thomas development of large scale hydrogen liquefaction ver03

Development of Large Scale Hydrogen Liquefaction

Development of Large Scale Hydrogen LiquefactionFaculty of Mechanical Science and Engineering // Institute of Power EngineeringBitzer-Chair of Refrigeration, Cryogenics and Compressor Technology // Thomas FunkeHydrogen Liquefaction & Storage Symposium, UWA // 27.09.2019

Slide 2

Agenda

0. TU Dresden and Bitzer Chair

1. Theory of (Cryogenic) Cooling

2. Hydrogen Liquefaction


Slide 3

Technische Universität Dresden

- 14 faculties- Approx. 37 000 students- 8500 employees- 507 professors

ð focus on engineering science

2012 & 2019: awarded into the status„University of Excellence“


Slide 4

BITZER Chair of Refrigeration, Cryogenics and Compressor Technology

- founded 1958

- 1993 – 2008 Prof. Hans QUACK (cryogenics officially added)

- Today: Prof. Dr.-Ing. U. Hesse Refrigeration + Compressors

Prof. Ch. Haberstroh Cryogenics

- Number of employees: 30

- Focus in Cryogenics: Helium plants; liquid heliumHydrogen technology, ortho-para conversionLNG; NeonTransfer linesDewars; Thermal insulationTeaching


Slide 5

- Refrigeration Technology (alternating in German / in English) Σ 200 students

- Piston Compressors Σ 80 students- others Σ 4 … 100 students/course

- Cryogenics (winter term, once per year) Σ 70 students

- Master Course in Hydrogen Technology (M.Sc. HT) - on hold –

- European Course of Cryogenics ~ 40 students from allover Europe

Teaching


Slide 6

Teaching

European Course of Cryogenics

- First course: 2008

- Engineering or PhD students from particpating universities or other institutions1st week Dresden (Hydrogen technology), 2nd week Wroclaw (He), 3rd week Trondheim (LNG)

Excursion to H2-liquefaction and air separationplant Leuna, 2017

ECC 2019 - TU Dresden Trondheim hiking 2013


Slide 7

Theory of (Cryogenic) Cooling


Slide 8


warm

cold

Q0

.

warm

cold

P

Qab= QO + P

Q0

.

. .

Not allowed !OK for energyconservation;

not OK for laws ofthermodynamics

Possible physical effect:o gas compression / expansiono fluid evaporation /

condensationo thermoelectric (Peltier)o magnetocaloric (Gd, …)o thermoacoustico …

any kind of Cooling Machine

extra ΔT ≈ 2 … 5 K needed for heat transfer !

warm

cold

Q0

.

warm

cold

P

Qab= QO + P

Q0

.

. .


Slide 9

0

00min T

TTQP amb -×= !

H

ambHH T

TTQP

-×= !max

TH Hot temp. level

Tamb Ambient temp.

T0 Low temp.

Theory of (Cryogenic) CoolingThermodynamic Limitiation - Carnot

Tamb

T0

T

s

Pmin ~ Tamb – T0

Q0 ~ T0

Second law of thermodynamics (“Carnot”)

Power plant: Maximum Power obtainable from heat flow

Refrigeration: Minimum Power needed to produce refrigeration


Slide 10


Tamb - ToTo

reference temperature: 288 K

cool

er m

inim

umen

ergy

inpu

t[W

/W]

Carnot Limit:

!"#$%&'() = +$%&'() = -̇./012

= 3.340563.

#78' = 340563.3.

9 :̇;

for Tamb = 288 K (ideal, reversible process without any losses!)

To = 280 K a min 0.03 W / W

To = 77 K a min 3 W / W

To = 20 K a min 13 W / W

To = 4 K a min 70 W / W

beware! Extra losses at cold and hot heat exchanger (ΔT ≈ 2 … 5 K)

Temperature [K]


Slide 11

0

100

200

300

400

500

TORESUPRA

RHIC TRISTAN CEBAF HERA LEP LHC

C.O

.P. [

W/W

@ 4

.5K

]

Carnot Limit

COP improvementsachieved for large cryogenic helium plants

Ph. Lebrun, CERN


Carnot fraction:

Efficiency h = e real / eCarnot

household refrigerator: typ. 1 W/W [ h » 5 %

in cryogenics: h = 35 % …. < 1 %

e.g.: input power Pel ≈ 0.5 MW @ 4 K

à min. 70 W/W à "̇# = 7143)

with h = 20% àcooling power "̇# = 1430)


Slide 12

Theory of (Cryogenic) CoolingHow to get a gas cold?

a) Joule-Thomson Effectsimple throttle valve, isenthalpicexpansion (without work extraction)

ΔH = O

a small effect (real gas property)

a below inversion curve only

b) Expansion Machineisentropic change of statework is extracted from the fluid

ΔSideal = O

a big effect at any starting temperture

(ideal gas property)


Slide 13

Cooling cycles with work extracting expansion

isentropic (work extracting) expansion: ΔSideal = 0

idealized:

isothermal compression and heat release

Isobaric cool-down / warm-up

isentropic expansion

Isothermal heat transfer


+ works always (ideal gas property)

+ much higher cooling effect

real: isentropic efficiency ηs

ηs = !" # !$!" # !$%

1

2

3 4

5

ṁ small: volumetric expander (e.g. piston)

ṁ large: turbines

– mechanically demanding


Slide 14

14

Theory: how to get a gas cold?

a) Joule-Thomson Effectsimple throttle valve, isenthalpicexpansion (without work extraction)

ΔH = O

a small effect (real gas property)

a below inversion curve only

b) Expansion Machineisentropic change of statework is extracted from the fluid

ΔSideal = O

a big effect at any starting temperture


a) Expansion maschineisentropic change of stateexpansion (without work extraction)

ΔSideal = Oó big effect any starting temperture


10bar

1bar

Helium Expansion in the T, s diagram

Throttle

Turbineηs = 1

Turbineηs = 0.75


Slide 15


Tì

Tî

T = const.

Inversions curves 4He, H2 , N2 and Joule-Thomson- (J-T-) cycle


Slide 16


Basic Cryogenic Cycles

Brayton ClaudeExpanders in parallel

(Collins)Expanders in seriesplus wet expander


Slide 17

“High-end” Helium Plant

Conceptual design for DESY, TESLA:

Ø 8 cycle compressors in two stages

Ø 9 expansion turbines

Ø 3 cold compressors

heat loads at three temperature levels

Theory of (Cryogenic) CoolingHX 1

HX 3

HX 4

HX 5

HX 6

HX 7

HX 10

HX 9

HX 11

HX 8

HX 2

5 - 8 KShield

40 - 80 KShield

2 KLoad

T 1

T 2/3

T 4/5

T 6T 7

T 8

T 9

CC 2

CC 1

CC 3


Slide 18

Hydrogen Liquefaction


Slide 19

- H2-FC car to lead the men's and women's olympic marathons- GM HydroGen1 5kg LH2 storage


HydroGen1 Photo: Opel


Slide 20

Liquefier arrangement TU Dresden, Dipl. thesis Th. Eisel, built by: D. Kirsten

Hydrogen LiquefactionHydrogen liquefaction plants

„personal“ H2 Liquefierà continuous ortho-para conversion (catalyst)à sub-cooling and Joule-Thomson throttling

~ 10 l LH2 / hr

cooling demand: ~ 2 l LHe / l LH2


Slide 22

Liquefier specific energy consumption = …. % of

lower heating value

Minimum exergy for liquefaction 14.2 MJ/kg = 3.9 kWh/kg 11.8 %

Optimized liquefier 22.4 MJ/kg = 6.2 kWh/kg 18.7 %Existing liquefiers (typ. 5 – 10 tpd) 43 … 54 MJ/kg = 12 … 15 kWh/kg 36 … 45 %

(ð intolerable)

TU Dresden, 10 l/hr, 2004Linde Leuna, 5 tpd, 2008

Rozenburg / NL, Air Products, 5 tpd, 1987Lille / F, Air Liquide, 10 tpd, 1987

Hydrogen Liquefiers worldwide


Slide 23

Hydrogen LiquefactionOrtho-Para Catalyst

IONEX-Type o-p Catalyst (Fe2O3 , today’s industrial standard)

Hydrogen liquefaction

(simplified process, catalyst applied)

ð development of a better catalyst possible!?


Slide 24

Hydrogen LiquefactionOrtho-/Parahydrogen

equilibrium hydrogen, e-H2normal hydrogen (n-H2)75 % o-H2 + 25 % p-H2

0.0

100.0

200.0

300.0

400.0

500.0

600.0

0.0 50.0 100.0 150.0 200.0 250.0 300.0 350.0temperature [K]

enthalpie of evaporation @ 1 bar

Enthalpie of conversion n-H2 à e-H2 [kJ/kg]


Slide 25

0

2

4

6

8

10

12

14

0 50 100 150 200 250 300sp

ecifi

c ex

ergy

e of

nor

mal

hy

drog

en in

MJ/

kgtemperature T in K

20

100

40 60

1 bar

1000

n - H2

ortho-para conversion


Theoretical Minimum Energy for LiquefactionTheoretical Minimum Energy for Liquefaction

typical boundary conditions (industry):

à pre-cooling not very helpfulà better: high feed pressure

H2 feed20 bar / 293 K / 99.99 % purity

LH2 -output

2 bar / 22.8 K / > 98 % para


Slide 26

Quack, H., Conceptual design of a high efficiency large scalehydrogen liquefier, Adv. Cryog. Eng. (2002) p. 255 - 263


How should an improved Large Scale hydrogen liquefier look like?

First study started in 2000, triggered by car industry

Findings:

• use of Neon-Helium mixture

• use of turbo cycle compressors

• Brayton process with 6 expansion turbines incl. power recovery

• efficient pre-cooling

• optimized feed parameters

à 23.7 MJ/kg, i.e. 60 % efficiency

should be possible with existing components


Slide 27

- Shell as consortium leader- KHI as associated participant

Scope develop generic process + plan for demonstration plant

Objective reduce liquefaction energy consumption by 50 % at simultaneouslyreduced investment cost

Timeline Nov. 2011 – Oct. 2013

Information and results available at www.idealhy.eu

Grant Agreement No. 278177

Hydrogen LiquefactionIDEALHY Project


Slide 28

Cryogenic Heat Exchangers

47%

Intercoolers29%

Compressors12%

Turbines and Valves12%

Exergy losses

Exergy loss analysis

Cryogenic cyle issuesdone by:

TUD, Sintef, Linde


Evaluation and Analysis of existing concepts and technology

• papers, proposed processes• machinery and components• turbo cycle compressors• expansion-compression turbine combinations• oil / gas / magnetic bearings• cold boxes and heat exchangers (visible scaling barriers)• catalyst material (activity, necessary amount vs. T)


Slide 29

Feed

LH2 Product

Nelium

MR I

T1

T2

T3

T5

T6

HX 101 HX 106 HX 107

HX 102 a

HX 102 c

HX 201 a

HX 203

HX 204

HX 102 b

C1

C2

C3

C6

C5

HX 202 a

HX 202 b/c/d

Nelium

C4

MR II

Nelium

T4

HX 201 b

HX 103

HX 104

HX 105

Chiller

T7 T8

H2

p-H2

Flash

H2 feed20 bar / 293 K / 99.99 % purity

LH2 outlet parameters

2 bar / 22.8 K / > 98 % para


Final IDEALHY proposed cycle

• 80 bar

• Mixed refrigerant pre-cooling cycle

• Brayton cycle (expander partly overlapping in temperature, power recovery)

• „Nelium“ as working fluid à highly efficient multi-stage turbo compressors

• 6 °C Chiller

• Liquid expander instead of JT valve

• Flash gas recycling


Slide 30

Findings / IDEALHY outcome:

• detailed concept for an advanced hydrogen liquefier 50 tpd• limited R&D / separate test still needed for some components• specific energy demand: 6.4 kWhel /kg LH2

• (6.76 kWhel /kg LH2 incl. auxiliaries) • i.e. 19 - 20 % of H2 lower heating value

• Plant investment costs: 105 M€• for: 20 yr payback period; 10 % rate of return, 0.1 €/kWhel (0,16 AUD/kg LH2)• Liquefaction costs: 1.72 €/kg LH2 (2,78 AUD/kg LH2)

• Evaluation of scale-down options:a) part load operation 100 % - 75 % - 50 % - 25 %b) „improved“ smaller plants (5 … 10 tpd)

à 8 … 9 kWhel / kg LH2 (state-of-the-art: 12 kWhel /kg LH2)

Cost factor €/kg LH2

Annuity 0.74 (43 %)

fixed O&M 0.25 (15 %)

input power 0.68 (39 %)

water, losses 0.04 ( 3 %)

total 1.72



Slide 31


North America:45 % Air Liquide45 % Air Products

Air Products:- 4 liquefiers operating,

ca. 110 tpd LH2

- over 100 LH2 trailer

31

Site operated by Capacity built

Painsville, OH / USA Air Products 3 tpd 1957 *

West Palm Beach, FL / USAAir Products

Air Products

3.2 tpd

27 tpd

1957 *

1959 *

Long Beach, CA / USA Air Products 30 tpd 1958

Mississippi (Test Fac.) Air Products > 36 tpd 1960 *

Ontario, CA / US Praxair 20 tpd 1962 *

Sacramento, CA / USAUnion Carbide, Linde Div.

Air Products

(54) 60 tpd

6 tpd

1966 *

1986

New Orleans, LA / USAAir Products

Air Products

34 tpd

34 tpd

1977 (1963)

1978

Niagra Falls, NY / USA Praxair 18 (40?) tpd 1981

Pace, FL / USA Air Products 30 tpd 1994 *

McIntosh, AL / USA Praxair 24 (29?) tpd 1995

East Chicago, IN / USA Praxair 30 tpd 1997

Sarnia, Ontario / Canada Air Products 30 tpd 1982

Montreal, Canada Air Liquide Canada Inc. 10 tpd 1986

Bécancour, Quebec /Can. Air Liquide 12 tpd 1988

Magog, Quebec /Canada (BOC) Linde 15 tpd 1989

Kourou, Franz. Guayana Air Liquide 5 tpd 1990

Lille (Wazier), France Air Liquide 10.5 tpd 1985

Rozenburg, Netherlands Air Products 5 tpd 1986

Ingolstadt, GER Linde 4.4 tpd 1992 *

Leuna (close to Leipzig,

GER)

Linde

Linde

5 tpd

5 tpd

2008

2021

Dresden TUD 10 l/h 2004* not operating

any more

2019 announced:

4 more liquefiers

to be built

(2 x Texas, 2 x California)


Slide 32

moreover:- China, liquefier Air Liquide, 1 … 2.55 tpd (built 2007 – 2012)- mini liquefier 1 … 3 kgLH2/h

Site operated by capacity builtAmagashi, Japan Iwatani 1.2 tpd 1978 *Tashiro, Japan Mitsubishi Heavy Industr. 0.6 tpd 1984 *Ooita, Japan Pacific Hydrogen Co, Jpn. 1.4 tpd 1986Tane-Ga-Shima, Japan Jpn Liquid Hydrogen 1.4 tpd 1986Minamitane, Japan Jpn Liquid Hydrogen 2.2 tpd 1987

Kimitsu, Japan Nippon Steel Corp. (Air Products?)

0.2 (0.3?) tpd 2004

Sakai, Japan Iwatani Gas 1.1 tpd 2006Osaka, Japan Iwatani (Hydro Edge) 11.3 tpd 2006Chiba (Tokio), Japan Iwatani (built by Linde) 10 (5?) tpd 2008Yamaguchi, West-Japan Iwatani (built by Linde) 5 tpd 2008

KHI Akashi, Japan Kawasaki Heavy Industries à own development!

(5 tpdprototyp) 2015

Indien Asiatic Oxygen 1.2 tpd k.A.Mahendragiri, Indien ISRO 0.3 tpd 1992Beijing, China CALT 0.6 tpd 1995

* not operating any more

1 metric ton = 1 tonne = 1000 kg1 tpd ≈ 600 lLH2/h

USA: 1 ton = 1 short ton = 2000 pound≈ 907.2 kg 1 tpd ≈ 534 lLH2/h



Slide 33

- H2-FC car to lead the men's and women's olympic marathons- GM HydroGen1 5kg LH2 storage


HydroGen1 Photo: Opel


Slide 34

Dipl.-Ing. Thomas FunkeTechnische Universität DresdenInstitute of Power EngineeringBitzer-Chair for Refrigeration, Cryogenics and Compressor Technology01062 DresdenTel.: +49 351 463 40728e-mail: [email protected]

thomas development of large scale hydrogen liquefaction ver03

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