Doped Hexagonal Lanthanum Oxycarbonate Catalysts for Higher C2 Yield

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Solution Overview

Problem

Existing methods for synthesizing lanthanum dioxide carbonate result in low yields of C2 hydrocarbons during methane oxidative coupling reactions, and there is a lack of reports on element doping during the preparation process.

Innovation Solution

A lanthanum dioxide carbonate catalyst comprising hexagonal crystalline lanthanum dioxide carbonate with a doping element R, prepared by adding an alkali solution to a lanthanum source, followed by aging, solid-liquid separation, and drying, then contacting with a doping element solution, and calcining in a carbon-containing atmosphere.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If element doping is performed by impregnating pre-synthesized lanthanum dioxide carbonate with doping element solutions, then the doping process is simple, but the doping efficiency is low and the distribution is uneven

Engineering Contradiction:
Improvedoping process simplicityVSAvoiddoping uniformity
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The doping element is introduced during the preparation process of lanthanum dioxide carbonate rather than as a post-treatment step. By adding the doping element solution during the formation of the carbonate structure, the doping occurs at the source, ensuring uniform distribution throughout the material matrix and improving doping efficiency.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The doping process is merged with the lanthanum dioxide carbonate synthesis process. The doping element solution is added to the reaction mixture during carbonate formation, combining two separate operations (synthesis and doping) into one integrated process, which improves both efficiency and uniformity.

Inventive Principle:
Principle #5Merging (Combining)

2Ease of manufacture

If conventional preparation methods are used to synthesize lanthanum dioxide carbonate, then the synthesis process is straightforward, but the C2 hydrocarbons yield in methane oxidative coupling reactions is low

Engineering Contradiction:
Improvesynthesis process simplicityVSAvoidC2 hydrocarbons yield
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The crystal structure parameter of lanthanum dioxide carbonate is changed from the conventional cubic phase to the hexagonal phase. This structural transformation, achieved by controlling the preparation conditions, fundamentally alters the catalytic properties of the material, resulting in significantly enhanced C2 hydrocarbons yield while maintaining a relatively simple synthesis approach.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite catalyst system by incorporating doping elements (such as Fe, Zn, or Mn) into the hexagonal lanthanum dioxide carbonate structure. This composite approach combines the unique catalytic properties of the hexagonal phase with the specific electronic and structural contributions of the doping elements, achieving high C2 hydrocarbons yield.

Inventive Principle:
Principle #40Composite materials

3Adaptability or versatility

If the molar ratio of lanthanum to doping element R is outside the range of 1:0.01 to 1:0.3, then the catalyst composition can be adjusted freely, but the catalytic activity for methane oxidative coupling decreases

Engineering Contradiction:
Improvecomposition flexibilityVSAvoidcatalytic activity
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The invention identifies and optimizes the critical parameter of doping element concentration, establishing the optimal molar ratio range of 1:0.01 to 1:0.3 between lanthanum and doping element R. This parameter optimization ensures maximum catalytic activity for methane oxidative coupling while still allowing flexibility within the defined range for different specific applications.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The catalyst achieves a higher yield of C2 hydrocarbons during methane oxidative coupling reactions, with a molar ratio of lanthanum to doping element R ranging from 1:0.01 to 1:0.3, ensuring a predominantly hexagonal crystalline phase and no metal salt peaks in the XRD spectrum.

Implementation Method 1

adding an alkali solution to a solution of lanthanum source, and then optionally performing an aging, performing a solid-liquid separation and a drying to obtain solid lanthanum hydroxide

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 2

adding a solution of a compound containing the doping element R to the solid lanthanum hydroxide obtained in step (1) so that the solution in an amount less than or equal to the saturated water absorption amount of the lanthanum hydroxide is in contact with the lanthanum hydroxide

Methodology Applied
Scientific EffectAbsorption: Absorption (physical)

Implementation Method 3

calcining the dried product of step (2) in a carbon-containing (e.g. CO and/or CO2) atmosphere to obtain a lanthanum dioxide carbonate catalyst

Methodology Applied
Scientific EffectThermal decomposition: Pyrolysis

Implementation Method 4

the total content of hexagonal crystalline lanthanum dioxide carbonate and hexagonal crystalline lanthanum dioxide carbonate containing a doping element R in the lanthanum dioxide carbonate catalyst is not less than 98wt%

Methodology Applied
Scientific EffectCrystallisation: Crystallisation

Data Source

PatentEP4596103A1Lanthanum oxycarbonate catalyst, preparation method therefor and use thereof
Publication Date: 2025.08.06 CHINA PETROLEUM & CHEMICAL CORP
  • EP4596103A1 patent drawingFigure 1~2
  • EP4596103A1 patent drawingFigure 3
  • EP4596103A1 patent drawing

AI summary

The invention relates to the technical field of lanthanum dioxide carbonate, and discloses a lanthanum dioxide carbonate catalyst, a preparation method and a use thereof. The lanthanum dioxide carbonate catalyst comprises hexagonal crystalline lanthanum dioxide carbonate and hexagonal crystalline lanthanum dioxide carbonate containing a doping element R. The method comprises: (1) adding an alkali solution to a solution of lanthanum source, and then performing a solid-liquid separation and a drying to obtain lanthanum hydroxide; (2) contacting a solution of a compound containing the doping element R with lanthanum hydroxide, and then performing a drying; (3) calcining the dried product of step (2) under a carbon-containing atmosphere to obtain a lanthanum dioxide carbonate catalyst. When the catalyst prepared by the invention is used in a methane oxidative coupling reaction, it has a high yield of C2 hydrocarbons.