# US 10,369,549 B2 · Use of nickel-manganese olivine and nickel-manganese spinel as bulk metal catalysts for carbon dioxide reforming of methane

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- Number: US 10,369,549 B2
- Document ID: US10369549B2
- Status: Granted
- Kind: B2
- Application number: 15/557,156
- Filed: 2016-01-27
- Published: 2018-02-15
- Granted: 2019-08-06
- Earliest claimed: 2015-03-20
- Assignees: Sabic Global Technologies B.V.
- Applicants: SABIC Global Technologies B.V.
- Inventors: Ugo Ravon; Lawrence D'Souza; Vinu Viswanath
- Web page: https://patentgrep.com/patent/US10369549B2

## CPC

- B01J 23/8892: {Manganese}
- B01J 23/005: {Spinels}
- B01J 23/892: {Nickel and noble metals}
- B01J 23/8986: {with manganese, technetium or rhenium}
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 37/0036: {Grinding}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C01B 3/40: characterised by the catalyst
- B01J 2235/15: X-ray diffraction
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C01B 2203/0238: the reforming step being a carbon dioxide reforming step
- C01B 2203/0244: the reforming step being an autothermal reforming step, e.g. secondary reforming processes
- C01B 2203/1058: Nickel catalysts
- C01B 2203/1064: Platinum group metal catalysts
- C01B 2203/107: Platinum catalysts
- C01B 2203/1241: Natural gas or methane
- Y02E 60/32: Hydrogen storage
- 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}
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed are bulk metal oxide catalysts, and methods for their use, that include at 5 least two or more metals or two or more compounds thereof (M1, M2) and having an olivine crystal phase or a spinel crystal phase, or both phases, wherein the bulk metal oxide catalyst is capable of producing the H2 and CO from the CH4 and the CO2 under substantially dry conditions.

## Claims

### Claim 1

A bulk metal oxide catalyst capable of producing hydrogen (H2) and carbon monoxide (CO) from methane (CH4) and carbon dioxide (CO2), wherein the bulk metal oxide catalyst consists of an olivine crystal structure that has discrete SiO44− anions and two metals (M1, M2) in the crystal lattice, a discrete spinel structure, or is a mixture thereof,
wherein M1 and M2 are different;
wherein the O− anions of the silicate are coordinated with the metals in the crystal lattice, and
wherein the bulk metal oxide catalyst does not include a carrier or a support.

### Claim 2 (depends on 1)

The bulk metal oxide of claim 1, wherein M1 comprises nickel (Ni) or a compound thereof, and M2 comprises manganese (Mn) or a compound thereof.

### Claim 3 (depends on 2)

The bulk metal oxide catalyst of claim 2, wherein the olivine crystal phase comprises a nickel-manganese olivine crystal phase having a structure of (NixMn1-x)2SiO4, where x is 0<x≤0.25 and wherein the catalyst further comprises a spinel crystal phase.

### Claim 4 (depends on 3)

The bulk metal oxide catalyst of claim 3, further comprising a metal oxide crystal phase having a structure of MnSiO3.

### Claim 5 (depends on 3)

The bulk metal oxide catalyst of claim 3, wherein the spinel crystal phase comprises a nickel-manganese spinel crystal phase having a structure of (NixMn3-x)O4, where x is 0<x≤1.

### Claim 6 (depends on 5)

The bulk metal oxide catalyst of claim 5, further comprising a metal oxide crystal phase having a structure of MnSiO3.

### Claim 7 (depends on 1)

The bulk metal oxide catalyst of claim 1, wherein the olivine crystal phase is represented by the formula of: (M1xM21-x)2SiO4, where x is 0<x≤0.25, wherein M1 and M2 are different.

### Claim 8 (depends on 1)

The bulk metal oxide catalyst of claim 1, wherein the catalyst consists of the olivine crystal structure.

### Claim 9 (depends on 1)

The bulk metal oxide catalyst of claim 1, wherein the catalyst consists of the spinel structure.

### Claim 10 (depends on 1)

The bulk metal oxide catalyst of claim 1, wherein the catalyst consists of a combination of the olivine crystal structure and the spinel structure.

### Claim 11 (depends on 1)

A reactant composition comprising the bulk metal oxide catalyst of claim 1, and one or both of CH4 and CO2.

### Claim 12 (depends on 1)

A method of producing H2 and CO comprising contacting a reactant gas stream that includes CH4 and CO2 with a bulk metal oxide catalyst catalysts of claim 1 under substantially dry reaction conditions and at a temperature of greater than 800° C. sufficient to produce a product gas stream comprising H2 and CO; wherein the bulk metal oxide catalyst consists of an olivine crystal structure that has discrete SiO44− anions and two metals (M1, M2) in the crystal lattice, or a discrete spinel structure, or is a mixture thereof,
wherein M1 and M2 are different;
wherein the O− anions of the silicate are coordinated with the metals in the crystal lattice, and
wherein the bulk metal oxide catalyst does not include a carrier or a support.

### Claim 13 (depends on 12)

The method of claim 12, wherein a ratio of CO to H2 ranges from 0.35:1 to 1:1 after 40 hours.

### Claim 14 (depends on 12)

The method of claim 12, wherein coke formation on the bulk metal oxide catalyst is substantially or completely inhibited.

### Claim 15 (depends on 1)

A method of making the bulk metal oxide of claim 1, the method comprising:
(a) obtaining a mixture comprising M1 oxide particles, silicon dioxide particles, and M2 oxide particles, and wherein the molar ratio of M2:Si is 1:1 to 3:1, and the molar ratio of M1:M2 is 0.01 to 0.5; and
(b) calcining the mixture at a temperature of 1000° C. to 1500° C., for a sufficient period of time to obtain a bulk catalyst having a M′-M2 olivine crystal phase, a spinel phase, or a combination thereof.

### Claim 16 (depends on 15)

The method of claim 15, wherein the calcining is conducted at a temperature of about 1100° C. to 1275° C. for about 22 to 48 hours and subsequently cooled to room temperature.

### Claim 17

A catalyst comprising:
a support comprising an olivine mineral having an olivine crystal phase, wherein the olivine mineral is selected from the group consisting of monticelite, calcio-olivine, lienbergite, glaucochroite, and any combination thereof; and
two or more additional metals (M1, M2) or two or more compounds thereof.