08_h2_plant_operating_experience_t.pdf

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26th September 2005 1 Stefan Brandes / LG / z3646.ppt

Linde Gas

Hydrogen Plant

Operating Experience

Tehran, September 26th 2005

Stefan BrandesLinde Gas


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Linde Gas

HYCO Plant Operating Experience

Content

Linde Gas HYCO Plant Overview

H2-Steam Reformer Operation in Leuna, Germany

H2 and CO (HYCO) Plants

Partial Oxidation based:

Singapore

Laporte, USA

Operation Support & Feed Back to Linde Engineering

and Linde Gas HQ


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Linde Gas

HYCO Plant Operating ExperienceLinde Gas HYCO Plants in Operation

Plants under construction or commissioning

Plant No. Country Main Process Units Supplier

Product H2

[Nm/h]

Product CO

[Nm3/h]

Product

Syngas

[Nm3/h]

Product

Steam [kg/h]

1 CN CB, PSA Linde 4.770 6.000

2 SG Resid-POX, Rectisol, CB, PSA, MW Kellogg, Texaco, Linde, 27.000 32.800

3 CN Cracker, PSA Caloric 600 0 0

4 CN Cracker, PSA Caloric 600 0 0

5 CN Cracker, PSA Caloric 1.300 0

6 HU SMR, MDEA, CB, PSA Linde 11.000 4.400 12.740

7 HU SMR, MDEA, CB, PSA Linde 11.000 4.400 12.740

8 IT SMR, HTS, PSA Linde 61.000 0 36.770

9 AT SMR, HTS, PSA Caloric 750 0

10 IT SMR, HTS, PSA Linde 2.500 0 0

11 FI SMR, HTS, PSA EVT Mahler 1.000 0 0



14 DE SMR, HTS, MDEA, CB, PSA Linde 20.000 2.500 6.000

15 DE SMR, HTS, PSA Hydrochem 7.500 0 3.900

16 FR SMR, HTS, PSA Linde 21.500 0 18.530

17 DE SMR, MDEA, CB, PSA Linde 18.000 7.000 6.000

18 DE Linde 1.800

19 DE SMR, HTS, PSA Linde 35.000 0 0

20 DE SMR, HTS, PSA Linde 35.000 0 61.500

21 DE SMR, HTS, PSA Carbotech 100 0 0 0

22 DE Shift, PSA Linde 53.000

23 FR SMR, HTS, PSA Linde 2.900 1.200

24 US SMR, SNCR, HTS, PSA Hydrochem 12.000 11.34025 US NG-POX, Rectisol, Membrane, DuPont, Linde, Texaco, Lurgi 15.600 25.470 180.000 163.000

26 US SMR, DEA, Membrane Hydrochem 0 455

27 US SMR, ATR, DEA, Membrane Hydrochem 0 830 4.082

28 CL SMR, HTS, MDEA, PSA Linde 45.000 0 40.000

29 AR SMR, HTS, PSA Hydrochem 200 0

Total 392.320 85.655 180.000 377.802


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Linde Gas

HYCO Plant Operating ExperienceLinde Gas HYCO Plants in Operation

Linde Design

Other Plant

Designs Linde Design

Other Plant

Designs Linde Design

Other Plant

Designs

Continent

No. of

Plants Nm3/h Nm3/h Nm3/h Nm3/h Nm3/h Nm3/h

Europe, operating 15 257.500 6.100 13.100 0 0 0

thereof Linde design: 11

North America, operating 3 12.000 15.600 455 25.470 0 180.000

hereof Linde design: 2

South America, operating 1 200 0 0 0 0 0

hereof Linde design: 1

Asia/Pacific, operating 3 0 28.200 0 32.800 0 0

thereof Linde design: 0

Total 269.700 49.900 13.555 58.270 0 180.000

Linde plant design regarding: Linde-Selas (Box-Type reformer) or Hydrochem reformer design, HyCO Cold Box, MDEA and PSA

Other plant suppliers than Linde: typically for H2 plants < 2500Nm3/h

Product H2 Product CO Product Syngas


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Linde Gas

Operation in Leuna, Germany

DOW/BSL(Poly-olefins)

WIG

ATOFINA

(H2O2)

Spezialchemie(Caproleuna) (Neuchem)

DOMO - Gruppe(Caprolactam)(Chemiefaser)

MIRAMID

LSE

(Caprolactam)

DOMO-Group

ChemtecPolymerTensideKataLeunaUCB

(Amine,DMF)Leuna Harze

ATOFINA(Resins)

MIDER(Refinery

+ POX)

InfraLeuna

RKB

Rhodia Syntech


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Linde Gas

Leuna I + II Steam Reforming Plant,Germany

Linde Gas in Leuna, Germany: Integration into the Leuna Chemical ParkLegend:

Linde Gas, SMR I & II

GAN Other units owned & operated by Linde Gas

ASU Buna GOX BSL Units owned & operated by others

Schkopau

LOX

LIN

LAR

Methanol-

ASU Leuna GOX Resid (VVR) H2S - HTS CO2- SynthesisPOX removal removal

LOX (Rectisol) (Rectisol)

LIN

LAR

CO2-Purification& Liquefaction

CO2

PSA

Isothermal H2

Shift Unit PSA

CO-Unit

SMR 2 x

I and II H2 - PSA

high purity H2 Trailer-

H2 - PSA filling station

Refinery-

fuel gas

Refinery-

H2-network

CO2, liq.

CO2, Pipelinedesulf.syngas

shifted

gas

desulfurized syngas (45,6% H2, 51,8% CO)

CO

Pipeline

HRSG

H2

PipelineNG-Feed

GOX

Pipeline

HRSG

N2-

Pipeline

Methanol

rawH2

(93,6% H2, 4,7% CO)

MP- Steam

System

MP-Steam


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Linde Gas


Capacity:35.000 Nm3/h each, (99.96% H2 ex PSAs)

Start-up: SMR I 1993

SMR II November 2002


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Linde Gas


Two SMR: top fired, down flow Linde-Selas box type NG reformers

Leuna I

45 Tubes per row, 4 rows = 180 tubes, 31.5 bara operating

more tubes than SMR II: original design was planned with COproduction but was never realized

Leuna II

42 Tubes per row, 3 rows = 126 tubes, G-X40NiCrNb 3525 micro,101.6mm I.D., 12m fired length, 31.5 bara operating

4 x 12 = 48 burners, Lanemark forced draft, Low-NOX, 1.4841 nozzles

61.5 t/h steam export (turbine quality) from separate system

2 PSA Units 9 beds with 8, 7, 6, 5 switch back at reduced capacity

99.96% H2


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Linde Gas


LEUNA II 35000 H2 Nm3/hLINDE GAS BOH - TECHNICAL SUPPORT / DESIGN DATA NSG RUN (NORTH SEA 100%) 0 CO Nm3/h

COMBUSTION AIR : 67595 Nm3/h

Pre-heated : 250 degC FLUE GAS TO ATM

DMW EXPORT STEAM (TURBINE QUALITY)

STEAM IMPORT FROM LEUNA I

H2 Recycle Compression

FUEL GAS PSA OFF GAS

Utilities : EXPORT CONDENSATE TO LEUNA I

CW 130 t/h (deltaT = 7, CW process = 117,6 t/h)

ELEC 675 kWh (shaft)

IA 180 Nm3/h

REFORMER SPECIFICATIONS : SHIFT SPECIFICATIONS : PSA SPECIFICATIONS :

No. Tubes / Rows : 126 / 3 S / C : 2,7 T IN HTS : degC 330 PSA EFF : 86,0%

No. Burners : 48 T OUT SR : degC 855 No. Adsorbers : 9FLUID 1 2 3 4 5 6 7 8 9 10 11 12 13

NG INLET PROCESS INLET SR OUTLET SR OUT HTS H2 EXP EXP STEAM OFF GAS NG FUEL STEAM IN DMW FLUE GAS CONDEN.

N2 % mol 3,46% 3,36% 0,23% 0,64% 0,64% 0,04% 0,00% 2,25% 3,46% 0,00% 0,00% 62,62% 0,00%

O2+AR % mol 0,00% 0,00% 0,00% 0,00% 0,00% 0,00% 0,00% 0,00% 0,00% 0,00% 0,00% 1,94% 0,00%

CH4 % mol 90,10% 87,48% 26,35% 4,63% 4,63% 0,00% 0,00% 16,72% 90,10% 0,00% 0,00% 0,00% 0,00%

C2+ % mol 4,36% 4,23% 0,13% 0,00% 0,00% 0,00% 0,00% 0,00% 4,36% 0,00% 0,00% 0,00% 0,00%

C3+ % mol 1,33% 1,29% 0,07% 0,00% 0,00% 0,00% 0,00% 0,00% 1,33% 0,00% 0,00% 0,00% 0,00%

H2 % mol 0,00% 2,91% 0,79% 47,99% 54,70% 99,96% 0,00% 27,64% 0,00% 0,00% 0,00% 0,00% 0,00%

CO % mol 0,00% 0,00% 0,00% 9,36% 2,65% 0,00% 0,00% 9,56% 0,00% 0,00% 0,00% 0,00% 0,00%

CO2 % mol 0,75% 0,73% 0,02% 5,32% 12,03% 0,00% 0,00% 43,29% 0,75% 0,00% 0,00% 18,22% 0,00%

H2O % mol 0,00% 0,00% 72,41% 32,05% 25,34% 0,00% 100,00% 0,54% 0,00% 100,00% 100,00% 17,22% 100,00%

P bar abs 35 34,5 31,5 28,6 27,8 25,3 34,3 1,3 35 34,3 - 0,982 -

T degC 15 380 580 855 403 37 339 19 15 358 - 141 -

FLOW Nm3/h 15048 14416 53402 75303 75303 35016 76886 20862 1052 38986 77663 85667 18996

t/h 11,885 11,092 42,428 42,428 42,428 3,165 61,799 23,917 0,831 31,336 62,423 111,761 15,288

HDS

STEAMREFORMER

HT

SHIFT PSA

HEATRECOVERY

3 4 5 6

8

1

A B

9

2

11

12

7

13

H2compression

10


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Linde Gas

H2 Plant Leuna I, Germany

0

200

400

600

800

1000

1200

1 2 3 4 5 6 7 8 9 10 11 12 13

year of operation

planneddowntime/

hrs

Leuna,Hydrogen Plant Operating Experience

year no. 7:repair of weldolets

year no. 13: planneds/d in Oct. 2005


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Linde Gas

H2 Plant Leuna I, Germany

9 4 0 1 3 2 1 0 1 1 0 1 0

0

50

100

150

200

250

300

350

1 2 3 4 5 6 7 8 9 10 11 12 13

year of operation

unplanneddowntime/hrs

80%

82%

84%

86%

88%

90%

92%

94%

96%

98%

100%

availab./reliab.in%

no. of trips hrs availability reliability


year no. 7:repair of weldolets


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Linde Gas


SMR Leuna I, 12+ years of operation:

Exceeding 110,000 hrs tube life by 05/2006

13 out of 23 trips caused by electrical failures (power dips ->installed 0.7kV UPS, ID Fan speed control card, etc.)

5 trips caused by instrument failures (missing insulation on instr.tubing, comb. air flow meter failed twice during rain storm ->changed flow meter)

2 valve failures: ESD fuel gas valve tripped once, PSA tripped duringvalve repair while unit was on-stream.

2 trips by human error, one trip reason remained unknown.

Reliability chart excluding 6 force majeure events (lightning, OSBLdamage of power supply)


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Linde Gas


SMR Leuna I, 12+ years of operation:

Scheduled maintenance alternating 5.5 and 12 days every otheryear

Extended, unplanned outage in 1999: 3 consecutive outages (total 1074 hrs) when defective welds

were found between weldolets and hot header. Subsequentscheduled stop to determine damage; third outage taken torepair weldolets.

Long term average maintenance cost is about 2.8% of invest


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Linde Gas


SMR Leuna II, 2+ years of operation:

7 unplanned outages during first year of operation, all caused byinstrument or DCS problems.

Average down time 12 hrs per event (84 hrs down during 1st year):

exchanged defective ESD card (HIMA)

exchanged defective HIMA relays configuration of PC network

update of DCS software

communication problem Freelance Operate IT

No trips since second operational year (2004)

Planned down time is approx. 140 hrs/yr With SMR I + II both units typically operate at 70% load on average.

100% H2 availability on-site since SMR II is on-stream.


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Linde Gas


Linde Gas HYCO Plants In Operation:

3 x SMR, MDEA wash unit with CO/CH4 cold box, H2-PSA

1 x SMR, MDEA, CO/CH4 cold box in start-up phase

1 x SMR, DEA, CO/H2-membrane separation 1 x CO/H2 membrane

1 x NG-POX, membrane, Rectisol, CO cold box, methanol loop, H2-PSA

1 x Resid-POX, Rectisol, CO cold box, H2-PSA


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Linde Gas


Linde Gas Partial Oxidation Plants (HYCO):

t/hr

Nm3/hr

Nm3/hr

Nm3/hr 177,400

1.77

72,500

0.95

Raw Syngas

H2/CO

2x 50% Texaco, 285 ft3

2xQuench and 2xWHB

2 x 100% Texaco, 285 ft3

Quench type

POX Reactor

155,300 (1600 t/d MeOH)

145

-

- (drive ASU compressor)

Syngas product

Steam product

25,400

16,700

33,200

27,000

CO Product

H2 Product

19992004Linde took over

1978 with resid feed stock

converted 1996 to NG operation

2001Start-up

NG-POX

Houston, USA

Resid-POX

Singapore


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Linde Gas


Linde Gas Partial Oxidation Plants (HYCO):

Nm3/hr

Nm3/hr

20,900 (124%), year 1996

25,480 (151%), year 2003

By increasing CO content inRectisol & cold box feed

Additional adsorber &cold box capacityrequired for furtherexpansion

Cold Box, CO capacityincrease

16,850 (100%), year 1978

(using resid feed stock)

30,200 (100%)

32,350 (107%)

Cold Box design, CO

Max. achieved

NG-POX

Laporte, USA

Resid-POX

Singapore

It seems that the new plants are ratherdesigned to the point!


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Linde Gas


Linde Gas Laporte, NG-POX Plant:

POX

153MM

Membrane Rectisol Coldbox

Methanol

PSA

AceticCustomer

86MM WHB Gas

41MM 22MM CO

320 mgal/d

20MM

67MM Quench+WHB Gas 143MM

25MM AOG+xxMM (1:1)

Import

5.5MM PSA-TGCompressed intoMethanol

43MM

4MM Purge-H2

14.5 MM H2into pipeline

19MM

5-8MM Fuel+ NG Fuel

23MMComp

Merchant MeOH

220 mgal/d

0.3MM CH4 Purge

NG:56,000mmbtu/d

O2:1650 ston/d

Boiler s/h & SteamSystem

Steam export to AAand internal use


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Linde Gas


Linde Gas Laporte, NG-POX Plant:

POX

153MM

Membrane Rectisol Coldbox

Methanol

PSA

AceticCustomer

86MM WHB Gas

41MM 22MM CO

320 mgal/d

20MM

67MM Quench+WHB Gas 143MM

25MM AOG+xxMM (1:1)

Import

5.5MM PSA-TGCompressed intoMethanol

43MM

4MM Purge-H2

14.5 MM H2into pipeline

19MM

5-8MM Fuel+ NG Fuel

23MMComp

Merchant MeOH

220 mgal/d

0.3MM CH4 Purge

NG:56,000mmbtu/d

O2:1650 ston/d

Boiler s/h & SteamSystem

Steam export to AAand internal use


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Linde Gas


Reliability Issues in Linde Gas NG-POX based HYCO plant:

POX Unit:

Feed System:

ZnO stability => changed catalyst supplier

Refractory lining and WHB tube inlets:

damage during periods of very high rate operation

POX Burner:

up to 417 days burner life, but we experienced also series of shortterm life (about 30 days)

Quench ring damage:

Stable POX operation, by avoiding quick variations in POX feed as wellas periods of excessive load, reduces drastically the risk of refractory,burner and WHB damage


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Linde Gas

NG-POX/WHB/Cold Box availability

HYCO, Linde Gas Laporte:

92.3%85.8%

99.97%

96.9%

99.5%

-

89.1%

84.0%

95.30%

S-POX

Unit

99.97%

97.05%

99.97%

96.9%

99.7%

-

99.4%

-

2003

AA 11 days TAR *)

99.4%91.8%

92.2%85.8%

90.5%80.6%

90.4%80.5%

200440/26/28 TAR **)

98.98%

-

98.9%

-

99.8%

97.5%

99.4%

97.1%

2002

Incl. 8 days TAR

99.4%

93.7%

89.1%

84.0%

95.4%

89.9%

95.4%

89.9%

2001

Incl. 21 days TAR

95.91%93.74%95.83%94.23%2000

CO Cold Box

Total

S-POX

Total

N-POX

Unit

N-POX

Total,

Total: Downtime including events that were caused by other process units => total on-stream

Unit: Counted only events when the unit or one of its components failed initially.

*) AA: Acetic Acid customer **) N-POX 40 days, S-POX 26 days, C/B 28 days TAR in 2004


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Linde Gas

NG-POX/WHB/Cold Box availability

Boundary conditions for high POX and cold-box on-stream factors:

As usual: there are preventive and predictive maintenance on criticalvessels, piping, valves and monitoring rotating machinery.

Linde Gas went through a learning curve and solved many problems withhelp from Linde Engineering.

On-going operator training

Not to exceed critical process parameters => be aware of your limits!

Stable CO off-take at high cold-box load

Methanol unit is a big fly-wheel:

Keep POX reactor(s) on-line while CO is reduced or shut down.

A CO only plant has to be shut down if CO goes down, to reduce flaring.

Methanol can take CO swing if acetic acid reactor is unstable.

Hydrogen balancing tool, if demand for co-produced H2 changes.

Auxiliary boiler reliability is crucial. Main compressors are steam turbinedriven.


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Linde Gas

Operation Support and Feed-Back

Nothing falls from the sky everything needs to be earned:

Valuable support for Linde Gas operating units from LindeEngineering

Soon there will be 29 Linde Gas HYCO plants in operation:

the experience in the field will then be gathered systematically

and evaluated centrally.

This will ensure that all possible feed back is being used tooptimize operating plants as well as specifications for new HYCOunits.

Current technical reporting will be partly replaced by a standardizedand at the same time flexible information system

More important than statistical on-stream data is the feed back ofexperience, know-how and detected, analyzed or resolvedproblems on a detailed level.


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Linde Gas

Thank you for your Attention.


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Linde Gas

NG-POX Unit with Quench and WHB

POX Reactor

Quench Section

Ash Pot

Waste Heat Boiler (WHB)


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Linde Gas

WHB Tube Inletsand Refractory Damage

Tubes damaged when auxiliary boilertripped, NG compressor sloweddown, NG feed flow ceased andOxygen control valve did not followquick enough to maintain NG/O2ratio. Tube ends overheated.

Brick damage due to(short term) highload operation


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Linde Gas

POX Burner

Typical finding of burner tip after upto 417 days of operation (usually

including several reactor starts andshut downs)

Crack in burner cooling water coil to burnertip weld

Long burner life is achieved by maintaining certain O2 and NGvelocities (tip design), adding O2 purge steam and stablePOX operation!


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Linde Gas

Quench Ring

Area of metal dusting in thecircumference of the quenchring/floor plate.

Opposite side with quench water inletnozzles. Blue scale is mainly phosphatedeposits on the dip tube.

08_h2_plant_operating_experience_t.pdf

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