Cyclic Amines for Selective H2S Capture

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Solution Overview

Problem

Current methods for selectively removing hydrogen sulfide (H2S) from fluid streams containing carbon dioxide (CO2) face challenges in achieving high selectivity and regenerability, particularly at low acid gas partial pressures, which affects the efficiency and performance of downstream processes like the Claus system.

Innovation Solution

The use of amines with specific structural features, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine and methyldiethanolamine, in aqueous solutions at concentrations of 10 to 60% by weight, which selectively absorb H2S over CO2 due to their sterically hindered secondary amino groups and tertiary amino groups, allowing for efficient separation and regeneration.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If highly sterically hindered secondary amines (e.g., TBAEE) are used for selective H2S removal, then H2S selectivity is improved, but H2S selectivity deteriorates at low acid gas partial pressures

Engineering Contradiction:
ImproveH2S selectivityVSAvoidH2S selectivity at low partial pressures
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The patent combines two different amine components with complementary properties: a highly sterically hindered secondary amine (providing high H2S selectivity at normal pressures) and a cyclic amine with tertiary amino groups (maintaining selectivity at low partial pressures). This composite absorbent formulation resolves the contradiction by leveraging the strengths of both amine types across different operating conditions.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent modifies the chemical structure parameters of the amine components by incorporating cyclic structures with specific tertiary amino groups. This structural parameter change enables the absorbent to maintain effective H2S selectivity even at low acid gas partial pressures, where conventional highly sterically hindered secondary amines fail.

Inventive Principle:
Principle #35Parameter changes

2Productivity

If conventional amines are used for acid gas removal, then H2S and CO2 are removed simultaneously, but H2S:CO2 ratio optimization for downstream Claus system deteriorates

Engineering Contradiction:
ImproveAcid gas removal efficiencyVSAvoidH2S:CO2 ratio optimization
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent applies local quality by creating an absorbent with differentiated functional groups that exhibit selective affinity: the highly sterically hindered secondary amine groups preferentially bind H2S, while the cyclic amine with tertiary amino groups provides complementary selectivity. This local functional differentiation enables preferential H2S absorption while maintaining controlled CO2 removal, optimizing the H2S:CO2 ratio for downstream Claus processing.

Inventive Principle:
Principle #3Local quality

3Manufacturing precision

If absorbents are used for selective H2S removal, then H2S selectivity is improved, but regeneration energy increases

Engineering Contradiction:
ImproveH2S selectivityVSAvoidRegeneration energy
Core Design Contradiction:
Manufacturing precisionVSUse of energy by moving object

Solution Approach 1:

The patent employs cyclic amines with specific structural parameters (tertiary amino groups in cyclic structures) that inherently provide lower regeneration energy requirements compared to conventional highly sterically hindered secondary amines. This parameter change in the amine structure reduces the energy input needed for desorption while preserving H2S selectivity.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

By combining two amine types with different regeneration characteristics, the composite absorbent achieves a balance: the highly sterically hindered secondary amine provides high H2S selectivity, while the cyclic amine component contributes lower regeneration energy requirements, resolving the contradiction between selectivity and energy consumption.

Inventive Principle:
Principle #40Composite materials

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

This approach achieves high selectivity for H2S over CO2, optimizing the H2S:CO2 ratio and reducing regeneration energy, thereby enhancing the performance and efficiency of gas treatment processes while adhering to stringent sulfur and CO2 concentration limits.

Implementation Method 1

When acid gases dissolve in the absorbent, ions form with the bases. The absorbent can be regenerated by relaxing to a lower pressure and/or stripping, whereby the ionic species react back to acid gases and/or are stripped out using steam.

Methodology Applied
Scientific EffectChemical absorption: Absorption (physical)

Implementation Method 2

The absorbent can be regenerated by relaxing to a lower pressure and/or stripping, whereby the ionic species react back to acid gases and/or are stripped out using steam.

Methodology Applied
Scientific EffectDesorption: Desorption

Data Source

PatentEP3356011B1Cyclic amines for selective capture of hydrogen sulphide
Publication Date: 2022.06.29 BASF SE
  • EP3356011B1 patent drawingFigure 1
  • EP3356011B1 patent drawingFigure 2
  • EP3356011B1 patent drawing

AI summary

The invention relates to the use of an amine of formula (I) where the groups R1 to R5 are defined as they are in the description, as well as to an absorption agent and a method for removing acid gases from a fluid flow, particularly for selectively removing hydrogen sulphide over carbon dioxide. The invention also relates to certain amines suitable for selectively removing hydrogen sulphide. Absorption agents based on the amines of formula (I) have a high degree of selectivity, high loading capacity and good regeneration capacity.