Flexible Hybrid separation system for H2 recovery from … · the economics of central hydrogen production from excess renewable energy ... (TLR 5) The environmental ... Working principle:

04/12/2017 Page 1 (Disclosure or reproduction without prior permission of HyGrid is prohibited).

Flexible Hybrid separation system for H2 recovery from NG Grids

HyGrid

This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 700355. This Joint Undertaking receives support from the European Union’s Horizon 2020

research and innovation programme and Hydrogen Europe and N.ERGHY

Duration: 3 years. Starting date: 01-May-2016 Contacts: [email protected]

The present publication reflects only the author’s views and the FCH JU and the Union are not liable for any use that may be made of the information contained therein.

https://www.hygrid-h2.eu/

mailto:[email protected]






Chemical Process Intensification, Chemical Engineering and Chemistry, Eindhoven University of Technology

Electricity consumption and CO2 emissions

Fuel share of electricity generation in the world

* IEA Keyworld 2016

Introduction


New actors in the CO2 emission frame: China and India

* IEA Keyworld 2016


Introduction


Chemical Process Intensification, Chemical Engineering and Chemistry, Eindhoven University of Technology

Regional share of CO2 emissions

* IEA Keyworld 2016


Introduction


Advantages of the H2 based economy: • Direct transformation chemical energy in electricity • Higher efficiency • No CO2 emissions • Few moving parts


Introduction


Introduction

One of the main problems for the implementation of the hydrogen based economy is the transportation from production centers to the end user.

One approach to solve this problem is to use the existing Natural Gas

network for storing and distributing hydrogen.

The HyGrid technology will provide a route to: Increase the value of hydrogen blended into the natural gas grid, improving

the economics of central hydrogen production from excess renewable energy couples with natural gas grid injection.

Reduced cost, and therefore increased use of hydrogen from very dilute hydrogen streams in energy and transport applications.

Further applications could be found in separating hydrogen from mixtures produced in chemical or biological processes, where it otherwise would be used to generate heat or even be vented.


General concept

HyGrid aims at developing of an advanced high performance, cost effective separation technology for direct separation of hydrogen from natural gas networks.

The system will be based on:

Design, construction and testing of an novel membrane based hybrid technology for pure hydrogen production (ISO 14687) combining three technologies for hydrogen purification integrated in a way that enhances the strengths of each of them: membrane separation technology is employed for removing H2 from the “low H2 content” (e.g. 2-10 %) followed by electrochemical hydrogen separation (EHP ) optimal for the “very low H2 content” (e.g. <2 %) and finally temperature swing adsorption (TSA) technology to purify from humidity produced in both systems upstream.

The project targets a pure hydrogen separation system with power and cost of < 5 kWh/kgH2 and < 1.5 €/kgH2. A pilot designed for >25 kg/day of hydrogen will be built and tested at industrially relevant conditions (TRL 5).


General concept

99.99% H2 purity (ISO14687)


Partnership

Multidisciplinary and complementary team: 7 top level European organisations from 4 countries: 2 research institutes and 5 top industries (3 SME) in different sectors (from materials development to membrane modules and separation systems, etc.).

1 TU/e, Netherlands 2 TECNALIA, Spain 3 HYG, Netherlands 4 SAES, Italy 5 HYET, Netherlands 6 QUANTIS, Switzerland 7 Nortegas Energía, Spain


Consortium

1 TU/e, Netherlands 2 TECNALIA, Spain 3 HYG, Netherlands 4 SAES, Italy 5 HYET, Netherlands 6 QUANTIS, Switzerland 7 Nortegas Energía, Spain


Project objectives

Development of a hydrogen separation system capable of targeting low (2-10%) and very low (<2%) H2 blends in natural gas. o Membranes for H2 recovery from low hydrogen content streams (2-10%). o EHP for H2 recovery from very low concentration streams (<2%) . o TSA for water removal from hydrogen/water streams.

Technical validation of the novel modules at lab scale.

Optimization of the hybrid system.

Energy analysis of the new HyGrid technology on different scenarios: o recovery of H2 from low concentration streams (2% -10%) up to 99.99%

H2 purity (ISO14687) in the whole range of pressures of the NG grid. o Different configurations/combinations of the three separation technologies

The validation of the novel hybrid system at prototype scale (TLR 5)

The environmental LCA of the complete chain.

Dissemination and exploitation of the results.


Work Structure - Partnership Synergies


Membranes development

Development of cost effective tubular supported membranes for the recovery of hydrogen from low concentration streams (2% -10%) in the whole range of pressures of the Natural Gas Network. Two different types of membranes will be developed as well as the final membrane module: Pd-based membranes for the medium to the lowest Natural Gas

Grid pressures with improved flux and selectivity. Carbon Molecular Sieve membranes for the high pressure range. Membrane module for the prototype.

Objectives:


Permation of H2 against H2/N2 selectivity

Mesoporous Ceramics (nm)

Zeolites Carbon

Microporous Ceramics (Å)

Palladium Palladium alloys

0.1

1

1000

100

10

10 100 1000 10000 ∞

Rela

tive

Hydr

ogen

per

mea

tion

H2/N2 selectivity

Inorganic, metallic & carbon membranes


Nanopores + constrictions

Membrane thickness

Transport mechanism

Carbon Molecular Sieve membranes


40 °C 4h 90 °C overnight

Dry

Carbonization

550 °C 2h 1°C/min under N2

vacuum

Dip coating

Preparation of composite Al2O3 – CMSM



Gas permeation of composite Al-CMSM at various temperatures


Robeson plot of the of composite Al-CMSM


Porous Support: Supplied by Rauschert 100nm pore size Al2O3

Pd-Ag membrane layer deposition by Electroless Plating technique

Join to dense ceramic tube at Tecnalia

~4 µm thick Pd-Ag membrane

Membrane length before

sealing: 14-15 cm

Pd-Ag

ZrO2 110 nm on Al2O3

Cross-section SEM image

Surface SEM image

Ceramic supported Pd-based membrane


Single gas permeation test

0 50 100 150 200 2500.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Temperature (°C) 385 455 490 545 598A

vera

ge h

ydro

gen

flux

(mol

s-1 m

-2)

Transmembrane pressure difference p0.5H2ret-p

0.5H2perm (Pa0.5)

Ea: 10 kJ/mol; P0: 6.93 x 10−8 mol m-1 s-1 Pa-0.5

Fernandez et al., Preparation and characterization of thin-film Pd-Ag supported membranes for high-temperature applications. International Journal of Hydrogen Energy 40:13463-13478, 2015.

Ceramic supported Pd-based membrane


0

50000

100000

150000

200000

250000

300000

350000

0.0E+00

4.0E-07

8.0E-07

1.2E-06

1.6E-06

2.0E-06

2.4E-06

2.8E-06

0 100 200 300 400 500 600 700 800

Idea

l sel

ectiv

ity H

2/N2

Perm

eanc

e H 2

(mol

/s/m

2 /Pa)

Time (h)

500 °C 525 °C 550 °C 575 °C 600 °C

SH2/N2 = 2650

Membrane M17-E94. Long-term stability test (500-600 ºC)

Metallic supported membrane M14. Long-term stability test over time at 400 ºC

Long-term stability test

Medrano et al., Pd-based metallic supported membranes: high-temperature stability and fluidized bed reactor testing, International Journal of Hydrogen Energy, 2015. http://dx.doi.org/10.1016/j.ijhydene.2015.10.094

Metallic supported Pd-based membrane


The thickness is controlled by the plating time There is a trade off between permeance and selectivity

Thickness versus plating time Selectivity and H2 permeance versus thickness

Ultra-thin (≈ 1 µm) supported Pd-Ag membranes by Electroless Plating

H2 permeance (400ºC)= 3.1x10-6 (mol m-2 s-1 Pa-1); H2/N2= 8,000 – 10,000 H2 permeance (400ºC)= 4.2x10-6 (mol m-2 s-1 Pa-1); H2/N2= 20,000

FluidCELL FCH JU – FP7 project (www.fluidcell.eu)

http://www.fluidcell.eu/


Membrane Thickness Porous support

H2 permeance x10-7 mol m-2 s-1 Pa-1 @ ΔP 1 atm

H2/N2 selectivity

Thin Pd-Ag 4-5 µm Metallic ≈ 10 at 400 °C >100.000 Alumina* ≈ 30 at 400 °C >20.000

Ultra-thin Pd-Ag ≈ 1 µm Alumina ≈ 100 at 400 °C > 2.000 CMSM 3-4 µm Alumina ≈1 at 30°C ≈ 500

Separation properties of membranes previously developed at TECNALIA

* Over DOE targets 2015

Membrane Thickness Porous support

H2 permeance x10-7 mol m-2 s-1 Pa-1 @ ΔP 1 atm

H2/N2 selectivity

Thin Pd-Ag 4-5 µm Alumina ≈ 3,3 at 400 °C >20.000 Ultra-thin Pd-Ag ≈ 1 µm Alumina ≈ 11.8 at 400 °C > 2.000

Permeation tests at gas compositions similar to the HyGrid (90% CH4 & 10% H2)

Background on Pd-based membranes


Electrochemical hydrogen separation development

Objectives: Development of an electrochemical hydrogen purifier (EHP) for the recovery of the hydrogen from very low concentration streams (≤ 2 %). Capable of recovering the majority of the remaining hydrogen from the

retentate of the membrane separator. Optimum configuration of membrane-electrode-assembly for low

concentration hydrogen extraction. Theoretical modelling assisted optimum design of stack and gas

distribution plate geometry for low concentration electrochemical hydrogen extraction (<3%).

Construction and testing of sub- and full size electrochemical

compressor stacks for model validation and prototype preparation.



Key performance indicators for EHP:

Working principle:



Modelling EHP: Model set up in Matlab for EHP system configurations to find setup of the system meeting the KPIs Iterations: Operating temperature Number of cells Type of membrane Hydrogen concentration Pressure

Conclusion: Meeting the KPIs for EHP is possible with the right number of cells, operating temperature, membrane and pressure for hydrogen concentration in the feed gas between 2 and 10%



Sub scale testing EHP: Platform HCS100 developed, capable of pure hydrogen pressure of 700 bar and pump rate (current density) of 1 A/cm2

Conclusions purification testing: Two flow field design tested and analysed. One has been selected Humifidication of feed gas highly influences stable performance of EHP Outlook: Review anode flow field design needed for HyGrid EHP cell: lowering

pressure drop and expanding holdup time in EHP cell Continuing testing on stability for multi-cell stacks



System development around EHP: Small scale system tested in Rozenburg (NL), started within project PurifHy. Established base-line EHP performance with sub-optimal EHP cell hardware. Conclusion: 90% recovery rate is feasible with high surface area and with

high energy demand

recovery rate

The Rozenburg test location Testing data Rozenburg


Temperature Swing Adsorption development

Objectives: Design, construction and test of the TSA unit. Better comprehension of the behaviour and performance of the

adsorption materials used in TSA. Understanding of the response of adsorbents to the dynamic

temperature control. Implementation of the know-how gained through lab tests onto the up-

scaled design. Design of prototype TSA unit for integration in pilot scale HyGrid

system.

Testing of pilot scale TSA unit.


Development of TSA strategy and sizing

Sorbent materials tested: Several materials tested in test rig

regarding sorption capacity as function of process variables

Sorbent material selected as function of product dew point

Most optimal regeneration procedure defined for prototype TSA based on optimized operational costs

Mathematical model validated and TSA sizing ready

Laboratory test rig


Prototype TSA

Prototype TSA: • Process flow diagram defined • Operational safety assessed • Control strategy implemented • Prototype assembly ready

Next steps: testing prototype integration with membrane and EHP module

Ads 1(producing)

Ads 2(regenerating)

Feed

Heater

Product

Cooler/condenser

Regeneration gas compressor

G/L separator

Water

cooling

heati ng

Regeneration gas

PFD prototype TSA Prototype TSA assembly


Lab scale testing

Objectives: Design and test a small version of the prototype and test it at lab scale especially in conditions not feasible for the prototype. Investigate the recovery of the membrane system at different pressures

and different concentrations of hydrogen.

Sorbents for the TSA selected will be further studied in TGA experiments to evaluate the cyclic sorbent capacity and adsorption isotherms.

Evaluation of different configurations to identify the optimum separation

system along the natural gas network.


A small test rig will be updated at TUE to be able to test smaller versions of the hybrid separation technology of HyGrid at different conditions. In particular the system will be designed to be able to work at up to 20 bar (now up to 50 bar) at low hydrogen contents recovery

Design and building of the lab scale rig


0.03

0.08

0.13

0.18

0.23

0.28

35 85 135 185

Hyd

roge

n re

cove

ry fa

ctor

[-]

Hydrogen partial pressure [Pa0.5]

0.3 l/min sweep gas

0.5 l/min sweep gas

0.7 l/min sweep gas

1 l/min sweep gas

1.5 l/min sweep gas

2 l/min sweep gas

3 l/min sweep gas

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

0 100 200 300 400

Hyd

roge

n pe

rmea

tion

[mol

/s/m

2 ]

Hydrogen partial pressure [Pa0.5]

T=418C ultra-thin E635T=382C ultra-thin E635T=426C ultra-thin E633T=370C ultra-thin E633T=427C ultra-thin E689T=391 C ultra-thin E689

Different Pd-Ag membranes has been tested changing the following operating conditions: Temperature and pressure

Type and amount of sweep gas

Testing of membranes and sorbents


0.04

0.06

0.08

0.1

0.12

0.14

0 2000 4000 6000 8000 10000 12000 14000

H2

perm

eate

[l/m

in]

Logarithmic partial pressure [Pa]

10% H2 1.5l/min sweepgas10% H21l/min sweepgas10% H2 0.8l/min sweepgas10% H2 0.9l/min sweepgas

0

500

1000

1500

2000

2500

3000

3500

0 200 400 600 800 1000 1200

H2

perm

eatio

n [m

l/min

]

pressure difference [Pa0.58]

70%CH4 30%H260%CH4 40% H250%CH4 50%H240%CH4 60%H230%CH4 70%H220%CH4 80%H210%CH4 90%H2

Changing H2 concentration

Changing H2 concentration

with sweep gas

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0 100 200 300 400 500 600

H2

perm

eate

[l/m

in]

Average partial pressure of hydrogen [Pa0.595]

20% H2 0.3l/min sweep gas




20% H2 1l/minsweep gas



0.0000

0.0200

0.0400

0.0600

0.0800

0.1000

0.1200

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0.1600

0.1800

0.2000

0.0000 0.0100 0.0200 0.0300 0.0400 0.0500 0.0600

weig

ht d

iffer

ence

[-]

H2O partial pressure [bar]

45C silica

55C silica

65C silica

45C zeolite 4A

55C zeolite 4A

65C zeolite 4A

Zeolite 4A, modified zeolite 4A, zeolite 13X and silica have been tested at different temperature and different steam content in order to study the adsorption capacity.

0

0.05

0.1

0.15

0.2

0.25

0.3

0 0.1 0.2 0.3 0.4 0.5 0.6

wei

ght d

iffer

ence

[-]

Steam partial pressure [bar]

100 C90C80C

There is a significant difference between zeolite and silica in adsorption capacity.



Prototype integration and validation

Objectives:

Design of the integrated hydrogen recovery pilot plant Construct and assemble the hydrogen recovery pilot plant

including controls Testing and assessment of hydrogen recovery pilot plant


System modelling and simulation

Objectives: To assess the energy analysis, and economic performance (in terms of primary energy consumption and cost of pure H2) of the HyGrid system for H2 separation from NG grid. Membrane module model and simulation. Development of dynamic model for TSA. Modelling of electrochemical separation and compression.

Simulation and economic optimization of integrated hydrogen recovery


PHb H2 partial

pressure in the bulk

PHl Hydrogen partial pressure in the

bulk

H2 partial pressure on the

surface PHs

There are 3 different possible mass transfers in the Pd membrane: Retentate side Porous support Permeate side

The difference between experimental and modelled results should be find in the mass transfer limitation due to a hydrogen-depleted layer adjacent to the membrane surface.

Membrane modelling


0

10000

20000

30000

40000

50000

60000

0.00 0.01 0.02 0.03 0.04 0.05 0.06

Pres

sure

[Pa]

Lenght [m]

retentate pressure = 5 bar

retentate pressure=4 bar

retentate pressure = 3.5

The pressure on the surface is remarkably different from the retentate partial pressure.

0

50

100

150

200

250

0 1 2 3 4 5

Hyd

roge

n flu

x [m

l/min

]

total pressure difference [bar]

experimentalresult

modeling withmass transferlimitation

modeling nomass transfer

𝐽𝐻 =𝑘𝐻 ∗

𝑃𝐻𝐻 − 𝑃𝐻𝑃𝑅𝑅

1 − (0.5 ∗ (𝑃𝐻𝐻 − 𝑃𝐻𝑃)/𝑃𝑅𝑃

𝑑𝑑𝐻𝑃𝑑𝑑 = −2 ∗ π ∗ 𝑅 ∗ 𝑄𝐻 ∗ (𝑃

𝐻𝐻

𝑛 − 𝑃𝐻𝐻

𝑛)

Surface partial pressure Retentate partial pressure

𝐽𝐻 =𝑘𝐻 ∗

𝑃𝐻𝐻 − 𝑃𝐻𝑃𝑅𝑅

1 − (0.5 ∗ (𝑃𝐻𝐻 − 𝑃𝐻𝑃)/𝑃𝑅𝑃 − 𝑄𝐻

∗ 𝑃𝐻𝐻

𝑛 − 𝑃𝐻𝐻

𝑛 = 0

Membrane modelling


Total electric consumption 3.9 kWh/kgH2 < 5 kWh/kgH2 Total hydrogen separated 27.26 kgH2/day > 25 kgH2/day

purity 99.98 % > 99.97 % HRF 90 % > 85 %

Total membrane area 3.33 m2

Total electric consumption 3.88 kWh/kgH2 < 5 kWh/kgH2 Total hydrogen separated 26.055 kgH2/day > 25 kgH2/day

purity 99.977 % > 99.97 % HRF 86.906 % > 85 %

Total membrane area 4.91 m2

Two different configuration has been modelled to optmize the targets required

First case: two membrane modules

Second case: one membrane module

Simulation of the hybrid system


Environmental LCA and economic assessment

The new H2 separation technology will be analysed and compared to other available technologies using LCA and LCC in an iterative process to guide the design and development of the novel technologies and products towards sustainable solutions.

Environmental

Constraints

Safety Constraints

Process Performance Constraints

An Environmental Life Cycle Assessment will be performed by applying and testing the most up-to-date life cycle impact assessment methods

Life Cycle Costing will be performed and the latest advances in monetary valuation of impacts will be tested

A business plan will be developed as part of the economic assessment


Overall, the main questions analysed during the goal and scope development include:

What is the aim of the study?

What is the function of the analysed system?

What systems exactly are going to be analysed?

What reference system/ technology will we compare our system against?

What are the system boundaries of the analysed product?

What environmental indicators will be calculated?

What is the data availability for the study?

Goal and scope definition


Functional unit: “The recovery from an average European natural gas grid of 1 kg of hydrogen with a purity of at least 99.97%.”

Reference technology (to compare with the HyGrid system): pressure swing adsorption (PSA)

Main outcomes of goal and scope definition


System boundaries


Flexible Hybrid separation system for H2 recovery from NG Grids

HyGrid

Thank you for your attention Contacts: [email protected]


mailto:[email protected]


Documents

Flexible Hybrid separation system for H2 recovery from … · the economics of central hydrogen production from excess renewable energy ... (TLR 5) The environmental ... Working principle: