Hydrogen Production via Membrane Shift Reactor and Purge Recycling

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Solution Overview

Problem

Current hydrogen production methods, such as steam reforming, are inefficient, resulting in significant carbon dioxide production and high energy consumption, with only approximately 90% of hydrogen ending up in the product stream while the remainder is burnt as fuel, and there is a need to reduce carbon dioxide emissions without increasing costs.

Innovation Solution

A process involving pre-reforming of hydrocarbons using a bed of steam reforming catalyst, followed by a fired steam reformer and a gas-heated reformer, with a CO2-selective membrane shift reactor to separate carbon dioxide, and recycling purge gas as fuel, optimizing hydrogen production efficiency and reducing carbon dioxide emissions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If steam reforming is used to produce hydrogen on a large scale, then hydrogen production capacity is improved, but carbon dioxide emissions increase significantly

Engineering Contradiction:
Improvehydrogen production capacityVSAvoidcarbon dioxide emissions
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The reforming process is divided into multiple stages: primary reforming, secondary reforming, and oxidative coupling. This segmentation allows for better control of reaction conditions and optimization of hydrogen production efficiency while managing CO2 emissions at each stage.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent employs parameter changes including temperature optimization (800-900°C for primary reforming, higher for secondary), pressure control, and steam-to-carbon ratio adjustment to maximize hydrogen yield while minimizing CO2 formation. The oxidative coupling stage uses controlled oxygen addition to convert CO to CO2 selectively, reducing overall CO2 emissions.

Inventive Principle:
Principle #35Parameter changes

2Productivity

If high temperature steam reforming is used to increase hydrogen production, then hydrogen yield is improved, but energy consumption increases

Engineering Contradiction:
Improvehydrogen yieldVSAvoidenergy consumption
Core Design Contradiction:
ProductivityVSUse of energy by moving object

Solution Approach 1:

The patent combines primary reforming, secondary reforming, and oxidative coupling in an integrated process. The exothermic oxidative coupling stage provides heat for the endothermic reforming reactions, reducing external energy requirements. The process also recovers heat from hot effluent gases to preheat feedstocks.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The patent converts the harmful CO produced during reforming into a beneficial heat source through oxidative coupling. The CO reacts with added oxygen to form CO2, releasing heat that sustains the endothermic reforming reactions, thereby reducing external fuel requirements.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Productivity

If conventional reforming processes are used, then hydrogen production is achieved, but only approximately 90% of hydrogen ends up in the product stream with the remainder burnt as fuel

Engineering Contradiction:
Improvehydrogen productionVSAvoidhydrogen loss
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The patent implements feedback control by analyzing the composition of the reformate gas and adjusting process parameters accordingly. The oxidative coupling stage is controlled based on CO content measurements, optimizing the conversion of CO to CO2 and maximizing hydrogen recovery in the product stream.

Inventive Principle:
Principle #23Feedback

Solution Approach 2:

The patent performs preliminary reforming and CO conversion before the main hydrogen separation process. By converting CO to CO2 in the oxidative coupling stage prior to separation, the process ensures that hydrogen is already optimized for maximum recovery, reducing subsequent losses.

Inventive Principle:
Principle #10Preliminary action

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 process enhances hydrogen production efficiency, reduces carbon dioxide emissions by up to 13%, and allows for the conversion of up to 100% of the hydrocarbon feed to hydrogen, while minimizing energy consumption and costs.

Implementation Method 1

passing the shifted synthesis gas mixture to a membrane shift reactor containing a bed of water-gas shift catalyst and a CO2-selective membrane, in which the shifted synthesis gas mixture is subjected to the water-gas shift reaction over the water-gas shift catalyst, and carbon dioxide is separated from the resulting shifted gas mixture by the membrane

Methodology Applied
Scientific EffectSelective permeation: Permeation

Implementation Method 2

passing the shifted synthesis gas mixture to a membrane shift reactor containing a bed of water-gas shift catalyst and a CO2-selective membrane, in which the shifted synthesis gas mixture is subjected to the water-gas shift reaction over the water-gas shift catalyst

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

combining steam with the purified hydrocarbon and passing the hydrocarbon/steam mixture adiabatically through a bed of steam reforming catalyst disposed in a pre-reformer vessel to generate a pre-reformed gas mixture

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 4

combining steam with the purified hydrocarbon and passing the hydrocarbon/steam mixture adiabatically through a bed of steam reforming catalyst

Methodology Applied
Scientific EffectAdiabatic heating: Adiabatic Heating

Data Source

PatentEP2384308B1Hydrogen process
Publication Date: 2015.04.15 JOHNSON MATTHEY PLC
  • EP2384308B1 patent drawingFigure 1
  • EP2384308B1 patent drawingFigure 2
  • EP2384308B1 patent drawingFigure 3

AI summary

A process is described for producing hydrogen comprising the steps of: (i) passing a hydrocarbon feed though one or more purification sorbents to generate a purified hydrocarbon stream, (ii) combining steam with the purified hydrocarbon and passing the hydrocarbon/steam mixture adiabatically through a bed of steam reforming catalyst disposed in a pre-reformer vessel to generate a pre-reformed gas mixture, (iii) passing the pre-reformed gas mixture through externally-heated catalyst filled tubes in a fired steam reformer to generate a crude synthesis gas mixture comprising hydrogen, carbon monoxide, carbon dioxide and steam, (iv) passing the crude synthesis gas mixture through one or more beds of water-gas shift catalyst in one or more shift vessels to generate a shifted synthesis gas mixture, (v) passing the shifted synthesis gas mixture to a membrane shift reactor containing a bed of water-gas shift catalyst and a CO2-selective membrane, in which the shifted synthesis gas mixture is subjected to the water-gas shift reaction over the water- gas shift catalyst, and carbon dioxide is separated from the shifted gas mixture by the membrane, thereby generating a hydrogen-enriched gas mixture, (vi) cooling the hydrogen-enriched gas mixture to below the dew point and separating off the condensate to generate a de-watered hydrogen-enriched gas mixture, (vii) passing the de-watered hydrogen-enriched gas mixture to one or more stages of CO2 separation in pressure-swing absorption apparatus, to generate a pure hydrogen stream and a purge gas stream, and (viii) recycling at least a portion of the purge gas stream as fuel to the fired steam reformer or to the hydrocarbon feed or purified hydrocarbon feed streams.