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Linde Gas

Hydrogen Plant Operating Experience
Tehran, September 26th 2005 Stefan Brandes Linde Gas
26th September 2005 1 Stefan Brandes / LG / z3646.ppt

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

26th September 2005

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Stefan Brandes / LG / z3646.ppt

770 AT SMR.655 180.740 IT SMR.500 0 0 FI SMR.000 AR SMR.802 Plants under construction or commissioning 26 September 2005 th 3 Stefan Brandes / LG / z3646. Rectisol.000 163.900 FR SMR.ppt .200 US SMR. 27. PSA Linde 61. PSA Hydrochem 7.470 180. PSA EVT Mahler 1. HTS. HTS. HTS. PSA Hydrochem 12. CB. Lurgi 15. DEA. Texaco.770 6.000 32. PSA Linde 35.400 12. PSA Linde 45.000 4.000 SG Resid-POX. Claus Texaco. Linde. HTS. CB.HYCO Plant Operating Experience Linde Gas HYCO Plants in Operation Linde Gas Plant No.082 CL SMR. Lurgi MW Kellogg. HTS. PSA. PSA Linde 11. PSA Caloric 1. CB. PSA Linde 4.340 US NG-POX. PSA Linde 11.000 2. HTS. PSA Linde 35. PSA Caloric 750 0 IT SMR.500 0 18. HTS. MDEA.000 7. DEA.000 0 0 DE SMR. PSA Linde 2.300 0 HU SMR. HTS. Membrane. PSA Linde 21.000 0 36.400 12.000 0 0 FI SMR.740 HU SMR. Linde. HTS. PSA Hydrochem 200 0 392.530 DE SMR. MDEA.500 6.900 1. CB. PSA Linde 20.000 0 40.000 0 61.800 CN Cracker. MeOH. SNCR.500 0 0 DE SMR.600 25. ATR.500 DE SMR. PSA Carbotech 100 0 0 0 DE Shift.000 DE Linde 1. PSA Caloric 600 0 0 CN Cracker. CB. MDEA. MDEA. HTS. CB. HTS.000 11. HTS. Membrane Hydrochem 0 455 US SMR. PSA Linde 18. PSA Linde 53. HTS.320 85. Rectisol. PSA DuPont.500 0 3.800 DE SMR. HTS.000 US SMR. HTS.000 6. MDEA. Membrane Hydrochem 0 830 4.000 377. Messer.000 4. PSA Caloric 600 0 0 CN Cracker.000 DE SMR.000 FR SMR. PSA Linde 2. PSA EVT Mahler 2. PSA EVT Mahler 2. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Total Product Product H2 Product CO Syngas Product Country Main Process Units Supplier [Nm³/h] [Nm3/h] [Nm3/h] Steam [kg/h] CN CB. ASU. HTS.500 0 0 FI SMR.

500 Nm3/h 6.100 Nm3/h 0 Product Syngas Other Plant Linde Design Designs Nm3/h 0 Nm3/h 0 12.470 0 180.200 0 32.555 58.000 200 0 0 0 0 0 0 28. operating thereof Linde design: North America.000 Linde plant design regarding: Linde-Selas (Box-Type reformer) or Hydrochem reformer design.800 0 0 269.100 Product CO Other Plant Linde Design Designs Nm3/h 13. of Plants 15 11 3 2 1 1 3 0 Nm3/h 257. operating thereof Linde design: Asia/Pacific.ppt .600 455 25.000 15.700 49. operating thereof Linde design: South America. HyCO Cold Box.HYCO Plant Operating Experience Linde Gas HYCO Plants in Operation Linde Gas Product H2 Other Plant Linde Design Designs Continent Europe.270 0 180. operating thereof Linde design: Total No.900 13. MDEA and PSA Other plant suppliers than Linde: typically for H2 plants < 2500Nm3/h 26th September 2005 4 Stefan Brandes / LG / z3646.

ppt .Linde Gas Operation in Leuna.Gruppe RKB InfraLeuna MIDER (Refinery + POX) ATOFINA (Resins) UCB KataLeuna Tenside Polymer (Amine.DMF) Rhodia Syntech Leuna Harze Chemtec (Caprolactam) DOMO-Group 26th September 2005 5 Stefan Brandes / LG / z3646. Germany Spezialchemie DOW/BSL (Poly-olefins) WIG (Caproleuna) (Neuchem) (Caprolactam)(Chemiefaser) MIRAMID LSE ATOFINA (H2O2) DOMO .

51.8% CO) shifted gas MethanolSynthesis Methanol ASU Leuna GOX LOX LIN LAR Resid (VVR) POX H2S removal (Rectisol) HTS CO2removal (Rectisol) HRSG desulf. syngas (93.PSA H2 Trailerfilling station 26th September 2005 6 Stefan Brandes / LG / z3646.Steam System CO-Unit CO Pipeline NG-Feed SMR I and II 2x H2 . 4.7% CO) raw H2 CO2-Purification & Liquefaction CO2.PSA H2 Pipeline high purity H2 .6% H2. Pipeline MP-Steam CO2 PSA HRSG Isothermal Shift Unit H2 PSA Refineryfuel gas RefineryH2-network MP. SMR I & II Other units owned & operated by Linde Gas Units owned & operated by others ASU Buna BSL Schkopau desulfurized syngas (45. Germany: Integration into the Leuna Chemical Park Legend: GAN GOX LOX LIN LAR Linde Gas.6% H2. N2Pipeline GOX Pipeline CO2.ppt .Leuna I + II Steam Reforming Plant. Germany Linde Gas Linde Gas in Leuna. liq.

000 Nm3/h each. (99.ppt . Germany Capacity: 35.96% H2 ex PSAs) Start-up: SMR I 1993 SMR II November 2002 Linde Gas 26th September 2005 7 Stefan Brandes / LG / z3646.Leuna I + II Steam Reforming Plant.

5 bara operating — more tubes than SMR II: original design was planned with CO production but was never realized Leuna II — 42 Tubes per row. 3 rows = 126 tubes. down flow Linde-Selas box type NG reformers Leuna I — 45 Tubes per row. Lanemark forced draft.96% H2 26th September 2005 8 Stefan Brandes / LG / z3646. 12m fired length. Germany Two SMR: top fired.4841 nozzles — 61. 7. 101. 31. 4 rows = 180 tubes. 1. 6.ppt .. Low-NOX. 5 switch back at reduced capacity — 99.Linde Gas Leuna I + II Steam Reforming Plant. G-X40NiCrNb 3525 micro.D.5 bara operating — 4 x 12 = 48 burners.6mm I.5 t/h steam export (turbine quality) from separate system 2 PSA Units — 9 beds with 8. 31.

25% 0.00% 0.00% 0.00% 0. CW process = 117.54% 1.35% 0.00% 0.6 855 75303 42.00% 99. Germany Linde Gas AB LINDE GAS BOH .62% 1.05% 28.02% 72.64% 9.00% 0. 0.10% 4.00% 25.32% 32.94% 0.6 t/h) kWh (shaft) Nm3/h S/C: 2 PROCESS 3.00% 100.00% 0.8 403 75303 42. Burners : 48 FLUID N2 O2+AR CH4 C2+ C3+ H2 CO CO2 H2O P T FLOW % mol % mol % mol % mol % mol % mol % mol % mol % mol bar abs degC Nm3/h t/h 1 NG INLET 3.428 5 OUT HTS 0.00% 100.73% 0.00% 0.00% 0.428 degC 6 H2 EXP 0.3 19 20862 23.00% 34.288 26th September 2005 9 Stefan Brandes / LG / z3646.3 37 35016 3.5 380 14416 11.00% 26.00% 87.00% 0.428 2.00% 0.36% 1.00% 0.00% 0.36% 0.72% 0.33% 0.00% 0.33% 0.00% 100.41% 31.00% 16.36% 1.00% 4.00% 0.00% 0.03% 25.00% 90.00% 0.00% 0.3 339 76886 61.22% 0.799 8 OFF GAS 2.00% 0.23% 1.00% 0.96% 0.00% 0. Adsorbers : 11 DMW 0.00% 0.ppt .00% 35 15 15048 11.00% 0.91% 0.00% 0.46% 0.29% 2.00% 0.13% 0.00% 0.04% 0.00% 0.5 580 53402 42.00% 0.00% 0.00% 0.00% 0.00% 47.99% 9.56% 43.48% 4.0% 9 13 CONDEN.423 12 FLUE GAS 62.TECHNICAL SUPPORT / DESIGN DATA COMBUSTION AIR : 67595 Nm3/h Pre-heated : 250 degC 11 LEUNA II NSG RUN (NORTH SEA 100%) 35000 H2 Nm3/h 0 CO Nm3/h 12 FLUE GAS TO ATM DMW 10 HEAT RECOVERY EXPORT STEAM (TURBINE QUALITY) 7 STEAM IMPORT FROM LEUNA I H2 Recycle Compression 1 2 3 HDS FUEL GAS 9 STEAM REFORMER 4 HT 5 6 SHIFT PSA OFF GAS 8 PSA H2 compression 130 675 IA 180 REFORMER SPECIFICATIONS : No.00% 0.00% 54.00% 0.092 3 INLET SR 0.00% 77663 62.70% 2.00% 27.00% 0.75% 0.00% 0.64% 0.34% 27.00% 4.00% 0.79% 0.165 SHIFT SPECIFICATIONS : T IN HTS : 330 degC 855 7 EXP STEAM 0.00% 0.00% 34.65% 12.00% 90.885 Utilities : CW ELEC EXPORT CONDENSATE TO LEUNA I 13 t/h (deltaT = 7.761 86.336 PSA SPECIFICATIONS : PSA EFF : No.00% 0.982 141 85667 111.36% 5.00% 0.00% 18.00% 34.00% 18996 15.00% 0.10% 4.7 T OUT SR : 4 OUTLET SR 0.23% 0.3 358 38986 31.46% 0.917 9 NG FUEL 3.07% 0.63% 0.00% 100.00% 0.00% 0.29% 0.64% 0.75% 0. Tubes / Rows : 126 / 3 No.00% 35 15 1052 0.00% 0.831 10 STEAM IN 0.00% 0.Leuna I + II Steam Reforming Plant.22% 17.00% 0.00% 0.00% 0.63% 0.

Germany 1200 1000 planned down time / hrs 800 600 400 200 0 1 2 3 4 5 6 7 8 9 10 year no.ppt . 7: repair of weldolets 11 12 13 year of operation 26th September 2005 10 Stefan Brandes / LG / z3646. Hydrogen Plant Operating Experience H2 Plant Leuna I.Linde Gas Leuna. 13: planned s/d in Oct. 2005 year no.

Germany 350 unplanned down time / hrs 300 250 200 150 100 50 9 0 1 2 3 4 5 6 7 8 9 10 11 12 13 year of operation no. in % . 7: repair of weldolets 92% 90% 88% 86% 84% 4 0 1 3 2 1 0 1 1 0 1 0 82% 80% hrs availability reliability 11 Stefan Brandes / LG / z3646.ppt availab.Linde Gas Leuna. of trips 26th September 2005 100% 98% 96% 94% year no. Hydrogen Plant Operating Experience H2 Plant Leuna I./reliab.

7kV UPS. Hydrogen Plant Operating Experience SMR Leuna I. ID Fan speed control card. tubing.ppt . PSA tripped during valve repair while unit was on-stream. etc. comb. OSBL damage of power supply) 26th September 2005 12 Stefan Brandes / LG / z3646.Linde Gas Leuna. — Reliability chart excluding 6 force majeure events (lightning. 12+ years of operation: — Exceeding 110. — 2 trips by human error. one trip reason remained unknown.000 hrs tube life by 05/2006 — 13 out of 23 trips caused by electrical failures (power dips -> installed 0. air flow meter failed twice during rain storm -> changed flow meter) — 2 valve failures: ESD fuel gas valve tripped once.) — 5 trips caused by instrument failures (missing insulation on instr.

Subsequent scheduled stop to determine damage. 12+ years of operation: — Scheduled maintenance alternating 5. Hydrogen Plant Operating Experience Linde Gas SMR Leuna I.ppt .8% of invest 26th September 2005 13 Stefan Brandes / LG / z3646. third outage taken to repair weldolets.Leuna.5 and 12 days every other year — Extended. — Long term average maintenance cost is about 2. unplanned outage in 1999: — 3 consecutive outages (total 1074 hrs) when defective welds were found between weldolets and hot header.

26th September 2005 14 Stefan Brandes / LG / z3646. 2+ years of operation: — 7 unplanned outages during first year of operation. 140 hrs/yr — With SMR I + II both units typically operate at 70% load on average. all caused by instrument or DCS problems.ppt . Hydrogen Plant Operating Experience SMR Leuna II. — 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. — 100% H2 availability on-site since SMR II is on-stream.Linde Gas Leuna.

CO/CH4 cold box in start-up phase — 1 x SMR. membrane. MDEA. H2-PSA — 1 x Resid-POX. CO/H2-membrane separation — 1 x CO/H2 membrane — 1 x NG-POX. DEA. CO cold box. methanol loop. CO cold box. Rectisol. Rectisol.ppt .Linde Gas HYCO Plant Operating Experience Linde Gas HYCO Plants In Operation: — 3 x SMR. MDEA wash unit with CO/CH4 cold box. H2-PSA — 1 x SMR. H2-PSA 26th September 2005 15 Stefan Brandes / LG / z3646.

USA 1978 with resid feed stock converted 1996 to NG operation 1999 177.300 (1600 t/d MeOH) 145 16 Stefan Brandes / LG / z3646.77 2x 50% Texaco.700 155. 285 ft3 Quench type Nm3/hr Nm3/hr t/hr 33.95 2 x 100% Texaco.ppt 2001 2004 Nm3/hr 72.000 . 285 ft3 2xQuench and 2xWHB 25.200 27.(drive ASU compressor) .Linde Gas HYCO Plant Operating Experience Linde Gas Partial Oxidation Plants (HYCO): Resid-POX Singapore Start-up Linde took over Raw Syngas H2/CO POX Reactor CO Product H2 Product Syngas product Steam product 26th September 2005 NG-POX Houston.400 16.500 0.400 1.

year 1978 (using resid feed stock) 20. year 2003 By increasing CO content in Rectisol & cold box feed — It seems that the new plants are rather designed to the point! 26th September 2005 17 Stefan Brandes / LG / z3646. year 1996 25.ppt . CO capacity increase Nm3/hr Nm3/hr 30.480 (151%).350 (107%) Additional adsorber & cold box capacity required for further expansion NG-POX Laporte. USA 16.Linde Gas HYCO Plant Operating Experience Linde Gas Partial Oxidation Plants (HYCO): Resid-POX Singapore Cold Box design.850 (100%). CO Max. achieved Cold Box.900 (124%).200 (100%) 32.

ppt 26th September 2005 .Linde Gas HYCO Plant Operating Experience Linde Gas Laporte. NG-POX Plant: 0.5 MM H2 into pipeline Boiler s/h & Steam System Steam export to AA and internal use 18 Stefan Brandes / LG / z3646.3MM CH4 Purge 43MM 41MM Membrane Rectisol Coldbox 19MM 22MM CO Customer 320 mgal/d Acetic 86MM WHB Gas POX 153MM 67MM Quench+WHB Gas 23MM Comp 25MM AOG +xxMM (1:1) Import 143MM Methanol Merchant MeOH 220 mgal/d 4MM Purge-H2 5-8MM Fuel + NG Fuel 20MM NG: 56.000mmbtu/d O2: 1650 ston/d PSA 5.5MM PSA-TG Compressed into Methanol 14.

5 MM H2 into pipeline Boiler s/h & Steam System Steam export to AA and internal use 19 Stefan Brandes / LG / z3646.3MM CH4 Purge 43MM 41MM Membrane Rectisol Coldbox 19MM 22MM CO Customer 320 mgal/d Acetic 86MM WHB Gas POX 153MM 67MM Quench+WHB Gas 23MM Comp 25MM AOG +xxMM (1:1) Import 143MM Methanol Merchant MeOH 220 mgal/d 4MM Purge-H2 5-8MM Fuel + NG Fuel 20MM NG: 56.000mmbtu/d O2: 1650 ston/d PSA 5. NG-POX Plant: 0.ppt 26th September 2005 .5MM PSA-TG Compressed into Methanol 14.Linde Gas HYCO Plant Operating Experience Linde Gas Laporte.

Linde Gas HYCO Plant Operating Experience 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. by avoiding quick variations in POX feed as well as periods of excessive load. burner and WHB damage 26th September 2005 20 Stefan Brandes / LG / z3646. but we experienced also series of short term life (about 30 days) — Quench ring damage: — Stable POX operation.ppt . reduces drastically the risk of refractory.

0% 98.97% 96.ppt .4% 91.1% 84.8% 94.5% 2002 Incl.97% 96.4% 90. 2000 2001 Incl.9% 92.4% 89.8% CO Cold Box Total 95.97% 97.98% 99.4% 80.9% 99.9% 92.9% 99.9% 99.3% 85. *) AA: Acetic Acid customer **) N-POX 40 days.2% 85.7% 98. 8 days TAR 2003 AA 11 days TAR *) 2004 40/26/28 TAR **) 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.23% 95. S-POX 26 days.4% 97.8% S-POX Unit 95. Linde Gas Laporte: N-POX Total.91% 99.Linde Gas NG-POX/WHB/Cold Box availability HYCO.7% 90.30% 89.5% 80.5% 99.0% 99.74% 89. C/B 28 days TAR in 2004 26th September 2005 21 Stefan Brandes / LG / z3646.4% 93.1% 99.6% S-POX Total 93.05% 99.83% 95.5% 99.8% 97. 21 days TAR N-POX Unit 95.1% 84.4% 89.

26th September 2005 22 Stefan Brandes / LG / z3646. to reduce flaring. — A “CO only plant” has to be shut down if CO goes down. Main compressors are steam turbine driven.ppt . piping.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 critical vessels. — 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. — Methanol can take CO swing if acetic acid reactor is unstable. valves and monitoring rotating machinery. if demand for co-produced H2 changes. — Hydrogen balancing tool. — Linde Gas went through a learning curve and solved many problems with help from Linde Engineering. — Auxiliary boiler reliability is crucial.

analyzed or resolved problems on a detailed level. — Current technical reporting will be partly replaced by a standardized and at the same time flexible information system — More important than statistical on-stream data is the feed back of experience. 26th September 2005 23 Stefan Brandes / LG / z3646.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 Linde Engineering — Soon there will be 29 Linde Gas HYCO plants in operation: — the experience in the field will then be gathered systematically and evaluated centrally.ppt . — This will ensure that all possible feed back is being used to optimize operating plants as well as specifications for new HYCO units. know-how and detected.

ppt . 26th September 2005 24 Stefan Brandes / LG / z3646.Linde Gas Thank you for your Attention.

ppt .Linde Gas NG-POX Unit with Quench and WHB Waste Heat Boiler (WHB) POX Reactor “Ash Pot” Quench Section 26th September 2005 25 Stefan Brandes / LG / z3646.

WHB Tube Inlets and Refractory Damage Linde Gas — Tubes damaged when auxiliary boiler tripped.ppt . Tube ends overheated. NG compressor slowed down. — Brick damage due to (short term) high load operation 26th September 2005 26 Stefan Brandes / LG / z3646. NG feed flow ceased and Oxygen control valve did not follow quick enough to maintain NG/O2 ratio.

adding O2 purge steam and stable POX operation! 26th September 2005 27 Stefan Brandes / LG / z3646.ppt .Linde Gas POX Burner — Typical finding of burner tip after up — Crack in burner cooling water coil to burner to 417 days of operation (usually tip weld including several reactor starts and shut downs) — Long burner life is achieved by maintaining certain O2 and NG velocities (tip design).

ppt . Blue scale is mainly phosphate deposits on the dip tube. — Opposite side with quench water inlet nozzles. 26th September 2005 28 Stefan Brandes / LG / z3646.Linde Gas Quench Ring — Area of metal dusting in the circumference of the quench ring/floor plate.