination and reduction at 730° C.

### Claim 29

A process for preparing a Ni—Ce2O3—LaO3 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.

### Claim 30

A catalyst which comprises 0.2% Rh w/w, 0.3% R Re w/w, 0.8% Pt w/w, 1.0% ZrO2 w/w, 1.0% La2O3 w/w, 6% Ni w/w and supported on a single refractory support, 3% Ce2O3 of magnesium aluminate for use in a thermoneutral reforming process.

### Claim 31 (depends on 30)

The catalyst according to claim 30 wherein the support is in the shape of a sphere, an extrudate, a honeycomb, a trilobe, a quadralobe or a Rasch ring.

### Claim 32

A catalyst which comprises 1% Pt w/w, 1% La2O3 w/w, 6% Ni w/w, 3% Ce2O3 and 2.7% K2O w/w supported on a single refractory support of magnesium aluminate for use in a thermoneutral reforming process.

### Claim 33 (depends on 32)

The catalyst according to claim 32, wherein the support is in the shape of a sphere, an extrudate, a honeycomb, a trilobe, a quadralobe or a Rasch ring.