# US 12,109,554 B2 · Shell impregnated catalyst and process for producing a shell impregnated catalyst body

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- Number: US 12,109,554 B2
- Document ID: US12109554B2
- Status: Granted
- Kind: B2
- Application number: 16/193,838
- Filed: 2018-11-16
- Published: 2019-03-28
- Granted: 2024-10-08
- Earliest claimed: 2014-04-07
- Assignees: Haldor TopsøE A/S
- Applicants: Haldor Topsoe A/S
- Inventors: Charlotte Vinding Ovesen; Fernando Morales Cano; Jens Henrik Hyldtoft; Michael Brorson
- Web page: https://patentgrep.com/patent/US12109554B2

## CPC

- B01J 23/78: with alkali- or alkaline earth metals
- B01J 23/005: {Spinels}
- B01J 23/58: with alkali- or alkaline earth metals
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 35/397: {Egg shell like}
- B01J 35/612: {less than 10 m2/g}
- B01J 35/613: {10-100 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 37/0201: {Impregnation}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0205: {in several steps}
- C01B 3/40: characterised by the catalyst
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0244: the reforming step being an autothermal reforming step, e.g. secondary reforming processes
- C01B 2203/0261: containing a catalytic partial oxidation step [CPO]
- C01B 2203/1058: Nickel catalysts
- C01B 2203/1064: Platinum group metal catalysts
- C01B 2203/1241: Natural gas or methane
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A process for producing a catalyst, comprising the steps of modifying a carrier by a first impregnation with at least one alkaline earth metal in a first metal precursor solution, the first metal precursor being decomposed to form at least one metal oxide or metal hydroxide, thereby obtaining a modified carrier. A second impregnation is carried out by incipient wetness by a second precursor solution comprising at least one metal Me in a second solution. Finally, the second precursor is decomposed, thereby obtaining a catalyst body having an enrichment of the at least one metal Me in the outer shell of the catalyst body, the metal being present in a concentration having either as an egg-shell profile or a hammock profile.

## Claims

### Claim 1

A process for producing a catalyst body, said process comprising the steps of:
providing a carrier comprising magnesium alumina spinel and/or Calcium aluminates, wherein the carrier has a pore volume 200-400 ml/kg and a BET surface area 2-50 m2/g,
modifying said carrier by a first impregnation with at least one alkaline earth metal in a first metal precursor solution, wherein the alkaline earth metal is selected from the group consisting of Mg, Ca, and Ba,
decomposing the first metal precursor at a temperature of from 300-900° C. to form an alkaline earth metal oxide or alkaline earth metal hydroxide layer on the carrier, thereby obtaining a modified carrier,
carrying out a second impregnation by a second precursor solution comprising at least one metal Me in a second solution, the metal Me comprising a catalytic metal, wherein the second precursor solution is Me-nitrate, Me-citrate, Me-Ethylenediaminetetraacetic acid (EDTA), or Me-Ethylenediamine (EDA) and
decomposing the second precursor to metal oxide, thereby obtaining a catalyst body having an enrichment of the at least one catalytic metal Me in an outer shell of the catalyst body, said at least one catalytic metal Me being present in a concentration having either an egg-shell profile and/or a hammock profile.

### Claim 2 (depends on 1)

A process according to claim 1, wherein the first precursor solution is a nitrate, carbonate or hydroxide of the alkaline earth metals.

### Claim 3 (depends on 1)

A process according to claim 1, wherein the first decomposition is carried out at 350-550° C.

### Claim 4 (depends on 1)

A process according to claim 1, wherein the alkaline earth metal concentration in the carrier is 0.5-10 wt %, after impregnation.

### Claim 5 (depends on 1)

A process according to claim 1, wherein the catalytic metal Me is Ni, Ru, Rh, Ir, Pd and/or Pt.

### Claim 6 (depends on 1)

A process according to claim 1, wherein the catalytic metal Me is Ni, Ru and/or Rh.

### Claim 7 (depends on 1)

A process according to claim 1, wherein the impregnated carrier is dried between the second impregnation and the second decomposition.

### Claim 8 (depends on 1)

A process according to claim 1, wherein the second decomposition is carried out at 350-600° C.

### Claim 9 (depends on 1)

A process according to claim 1, wherein the alkaline earth metal oxide/hydroxide concentration is 1-6 wt % of the carrier.

### Claim 10 (depends on 1)

A process according to claim 1, wherein 90% of the catalytic metal Me present within an outer later having a thickness of up to 500 μm.

### Claim 11 (depends on 1)

A process according to claim 1, wherein the second impregnation is carried out by incipient wetness.

### Claim 12 (depends on 1)

A process according to claim 1, wherein the obtained catalyst body comprises a core section and the outer shell, wherein the core comprises carrier material impregnated with the alkali earth metal oxide or alkali earth metal hydroxide, wherein the outer shell comprises the carrier material impregnated with the alkali earth metal oxide or alkali earth metal hydroxide and the catalytic metal Me.

### Claim 13 (depends on 1)

A process according to claim 1, wherein the catalytic metal Me is Ni.

### Claim 14

A process for producing a catalyst body, said process comprising the steps of:
providing a carrier comprising magnesium alumina spinel and/or Calcium aluminates, wherein the carrier has a pore volume 200-400 ml/kg and a BET surface area 2-50 m2/g,
modifying said carrier by a first impregnation with at least one alkaline earth metal in a first metal precursor solution,
decomposing the first metal precursor at a temperature of from 300-700° C. to form an alkaline earth metal oxide or alkaline earth metal hydroxide layer on the carrier, thereby obtaining a modified carrier,
carrying out a second impregnation by a second precursor solution comprising at least one metal Me in a second solution, the metal Me comprising a catalytic metal, wherein the second precursor solution is Me-nitrate, Me-citrate, Me-Ethylenediaminetetraacetic acid EDTA), or Me-Ethylenediamine (EDA), and
decomposing the second precursor to metal oxide, thereby obtaining a catalyst body having an enrichment of the at least one catalytic metal Me in an outer shell of the catalyst body, said at least one catalytic metal Me being present in a concentration having either an egg-shell profile and/or a hammock profile.

### Claim 15 (depends on 14)

A process according to claim 14, wherein the alkaline earth metal is selected from the group consisting of Mg, Ca and Ba.

### Claim 16 (depends on 14)

A process according to claim 14, wherein the catalytic metal Me is Ni, Ru and/or Rh.

### Claim 17 (depends on 14)

A process according to claim 14, wherein the second decomposition is carried out at 350-600° C.

### Claim 18 (depends on 14)

A process according to claim 14, wherein 90% of the catalytic metal Me present within an outer later having a thickness of up to 500 μm.

### Claim 19 (depends on 14)

A process according to claim 14, wherein the second impregnation is carried out by incipient wetness.

### Claim 20 (depends on 14)

A process according to claim 14, wherein the obtained catalyst body comprises a core section and the outer shell, wherein the core comprises carrier material impregnated with the alkali earth metal oxide or alkali earth metal hydroxide, wherein the outer shell comprises the carrier material impregnated with the alkali earth metal oxide or alkali earth metal hydroxide and the catalytic metal Me.

### Claim 21 (depends on 14)

A process according to claim 14, wherein the catalytic metal Me is Ni.