# US 11,298,684 B2 · Catalyst for oxidative coupling of methane, preparation method thereof and application thereof

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- Number: US 11,298,684 B2
- Document ID: US11298684B2
- Status: Granted
- Kind: B2
- Application number: 16/494,173
- Filed: 2018-03-12
- Published: 2020-01-09
- Granted: 2022-04-12
- Earliest claimed: 2017-03-13
- Assignees: East China Normal University; Zhejiang Jiruitong New Material Co., Ltd.
- Applicants: East China Normal University; Zhejiang Jiruitong New Material Co., Ltd.
- Inventors: Yong Lu; Xin Zhang; Pengwei Wang; Guofeng Zhao; Ye Liu; Mingyuan He
- Web page: https://patentgrep.com/patent/US11298684B2

## CPC

- B01J 23/34: Manganese
- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 23/005: {Spinels}
- B01J 23/30: Tungsten
- B01J 23/8892: {Manganese}
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/617: {500-1000 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/653: {500-1000 nm}
- B01J 35/657: {larger than 1000 nm}
- B01J 37/0205: {in several steps}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/088: {Decomposition of a metal salt}
- B01J 37/343: {of ultrasonic wave energy}
- C07C 2/84: catalytic
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 35/733: {Perovskite-type}
- B01J 2235/15: X-ray diffraction
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C07C 2523/30: Tungsten
- C07C 2523/34: Manganese
- C07C 2523/889: Manganese, technetium or rhenium
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A catalyst for oxidative coupling of methane, and preparation and application thereof. The catalyst comprises: a manganese sesquioxide, a tungstate, a manganese composite oxide having a perovskite structure and/or a spinel structure, and a carrier. The manganese sesquioxide, tungstate, and manganese composite oxide having a perovskite structure and/or a spinel structure are supported on the carrier, or the manganese sesquioxide and tungstate are supported on the admixture of the said manganese composite oxide having a perovskite structure and/or a spinel structure and the said carrier. Based on 100 parts by weight of the catalyst, the content of the manganese sesquioxide is a parts by weight, the content of the tungstate is b parts by weight, the content of the manganese composite oxide having the perovskite structure and/or the spinel structure is c parts by weight The content of the carrier is d parts by weight. 0<a≤20, 1≤b≤20, 1≤c≤40, 20≤d<98.

## Claims

### Claim 1

A catalyst for oxidative coupling of methane consisting of three active components of manganese sesquioxide, sodium tungstate, manganese titanate, and a carrier of silica,
wherein the catalyst has a composition represented by the following formula: xMn2O3-yNa2WO4-zMnTiO3-(100-x-y-z)SiO2,
wherein x, y and z respectively representing the weight fraction occupied by manganese sesquioxide, sodium tungstate, manganese titanate in the catalyst, and wherein 0<x≤20, 1≤y≤20, 1≤z≤40.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein 1.5≤x≤18, 4≤y≤18, and 2≤z≤35.

### Claim 3

A catalyst, comprising a manganese sesquioxide, a tungstate, a manganese composite oxide having a perovskite structure and/or a spinel structure, and a carrier,
wherein the manganese sesquioxide, the tungstate, the manganese composite oxide having a perovskite structure and/or a spinel structure are supported on the carrier,
or
the manganese sesquioxide and the tungstate are supported on an admixture of the said manganese composite oxide having a perovskite structure and/or a spinel structure and the said carrier,
wherein, based on 100 parts by weight of the catalyst, the content of the manganese sesquioxide is a parts by weight, the content of the tungstate is b parts by weight, the content of the manganese composite oxide having the perovskite structure and/or the spinel structure is c parts by weight, and the content of the carrier is d parts by weight, and wherein 0<a≤20, 1≤b≤20, 1≤c≤40, 20≤d≤98.

### Claim 4 (depends on 3)

The catalyst of claim 3, wherein the catalyst is consisted of a manganese sesquioxide, a tungstate, a manganese composite oxide having a perovskite structure and/or a spinel structure, and a carrier,
wherein based on 100 parts by weight of the catalyst, the content of the manganese sesquioxide is ranged from >0 parts by weight to ≤20 parts by weight,
the content of the tungstate is ranged from 1.0 parts by weight to 20 parts by weight,
the content of the manganese composite oxide having a perovskite structure and/or a spinel structure is ranged from 1 part by weight to 40 parts by weight,
the balance is the carrier.

### Claim 5 (depends on 3)

The catalyst of claim 3, wherein the manganese composite oxide having the perovskite structure and/or the spinel structure comprises at least one element selected from Ti, Fe, Co, Ni, Li, Pb, Cd, Sn, In, Ge, Ga, Sb, Bi, Te, Se, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Ba, Mg, Ce, La, Pr, Nd, Sm, Ca, Sr, K or combinations thereof.

### Claim 6 (depends on 3)

The catalyst of claim 3, wherein the manganese composite oxide having a perovskite structure and/or a spinel structure is at least one selected from manganese titanate, manganese ferrite, manganese cobaltate, manganese nickelate, lithium manganite, lithium nickel cobalt manganese oxide, manganese plumbite, cadmium acid manganese, manganese stannate, manganese germanate, manganese gallate, bismuth manganate, manganese tellurite, manganese selenate, vanadium manganate, manganese niobate, manganese tantalite, manganese chromate, barium manganate, magnesium manganate, LnAFeMnO6(Ln=La, Pr, Nd, Sm, Ce; A=Ca, Sr, Ba), La0.5Sr0.5Mn1-mFemO3, CaαLaβK1-α-βMn0.5Fe0.5O3, CapLaqK1-p-qMn0.78Fe0.22O3, Bi0.5Ca0.5-nLanFe0.3Mn0.7O3 or combinations thereof; 0<m≤0.25, 0<α≤0.25, 0<β≤0.25, 0<p≤0.25, 0<q≤0.25, 0<n≤0.25
the manganese composite oxide having a perovskite structure and/or a spinel structure comprises particles having a size varied from 100 to 2000 mesh.

### Claim 7 (depends on 3)

The catalyst of claim 3, wherein the carrier is selected from SiC, Fe2O3, Fe3O4, TiO2, ZrO2, Al2O3, La2O3, CaO, SrO, MgO, SiO2 or combinations thereof,
the carrier having a particle size varied from 100 to 2000 mesh,
wherein the carrier having a specific surface varied from 10 to 1000 m2/g,
wherein the carrier having a pore volume varied from 0.1 to 1.2 mL/g,
wherein the carrier having a most probable pore size varied from 2.0 to 20.0 nm.

### Claim 8 (depends on 7)

The catalyst of claim 7, wherein the carrier is SiO2,
wherein the carrier having a particle size varied from 100 to 1000 mesh,
wherein the carrier having a specific surface varied from 50 to 250 m2/g,
wherein the carrier having a pore volume varied from 0.5 to 0.9 mL/g,
wherein the carrier having a most probable pore size varied from 2.0 to 10.0 nm.

### Claim 9 (depends on 3)

A method for oxidative coupling of methane, comprising: bringing the catalyst of claim 3 into contact with a feed gas stream containing methane and oxygen to have the methane reacting with oxygen under oxidative coupling of methane conditions.

### Claim 10 (depends on 9)

The method of claim 9, wherein the methane to oxygen volume ratio in the feed gas stream is 3:1˜8:1; the reaction temperature is from 620 to 900° C., the reaction pressure is from 0.1 to 2 MPa, on the basis of the total amount of methane and oxygen, the gas hourly space velocity is from 3000-50000 mL·h−1·g−1.