Membrane and Fluidized Bed Reactor Research at MRT and NORAM

Towards Industrial Applications:

Membrane and Fluidized Bed Reactor Research at MRT and NORAM

Anwu Li 1, Tony Boyd 1, Ali Gulamhusein 1 & Andres Mahecha-Botero 1

NORAM Engineering and Constructors Ltd.

John Grace 1, Jim Lim 1 & Nong Xu

University of British Columbia, Chemical & Biologic al Engineering

1. Past associates of Membrane Reactor Technologies Ltd.

ECN Workshop on Pd-membrane technology scale-upNovember 20-21st, 2014

2014 NORAM Engineering and Constructors Ltd

Nitration Sulphuric Acid Waste water Pulp & PaperElectrochemical


NORAM Engineering www.noram-eng.com

• Private owned group serving the process industries

• Engineering: NORAM Engineering (Vancouver), NORAM International (Sweden)

• Technology development: BC Research (Vancouver)

• Equipment fabrication: Axton (Vancouver)

• Providing novel technology, equipment & engineering packages

Highlights of Pd Membrane Commercialization at Membrane Reactor Technologies / NORAM

2002 2006 20101998 2014

MRT founded

based on work

of Adris (UBC)

& Roy (U of C)

DOE FBMR

awarded

NORAM

buys all

MRT

shares

PdRu tests

on bio-

syngas

NORAM

invests in

MRT

2nd Tokyo

Gas FMBR

with CO2

sorbent

Pd purifier

demos (PdAg,

PdRu)

Foil

bonding

patent


NORAM / MRT Research Summary

• Autothermal Fluidized Bed Membrane Reactors (FBMR)• Internally circulating FBMR• DOE / Linde demonstration project• Sorbent enhanced FBMR (Tokyo Gas)

• Pd based membranes• PdAg foil membranes• Electroless plated PdRu membranes


• Autothermal• Air addition provides energy directly• No reactor heat transfer area

• Fluidized bed• Excellent heat and mass transfer• Relatively isothermal conditions for H2

membranes• Can separate reforming (membrane) zone

from oxidation • Solids (and CO2 sorbents) move through

(and out of) the reactor

• Membrane Reactor• High conversion at lower temperatures• In-situ H2 production eliminates shift

reactors and PSA• Foil based PdAg membranes used at

~550ºC and up to 25 bar

Membrane modules

CH4/steam

Pure H2

Exit gases

Air

Fluidized bed

Autothermal Fluidized Bed Membrane Reactorsfor H 2 Production using SMR


• Planar membranes in draft box, which inducing catalyst circulation

• Separation of membranes from oxidant addition zone

• Diluting N2 exits reactor without reduction in membrane permeation

Learnings:

• Internal circulation works, but complicates mechanical design at smaller scale

• Startup / shutdown critical to membrane longevity

• Need to simplify reactor and improve membranes

Effluent Gases

Planar membrane modules

Reactants (natural gas & steam)

Product H2

Draft box

Internally Circulating FBMR(US patent 7141231)

Air


FBMR –15 Nm 3/h H2 production(Sponsored by US DOE and BOC / Linde)

• 15 Nm3/h H2 design

• 100 bar H2 using metal hydride compressor

• 2.2 m2 of improved 25 µm PdAgmembranes in a novel reactor

• Operated for >500 h, 1 week unattended

Learnings:

• Stable operations, results agreed with model predictions

• Some catalyst deactivation noted

• H2 Purity 99.9 to > 99.99%


Sorbent Enhanced FBMR(Sponsored by Tokyo Gas and NEDO)

Pure H2

CH4/steam Steam

Exit gases CO2/steam

HeatFBMR /Carbonator

CaCO3

CaO

Calciner

• Combine CO2 capture with membrane reforming

• CaO + catalyst, solids move between reactors

• 1 Nm3/h H2

Learnings:

• Best results showed 80% CO2capture and 99.99% H2

• Proved CO2 removal increases H2production

• Difficult to match reactor temperatures and pressures

• Challenging to circulate solids reliably at small scale


FBMR Summary / Remarks

• FBMRs work and can operate stably and reliability

• Technical / product challenges remain :• Membrane stability over months of operation

• H2 purity: >99.99% for most consumers

• Business challenges• Distributed hydrogen generation market has yet to f ully develop

• H2 is a bulk chemical effectively made by conventional SMR at larger scale


NORAM / MRT Membranes

PdAg foils Electroless plating (Pd / PdRu)


Pd Membranes at NORAM / MRT

Foil based Electroless plating

H2 purity > 99.99% >99.5%

Thickness 15 to 25 µm 3 to 10 µm

Main alloy focus Pd – Ag 25% Pd - Ru (1 to 11+%)

Form Planar, double-sided Planar or tubular

Substrate Metallic Metallic or ceramic

Current service conditions 25 bar, 575ºC 10 bar, 475ºC

Pd components 3rd party foils In-house from Pdchemicals

Applications? Membrane reactors, high purity separators

Industrial scale separators


PdAg Foil Membranes

Hydrogen Assisted Diffusion Bond (US patent 7,353,9 82): an effective sealing technique to modularize membranes

• Easy to join with the other metallic parts of the s ystem

• No erosion issues noted in fluidized bed service

• Extensive service testing (up to 14,000 h)

PressingMembrane foil

Solid SS

Porous SS

Schematic of bonding process for planar module

Diffusionbarrier


25 µm: 75 x 280 mm, double-sided

25 µm: 150 x 300 mm, double-sided

PdAg Foil Membranes: Examples

Purifier assembly (1.1 m 2)


Objectives of NORAM’s composite membrane program:• Improved robustness and mechanical stability throug h alloying

• Higher flux and cost reductions compared to our foi l modules

Why electroless plating?• Reliable, low cost technique

• Easily adapted to different substrate shapes and ma terials

Why alloy with ruthenium? • Increased strength and hardness: Pd4.5%Ru 5x strong er than Pd at 550 ºC

• No H2 permeability penalty: measured flux rates very clos e to pure Pd

• Higher melting points: less potential for segregati on

• Lower H 2 solubility: less swelling and embrittlement

� Key challenges: Electroless Ru plating and alloying of PdRu

Electroless Plating of PdRu Membranes


Ru bath for electroless plating

• Novel Ru plating bath developed (US patent applicat ion)

• Dense PdRu membranes successfully fabricated & test ed• Substrates: ceramic disks / tubes and porous stainl ess steel

• 2 to 10 µm thick (typically ~4 µm)

• Ru content 3 to 11%, alloying confirmed by XRD & ED X through depth of film

(1) Mild plating temperature

(2) High plating rate, very short plating time

(3) High plating efficiency of Ru in bath

(4) Stable chemical solution over time

(5) Controllable Ru content (up to 11 wt%)

(6) High reproducibility

The features of Ru bath The surface of Pd-Ru on ceramic tube


Fabrication of a PdRu membrane on porous sintered stainless steel

Surface modification

Multiple stages of Pd and Ru plating

PdRu film(post-platingannealling)


Tubular Pd-Ru composite membraneTubular Pd composite membrane

PdRu Membrane TestingBetter resistance of PdRu to H 2 embrittlement at low temperatures


Cracks formed after 9 temperature cycles between 180 ℃ and 350 ℃

(Pd 7.6 µm on PSS disc, membrane area 6.6 cm2)

Remaining stable after 26 temperature cyclesbetween 180 ℃ and 350 ℃

(Pd-Ru 7.9 µm on PSS disc, Ru 8 wt%, membrane area 6.6 cm2)

0 200 4000

90

180

270

360

Total, 9 temperature cycles

Temperature from 180 to 350 oC Permeation flux of hydrogen at 101 kPa ( ∆p)

Time (hours)

Tem

pera

ture

(0 C

)

Here,gas leakage at 180 oC

0

3

6

9

12

15

18

Perm

eation flux of hydrogen (m3 / (m

2h))0 300 600

0

90

180

270

360

Temperature from 180 to 350 oC Permeation flux of hydrogen at 101 kPa ( ∆p)

Time (hours)

Tem

pera

ture

(0 C

)0

3

6

9

12

15

18

21 Perm

eation flux of hydrogen (m3 / (m

2h))

Pd-Ru/ceramic/PSS

composite membrane

Pd/ceramic/PSS

composite membrane

PdRu Membrane TestingBetter stability than Pd against temperature cyclin g


Long-term performance study of Pd-Ru membrane under different temperatures and pressures (Pd-Ru 6.4 µm, Ru 8 wt%, membrane area 6.6 cm2)

PdRu Membrane TestingExtensive service testing up to 20 bar and 450ºC


Membrane testing unitand its control system

PdRu Membrane TestingTesting on slipstream from 5 MW biomass gasifier


Summary of PdRu Membrane Development

• After several years of development, electroless PdRumembranes can now be made reliably:

• New electroless bath developed

• Ru content up to 11%, alloying confirmed

• Sintered metal and ceramic substrates used

• H2 flux characteristics similar to pure Pd

• Thin PdRu membrane characteristics are promising:• Thousands of hours of service testing

• High (but not perfect) H 2 selectivity

• Service temperature currently limited to ~475ºC. Le aks develop with time at 550ºC

• Far less susceptibility to H 2 embrittlement at lower temperatures

� Significant increase in robustness during cycling / startup / shutdown


Concluding Remarks

• FMBR’s / membrane reactors work, but challenges rem ain• Only as effective as the membranes • Can niche applications be found on higher value pro cesses than H 2 for

energy?

• NORAM Pd membranes • PdAg foil membranes:

• Technically mature product

• Monitoring foil improvement from 3 rd parties

• PdRu composite membranes:• Working to increase service temperature and pressur e

• Looking for a first industrial demonstration projec t

NORAM is open to commercial and technical collabora tion


Membrane and Fluidized Bed Reactor Research at MRT and NORAM

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