Catalytic system for catalytic partial oxidation processes with a short contact time

Patent metadata

Field	Value
Publication number	US-9987620-B2
Application number	US-201715450237-A
Country	US
Kind code	B2
Filing date	Mar 6, 2017
Priority date	Jun 3, 2010
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

The present invention relates to a catalytic system comprising at least two catalytic zones of which at least one zone exclusively contains one or more noble metals selected from the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum and at least another zone contains Nickel, said catalytic system characterized in that at least one zone exclusively containing noble metals selected from the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum is always distinct but in contact with at least one zone containing Nickel.
One or more metals selected from the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum are possibly added to the catalytic zone or zones comprising Nickel.

First claim

The invention claimed is:

1. A process of catalytic partial oxidation for the production of Synthesis Gas and, with further steps, of hydrogen, using a catalytic system comprising a first catalytic zone comprising at least one noble metal selected in the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum and a second catalytic zone comprising Nickel, wherein the first catalytic zone is always distinct but in contact with the second catalytic zone containing Nickel;
starting from the following reagents:
hydrocarbons and/or oxygenated compounds which are either liquid or gaseous at the inlet temperature and pressure of at least one reaction equipment, wherein the liquid hydrocarbons are selected from naphtha, gas oils, heavy gas oils, deasphalted oils and mixtures thereof, wherein the oxygenated compounds are selected from ethanol, ethylene glycol, triglycerides of fatty acids, glycerine and carbohydrates with formula C n (H 2 O) n H 2 and mixtures thereof, wherein the gaseous hydrocarbons are selected from methane, Natural Gas, Refinery Fuel Gas, liquefied petroleum gas and mixtures thereof;
air, enriched air with oxygen at any volumetric percentage ranging from 21% to 100%;
optionally steam and/or carbon dioxide;

said process comprising the following steps:
preheating said reagents at a temperature ranging from 25° C. to 350° C. and bringing said reagents to a pressure which ranges from 2 atm and 50 atm,
premixing reagents in one or more passages so as to form a homogeneous mixture,
reacting the so obtained reagent mixture on said catalytic system, so that said mixture first meets the catalytic zone including one or more noble metals selected in the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum, and so that the oxygen is all consumed before said mixture meets the catalytic zones containing Nickel; at a pressure which ranges from 2 atm to 50 atm, for a contact time ranging from 1 ms to 1000 ms, at a space velocity comprised from 10000 Nl/kg/h and 1000000 Nl/kg/h, so as to form Synthesis Gas at a maximum temperature of 1200° C.,
cooling down said Synthesis Gas at temperatures lower than 400° C.;
optionally reacting said Synthesis Gas according to a Water Gas Shift reaction to form a mixture enriched in carbon dioxide and hydrogen,
optionally purifying said mixture so as to obtain a stream of pure hydrogen.

2. The process according to claim 1 wherein the catalytic zone or zones including Nickel is added with one or more metals selected in the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum.

3. The process according to claim 1 wherein at least one zone comprises Rhodium and the second catalytic zone contains Nickel.

4. The process of catalytic partial oxidation according to claim 1 wherein said catalytic zones are arranged in such a way as to form a catalytic bed.

5. The process of catalytic partial oxidation according to claim 1 wherein the noble metal amount ranges from 0.2% weight to 10% weight with respect to the total catalyst weight.

6. The process of catalytic partial oxidation according to claim 5 wherein the noble metal amount ranges from 0.5% weight to 2% weight with respect to the total catalyst weight.

7. The process of catalytic partial oxidation according to claim 1 wherein the Nickel amount ranges from 0.5% weight to 20% weight with respect to the total catalyst weight.

8. The process of catalytic partial oxidation according to claim 7 wherein the Nickel amount ranges from 2% weight to 10% weight with respect to the total catalyst weight.

9. The process of catalytic partial oxidation according to claim 1 wherein the gaseous hydrocarbons consist of Natural Gas and Refinery Fuel Gas.

10. The process of catalytic partial oxidation according to claim 1 wherein the oxygenated compound is glycerine.

11. The process of catalytic partial oxidation according to claim 1 , wherein the reagents are preheated at a temperature ranging from 100° C. and 350° C., wherein the reaction pressure ranges from 10 atm and 30 atm, wherein the contact time of the reagents mixture with said catalytic system ranges from 10 ms to 100 ms, wherein, the Synthesis Gas exits at a maximum temperature of 1150° C., wherein the space velocity of the reactant mixture ranges from 20000 Nl/kg/h and 200000 Nl/kg/h.

12. The process of catalytic partial oxidation according to claim 11 wherein reagents are preheated at a temperature ranging from 200° C. and 350° C.

13. The process of catalytic partial oxidation according to claim 1 wherein reagents are desulphurated or hydro-desulphurated.

14. The process of catalytic partial oxidation according to claim 1 wherein the catalytic partial oxidation reaction occurs in at least one reaction equipment comprising:
a mixing section,
a reaction chamber including:
at least two thermal shields, placed respectively upstream and downstream a catalytic system;
said catalytic system comprising a first catalytic zone comprising at least one noble metal selected in the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum and a second catalytic zone comprising Nickel, wherein the first catalytic zone is always distinct but in contact with the second catalytic zone containing Nickel;
said catalytic system wherein the catalytic zones are arranged in such a way as to form a catalytic bed and wherein the catalytic zone including at least one noble metal selected in the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum, is in contact and it always precedes the catalytic zone containing Nickel,

a cooling section of the reaction products.

15. The process of catalytic partial oxidation according to claim 14 wherein the mixing section comprises a cylindrical or truncated conical chamber, designed so that the residence times of said reagents are lower than flame delay times and that the linear rates of said reagents are higher than flame rates.

16. The process of catalytic partial oxidation according to claim 14 wherein said reaction chamber has cylindrical or truncated-conical or truncated-pyramidal geometry, and wherein the generatrix of the envelope curve surface and the parallel to the vertical axis of said reaction chamber form an angle ranging from 5° to 65°.

17. The process of catalytic partial oxidation according to claim 14 wherein in case the reaction chamber has truncated cone geometry, the height of the zone of said catalytic bed, comprising at least one noble metal selected from the group consisting of Rhodium, Ruthenium, Iridium, Palladium and Platinum, is at least one third of the total height of the catalytic bed.

Assignees

• Eni Spa

Inventors

• Basini Luca Eugenio
• Guarinoni Alessandra
• Carluccio Luciano Cosimo

Classifications

• C01B2203/1247

  Higher hydrocarbons · CPC title

• C01B2203/107

  Platinum catalysts · CPC title

• C01B2203/1064

  Platinum group metal catalysts · CPC title

• C01B2203/0261

  containing a catalytic partial oxidation step [CPO] · CPC title

• C01B2203/0238

  the reforming step being a carbon dioxide reforming step · CPC title